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International audience; Glycolaldehyde (GAld) is a C2 water-soluble aldehyde produced during the atmospheric oxidation of isoprene and many other species and is commonly found in cloudwater. Previous work has established that glycolaldehyde evaporates more readily from drying aerosol droplets containing ammonium sulfate (AS) than does glyoxal, methylglyoxal, or hydroxyacetone, which implies that it does not oligomerize as quickly as these other species. Here, we report NMR measurements of glycolaldehyde’s aqueous-phase reactions with AS, methylamine, and glycine. Reaction rate constants are smaller than those of respective glyoxal and methylglyoxal reactions in the pH range of 3–6. In follow-up cloud chamber experiments, deliquesced glycine and AS seed particles were found to take up glycolaldehyde and methylamine and form brown carbon. At very high relative humidity, these changes were more than 2 orders of magnitude faster than predicted by our bulk liquid NMR kinetics measurements, suggesting that reactions involving surface-active species at crowded air–water interfaces may play an important role. The high-resolution liquid chromatography–electrospray ionization–mass spectrometric analysis of filter extracts of unprocessed AS + GAld seed particles identified sugar-like C6 and C12 GAld oligomers, including proposed product 3-deoxyglucosone, with and without modification by reactions with ammonia to diimine and imidazole forms. Chamber exposure to methylamine gas, cloud processing, and simulated sunlight increased the incorporation of both ammonia and methylamine into oligomers. Many C4–C16 imidazole derivatives were detected in an extract of chamber-exposed aerosol along with a predominance of N-derivatized C6 and C12 glycolaldehyde oligomers, suggesting that GAld is capable of forming brown carbon SOA

Atmospheric aerosols make significant contributions to several atmospheric chemical and physical processes. Aerosols from anthropogenic emissions have negative impact on air quality and human health. In recent years, significant progress has been made in understanding the anthropogenic pollutants. However, it is still not clear how mixtures of anthropogenic and biogenic emissions impact the regional climate and human health. To better understand aerosol physicochemical properties within the Paris urban plume when mixed with biogenic emissions, a comprehensive airborne measurement platform was deployed in the Île-de-France region in summer 2022 as part of the ACROSS (Atmospheric ChemistRy Of the Suburban foreSt) campaign. In this study, the vertical and spatial distributions of aerosol chemical composition, size distributions, and optical properties during urban plume aging are characterized based on couples of in-situ measurement techniques like aerosol mass spectrometer (c-ToF-AMS), Ultra-High Sensitivity Aerosol Spectrometer (UHSAS) and AVIRAD staged onboard the Safire ATR 42 research aircraft. Gas phase components are also detailed characterized by Proton-transfer-reaction mass spectrometry (PTR-ToF-MS) to act as tracers of anthropogenic and biogenic emissions. Based on gas and particulate phase organic information provided by laser-induced fluorescence technique (TDLIF), the production rate of particulate organic nitrate (pON) can also be estimated. These detailed airborne measurements of aerosol properties provide data that can contribute to modelling studies of aerosol characteristics.

The mineralogy of dust aerosols (i.e. the abundance, relative proportions and state of mixing of the different minerals composing the aerosols, including mainly silicates in the form of clays, quartz, and feldspars, carbonates, sulfates, and iron and titanium oxides) is of key relevance in driving its climatic and environmental effects. Ground–based and airborne observations support the evidence that the dust mineralogy is heterogeneous in the atmosphere, varying from local to global scale due to changes in the mineralogical composition of the emitting source soils and atmospheric processing. However, the capability to get regional and global mapping of airborne dust mineralogy is still missing to date. This gap represents a fundamental limitation for properly developing and validating the representation of dust in Earth System Models and constraining its regional and global climate forcing.Because the different minerals composing the fine and coarse fractions of dust show different spectral absorption signatures, remote sensing spectral and hyperspectral observations can be used to fill this gap by detecting the presence of diverse minerals and reconstructing their relative proportions in the dust aerosols. Based on this idea, recent efforts move into this direction, including the EMIT mission (Earth Surface Mineral Dust Source Investigation) started in 2022.In this study we demonstrate, starting from exemplary data acquired in the CESAM simulation chamber on dust aerosols from global sources (Di Biagio et al., 2017), that the extinction signature of suspended dust aerosols in the 740−1475 cm−1 infrared spectral range (6.8−13.5 µm) can be used to derive dust mineralogy in terms of its infrared−active and coarse−sized minerals: quartz, clays, feldspars and calcite. We show that diverse spectral infrared signatures allow to distinguish dust aerosols from different sources worldwide with variable composition, and that following the changes of the dust extinction spectra with time informs on particles size−selective mineralogy changes during atmospheric transport. Results from the present study confirm the major advance that hyperspectral infrared remote sensing observations, as those by IASI (Infrared Atmospheric Sounding Interferometer) and the IASI−NG (Next Generation) instruments, can provide to dust science. Di Biagio, C., Formenti, P., Balkanski, Y., Caponi, L., Cazaunau, M., Pangui, E., Journet, E., Nowak, S., Caquineau, S., Andreae, M. O., Kandler, K., Saeed, T., Piketh, S., Seibert, D., Williams, E., and Doussin, J.-F.: Global scale variability of the mineral dust long-wave refractive index: a new dataset of in situ measurements for climate modeling and remote sensing, Atmos. Chem. Phys., 17, 1901–1929, https://doi.org/10.5194/acp-17-1901-2017, 2017.

Mineral dust aerosols, which account for about 40% of global annual aerosol emissions, contribute to the persistent and large uncertainties on the global radiative budget and the oxidative capacity of the atmosphere.Indeed, the uptake of atmospheric volatile organic compounds (VOCs) on mineral dust particles can contribute to the formation of secondary organic aerosols (SOA), with consequent modification of the chemical and optical properties of the dust.Glyoxal, one of the most important VOC in the atmosphere, is a precursor of SOA, capable of interacting with mineral dust and forming SOA as a consequence of the interaction.In this experimental study we investigate the formation of SOA by the uptake of glyoxal on mineral dust particles. We present the results of the heterogeneous interaction obtained in the CESAM atmospheric simulation chamber (Chambre Expérimentale de Simulation Atmosphérique Multiphasique), used to conduct aging experiments in various controlled conditions in terms of relative humidity, irradiation, and gas phase composition. Prior entering the chamber, particles from a real soil sample (Gobi Desert) are size-selected using an aerodynamic aerosol classifier (AAC) in order to obtain a monodispersed size distribution centered at 300 nm in mobility diameter, narrow enough to be able to appreciate a dimensional variation from glyoxal condensation.In experiments conducted in humid conditions (RH=80%), a rapid uptake of glyoxal was observed on sub micrometric dust particles. 15 minutes after the injection of 1 ppm of glyoxal into the chamber, the mass of the particles increased by about 10%, with a variation of the modal diameter of the size distribution. As a consequence of glyoxal uptake in humid conditions, an increase of the aerosol organic mass concentration occurred immediately after the interaction, which was not observed in dry conditions. At the same time, the aerosol chemical speciation monitor (ACSM) mass spectra of the organic fraction show the increase in intensity of the glyoxal marker signals at m/z 58 and m/z 29. It is interesting to note also the drop of O/C ratio of the dust organic fraction after the injection of the glyoxal from 1.5 (the one of the dust itself) to a value close to 1, that is the one of the glyoxal.Hence, the first results of the study suggest the presence of a fast glyoxal uptake on submicronic mineral dust particles in high relative humidity conditions. This process modifies the mass and the size distribution of the aerosol, as well as the chemical composition of its organic fraction.

The nitrate radical (NO3) is mainly formed in the atmosphere through the reaction of nitrogen dioxide (NO2) with ozone (O3). It accumulates at night because during the day its photolysis in sunlight and its rapid reaction with nitric oxide (NO) can rapidly consume it. NO3 radical is a major nighttime atmospheric oxidant of biogenic volatile organic compounds (BVOCs), which represent alone 75 to 90% of global non-methane VOC emissions.Nighttime chemistry between NO3 and BVOCs has received increased attention in the recent literature due to its potential influences on climate, air quality, health and visibility through the formation of many gaseous and particulate secondary pollutants such as organic nitrates, secondary organic aerosol (SOA), ozone and other functionalized products. In several studies conducted in clean forested environments, NO3 concentrations were found to be very low, mostly below the detection limits (2-6pptv), which can be explained by the low concentrations of precursors (NO2 and O3) and the high reactivity of NO3 with unsaturated BVOCs. However, significant contribution of NO3-BVOC reactions to the secondary pollutants formation in these clean areas have been found.Since NO3 radicals are formed more rapidly in polluted air masses, it is expected that reactions with BVOCs are even more important in mixed atmospheres, i.e. influenced by both biogenic and anthropogenic sources and characterized by relatively high concentrations of both VOCs and NO2. The ACROSS (Atmospheric ChemistRy Of the Suburban foreSt) field campaign was carried out in June and July 2022 in Ile-de-France region and aims, among other objectives, to assess the potential impact of NO3-BVOC nocturnal processes on SOA formation. For this purpose, a newly developed field instrument, called "NOyBox", was deployed on top of a 40-meter tower, which is above the canopy, located at the Rambouillet Forest supersite southwest of Paris. The instrument allows the measurement of NO3 radicals, N2O5 and HONO (IBB-CEAS, Incoherent Broad Band Cavity Enhanced Absorption Spectroscopy), NO2 (CAPS, Cavity Attenuated Phase Shift) and NOy (gold heated converter coupled with a NO chemiluminescence analyzer). Significant concentrations of NO3 and N2O5 were detected on several nights with situations characterized by air masses coming from the direction of Paris, high concentrations of ozone and NO2, and moderate relative humidity levels. Concentrations of these species as well as concentrations of species of interest for NO3 chemistry are presented and the resulting implications on nighttime chemistry are discussed.

Biogenic volatile organic compounds (BVOCs) are intensely emitted by forests and crops into the atmosphere. They can rapidly react with the nitrate radical (NO3) during the nighttime to form a number of functionalized products. Among them, organic nitrates (ONs) have been shown to behave as reservoirs of reactive nitrogen and consequently influence the ozone budget and secondary organic aerosols (SOAs), which are known to have a direct and indirect effect on the radiative balance and thus on climate. Nevertheless, BVOC + NO3 reactions remain poorly understood. Thus, the primary purpose of this study is to furnish new kinetic and mechanistic data for one monoterpene (C10H16), terpinolene, and one sesquiterpene (C15H24), β-caryophyllene, using simulation chamber experiments. These two compounds have been chosen in order to complete the few experimental data existing in the literature. Rate constants have been measured using both relative and absolute methods. They have been measured to be (6.0 ± 3.8) ×10-11 and (1.8 ± 1.4) ×10-11 cm3 molec.−1 s−1 for terpinolene and β-caryophyllene respectively. Mechanistic studies have also been conducted in order to identify and quantify the main reaction products. Total organic nitrates and SOA yields have been determined. Both terpenes appear to be major ON precursors in both gas and particle phases with formation yields of 69 % for terpinolene and 79 % for β-caryophyllene respectively. They are also major SOA precursors, with maximum SOA yields of around 60 % for terpinolene and 90 % for β-caryophyllene. In order to support these observations, chemical analyses of the gas-phase products were performed at the molecular scale using a proton transfer reaction–time-of-flight–mass spectrometer (PTR-ToF-MS) and FTIR. Detected products allowed proposing chemical mechanisms and providing explanations through peroxy and alkoxy reaction pathways.

Biogenic volatile organic compounds (BVOCs) are intensely emitted by forests and crops into the atmosphere. During the night, they react very rapidly with the nitrate radical ( NO3 ), leading to the formation of a variety of functionalized products including organic nitrates and to large amounts of secondary organic aerosols (SOAs). Organic nitrates (ONs) have been shown not only to play a key role in the transport of reactive nitrogen and consequently in the ozone budget but also to be important components of the total organic-aerosol mass, while SOAs are known to play a direct and indirect role in the climate. However, the reactivity of BVOCs with NO3 remains poorly studied. The aim of this work is to provide new kinetic and mechanistic data for two monoterpenes ( C10H16 ), α - and γ -terpinene, through experiments in simulation chambers. These two compounds, which have very similar chemical structures, have been chosen in order not only to overcome the lack of experimental data but also to highlight the influence of the chemical structure on the reactivity. Rate constants have been measured using both relative and absolute methods. They were found to be ( 1.2 ± 0.5 ) × 10 - 10 and ( 2.9 ± 1.1 ) × 10 - 11 cm 3 molecule −1 s −1 for α - and γ -terpinene respectively. Mechanistic studies have also been conducted in order to identify and quantify the main reaction products. Total organic nitrate and SOA yields have been determined. While organic nitrate formation yields appear to be similar, SOA yields exhibit large differences with γ -terpinene being a much more efficient precursor of aerosols. In order to provide explanations for this difference, chemical analysis of the gas-phase products was performed at the molecular scale. Detected products allowed for proposing chemical mechanisms and providing explanations through peroxy and alkoxy reaction pathways.

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...

Mineral dust is a natural tracer of atmospheric composition and climate variability. Yet, there is still much to be known about the Southern Hemisphere dust cycle during the last Pleistocene. Major efforts have attempted to solve the ‘puzzle’ of the origin of the potential source areas that contribute dust to the Southern Ocean and East Antarctica (EA). Here we present a comprehensive geochemical characterization of an important potential source area, which role as a dust supplier to different environments of the SH has significantly been underestimated, that is, the Southern Africa (SAF) region. On the basis of Sr-Nd-Pb isotope ratios and rare earth element concentrations analyzed in sediments collected along the major dust-producing areas in the Namibian coast (Kuiseb, Omaruru and Huab riverbeds and the Namibian sand sea region), this study demonstrates for the first time that SAF emerges as the second most important dust source to EA during interglacial times.

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 (...

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.

Biogenic volatile organic compounds (BVOCs) are intensely emitted by forests and crops into the atmosphere. During the night, they react very rapidly with the nitrate radical (NO3), leading to the formation of a variety of functionalized products including organic nitrates and to large amounts of secondary organic aerosols (SOAs). Organic nitrates (ONs) have been shown not only to play a key role in the transport of reactive nitrogen and consequently in the ozone budget but also to be important components of the total organic-aerosol mass, while SOAs are known to play a direct and indirect role in the climate. However, the reactivity of BVOCs with NO3 remains poorly studied. The aim of this work is to provide new kinetic and mechanistic data for two monoterpenes (C10H16), α- and γ-terpinene, through experiments in simulation chambers. These two compounds, which have very similar chemical structures, have been chosen in order not only to overcome the lack of experimental data but also to highlight the influence of the chemical structure on the reactivity. Rate constants have been measured using both relative and absolute methods. They were found to be (1.2±0.5)×10-10 and (2.9±1.1)×10-11 cm3 molecule−1 s−1 for α- and γ-terpinene respectively. Mechanistic studies have also been conducted in order to identify and quantify the main reaction products. Total organic nitrate and SOA yields have been determined. While organic nitrate formation yields appear to be similar, SOA yields exhibit large differences with γ-terpinene being a much more efficient precursor of aerosols. In order to provide explanations for this difference, chemical analysis of the gas-phase products was performed at the molecular scale. Detected products allowed for proposing chemical mechanisms and providing explanations through peroxy and alkoxy reaction pathways.

Iceland is a highly active source of natural dust. Icelandic dust has the potential to affect directly the climate via dust-radiation interaction, and indirectly via dust-cloud interaction, snow/ice albedo effect and impacts on biogeochemical cycles. The impacts of Icelandic dust depend on its mineralogical and chemical composition. However, lack of data has prevented an accurate assessment of the role of Icelandic dust in the Earth system. Here, we collected surface sediment samples from five major Icelandic dust hotspots. Dust aerosols were generated and suspended in atmospheric chambers, and PM10 and PM20 fractions were collected for further analysis. We found that the dust samples primarily consist of amorphous basaltic material ranging from 8 wt% (from the Hagavatn hotspot) to 60–90 wt% (other hotspots). Samples had relatively high total Fe content (10–13 wt%). Sequential extraction of Fe to determine its chemical form shows that dithionite Fe (Fe oxides such as hematite and goethite) and ascorbate Fe (amorphous Fe) contribute respectively 1–6 %, and 0.3–1.4 % of the total Fe in Icelandic dust. The magnetite fraction is 7–15 % of total Fe and 1–2 wt% of PM10, which is orders of magnitude higher than in mineral dust from North Africa. Nevertheless, about 80–90 % of the Fe is contained in pyroxene and amorphous glass. The initial Fe solubility (ammonium acetate extraction at pH 4.7) is from 0.08–0.6 %, which is comparable to low latitude dust such as that from North Africa. The Fe solubility at low pH (i.e., 2) is significantly higher than typical low latitude dust (up to 30 % at pH 2 after 72 hrs). Our results revealed the fundamental differences in composition and mineralogy of Icelandic dust from low latitude dust. We attribute these differences to the low degree of chemical weathering, the basaltic composition of the parent sediments, and glacial processes. Icelandic dust contributes to the atmospheric deposition of soluble Fe and can impact primary productivity in the North Atlantic Ocean. The distinct chemical and mineralogical composition, particularly the high magnetite content (1–2 wt%), indicates a potentially significant impact of Icelandic dust on the radiation balance in the sub-polar and polar regions.

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 NO3 radical is the main atmospheric oxidant at night. The night period is favorable to the formation and accumulation of NO3 radicals in the atmosphere. On the one hand, it is formed by the reaction of nitrogen dioxide with ozone while, on the other hand, NO3 being highly photosensitive, it cannot accumulate significantly during the day (S. S. Brown and J. Stutz, Chem. Soc. Rev. 2012). In addition, the reaction between NO and NO3 is very fast and so, urban environment is considered so far, being not favorable to the occurrence of NO3 radicals. However, atmospheric nitrogen chemistry near the earth surface is strongly linked to the dynamics of the boundary layer and in summer NO is rapidly depleted by ozone. A large variability of the mixing ratios for NO3 as a function of height above the ground is thus expected with non-negligible concentrations in altitude (Brown et al., Atmos. Chem. Phys., 2007). The contribution of NO3 radical to the atmospheric evolution of VOCs in urban and sub-urban areas may therefore also be influenced by this vertical distribution.To demonstrate the potential importance of NO3 radical even in urban environment, a field campaign was carried out at night during July 2018 inside Paris. A newly developed field instrument dedicated to the measurement of NO3 radical was deployed on a high payload touristic tethered balloon located in Paris 15th district that was used as vertical vector. The NO3 instrument is a compact, robust and easily deployable on field instrument based on the IBB-CEAS (Incoherent Broad band Cavity Enhanced Absorption Spectroscopy) technique. NO3 measurements were completed by ground and airborne measurements of NO (chemiluminescence analyzer), NO2 (CAPS cavity) and O3 (absorption analyzer) concentrations as well as particle number concentrations (OPC GrimmTM) and 355 nm lidar (Leosphere ALS300) measurement for mixing layer probing.Vertical profiles from 0 to up to 300 m were obtained at night characterized by high concentrations of ozone and moderate humidity. In this presentation, vertical profiles of the species measured and implications for VOC oxidation in urban environment will be discussed.

The conformer-specific reactivity of gas-phase pyruvic acid following the S1(nπ*) ← S0 excitation at λmax = 350 nm (290-380 nm) and the effect of water are investigated for the two lowest energy conformers. Conformer-specific gas-phase pyruvic acid photolysis rate constants and their respective populations are measured by monitoring their distinct vibrational OH-stretching frequencies. The geometry, relative energies, fundamental vibrational frequencies, and electronic transitions of the pyruvic acid conformers and their monohydrated complexes are calculated with density functional theory and ab initio methods. Results from experiment and theory show that the more stable conformer with an intramolecular hydrogen bond dominates the gas-phase photolysis of pyruvic acid. Water greatly affects the gas-phase pyruvic acid conformer population and photochemistry through hydrogen bonding interactions. The addition of water decreases the gas-phase relative population of the more stable conformer and decreases the molecule's gas-phase photolysis rate constants. The theoretical results show that even a single water molecule interrupts the intramolecular hydrogen bond, which is essential for the efficient photodissociation of gas-phase pyruvic acid. Results of this study suggest that the aqueous-phase photochemistry of pyruvic acid proceeds through hydrogen-bonded conformers lacking an intramolecular hydrogen bond.

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...

This paper presents new laboratory measurements of the mass absorption efficiency (MAE) between 375 and 850 nm for 12 individual samples of mineral dust from different source areas worldwide and in two size classes: PM10. 6 (mass fraction of particles of aerodynamic diameter lower than 10.6 µm) and PM2. 5 (mass fraction of particles of aerodynamic diameter lower than 2.5 µm). The experiments were performed in the CESAM simulation chamber using mineral dust generated from natural parent soils and included optical and gravimetric analyses. The results show that the MAE values are lower for the PM10. 6 mass fraction (range 37–135 × 10−3 m2 g−1 at 375 nm) than for the PM2. 5 (range 95–711 × 10−3 m2 g−1 at 375 nm) and decrease with increasing wavelength as λ−AAE, where the Ångström absorption exponent (AAE) averages between 3.3 and 3.5, regardless of size. The size independence of AAE suggests that, for a given size distribution, the dust composition did not vary with size for this set of samples. Because of its high atmospheric concentration, light absorption by mineral dust can be competitive with black and brown carbon even during atmospheric transport over heavy polluted regions, when dust concentrations are significantly lower than at emission. The AAE values of mineral dust are higher than for black carbon (∼ 1) but in the same range as light-absorbing organic (brown) carbon. As a result, depending on the environment, there can be some ambiguity in apportioning the aerosol absorption optical depth (AAOD) based on spectral dependence, which is relevant to the development of remote sensing of light-absorbing aerosols and their assimilation in climate models. We suggest that the sample-to-sample variability in our dataset of MAE values is related to regional differences in the mineralogical composition of the parent soils. Particularly in the PM2. 5 fraction, we found a strong linear correlation between the dust light-absorption properties and elemental iron rather than the iron oxide fraction, which could ease the application and the validation of climate models that now start to include the representation of the dust composition, as well as for remote sensing of dust absorption in the UV–vis spectral region.

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...

Reaction rate constants for the reaction of

The optical properties of airborne mineral dust depend on its mineralogy, size distribution, shape, and might vary between different source regions. To date, large differences in refractive index values found in the literature have not been fully explained. In this paper we present a new dataset of complex refractive indices (m=n‒ik) and single scattering albedos (SSA) for 19 mineral dust aerosols over the 370–950 nm range in dry conditions. Dust aerosols were generated from natural parent soils from eight source regions (Northern Africa, Sahel, Middle East, Eastern Asia, North and South America, Southern Africa, and Australia). These were selected to represent the global scale variability of the dust mineralogy. Dust was re‒suspended into a 4.2 m3 smog chamber where its spectral shortwave scattering (βsca) and absorption (βabs) coefficients, number size distribution, and bulk composition were measured. The complex refractive index was estimated by Mie calculations combining optical and size data, while the spectral SSA was directly retrieved from βsca and βabs measurements. Our results show that the imaginary part of the refractive index (k) and the SSA largely vary from sample to sample, with values for k in the range 0.001 to 0.009 at 370 nm and 0.0003 to 0.002 at 950 nm, and values for SSA in the range 0.70 to 0.96 at 370 nm and 0.95 to 0.99 at 950 nm. In contrast, the real part of the refractive index (n) is mostly source (and wavelength) independent, with an average value between 1.48 and 1.55. The sample‒to‒sample variability in our dataset of k and SSA is mostly related to differences in the dust’s iron content. In particular, a wavelength‒dependent linear relationship is found between the magnitude of k and SSA and the mass concentrations of both iron oxide and total elemental iron. As an intrinsic property of matter, k is independent of size. When the iron oxide content exceeds > 3 %, the SSA linearly decreases with increasing fraction of coarse particles at short wavelengths ( We recommend that source‒dependent values of the SW spectral refractive index and SSA are used in models and remote sensing retrievals instead of generic values. In particular, the close relationships found between k/SSA and the iron content in dust enable establishing predictive rules for spectrally‒resolved SW absorption based on particle composition.

We report laboratory measurements of H2O-broadening coefficients of O2 absorption lines in the A-band near 13,000 cm−1. For this, four spectra of oxygen gas mixed with water vapor were recorded with a high resolution Fourier transform spectrometer for total pressures ranging from 125 to 175 Torr at 323 K, and a fifth at 175 Torr and 365 K. Broadening coefficients of 39 transitions (up to J ″ = 21 ) were retrieved from the measured spectra through fits using Galatry line profiles. Values at room temperature (296 K) were then extrapolated and compared with previous determinations in the A-band and millimeter waves region. This enables to resolve some controversial issues related to the inconsistencies between these studies. Finally, comparing our results with the line broadening coefficients by dry air confirms that H2O-broadenings of oxygen lines are, on average, 10% larger than those by dry air.

Transmission spectra of CO 2 highly diluted in water vapor have been recorded at 50 and 95 °C for four pressures between 0.02 and 0.1 atm using a high resolution Fourier Transform spectrometer. The collisional (Lorentz) widths of many lines of the ν 3 band (and of some of the ν 3 + ν 2 − ν 2 hot band) have been retrieved from each spectrum through fits using Voigt line shapes. Our result are about 4% lower than the values recommended in a previous study but they confirm the relative variations of the line broadening on the rotational quantum numbers. We also provide the first determination of H 2 O-induced line shifts of CO 2 lines.

Reflection spectra of pure CO2 gas have been recorded in the 4.3 μ m region by using a high resolution Fourier transform spectrometer, providing measured values of the refractive index. Comparisons with the results of calculations using available spectroscopic data, and free of any adjusted line parameter, show a very good agreement. This confirms that this experimental technique provides an alternative approach for the test or determination of spectroscopic parameters. Its advantages for studies of extremely strongly absorbing species and investigations of spatially (tightly) confined molecular gases are discussed.

H2O-broadening and shifting coefficients of 76 ro-vibrational transitions of methane in the mid-and near-infrared regions were measured for the first time. For this, eight spectra of methane diluted in water vapor were recorded with a high resolution Fourier Transform spectrometer for pressures ranging from 20 to 80 Torr and at 323 and 367 K. Line broadening and shifting coefficients were retrieved from the measured spectra through fits using Voigt profiles. Values at room temperature (296 K) were then deduced and compared with those of dry air. The results show that H2O-broadenings of methane lines are, on average, 34% larger than those for dry air.

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.

International audience; An approach consisting in combining in situ and laboratory experiments is often favoured for investigating the mechanisms involved in the weathering of the materials of the cultural heritage. However, the realistic simulation in the laboratory of the environmental conditions ruling the interactions of atmospheric compounds with materials is a very complex task. The aim of this work is to characterise CIME, a new chamber specially built to simulate the interactions between materials of the cultural heritage and the environment. The originality of this instrument is that beside the usual climatic parameters (temperature, relative humidity, solar radiation) and gaseous pollutants, it also allows the controlled injection of different types of particulate matter such as terrigenous, marine and anthropogenic. Therefore, varied realistic atmospheric environments (marine or urban) can be easily simulated within CIME. In addition to the technical description of CIME, this paper shows the first results obtained by the impact of gaseous pollutants on non-durable glass, bronze and limestone. The first experiments for the deposition of different particles (calcite, clays, soot and halite) are also presented.

Absorption spectra of pure 16 O 12 C 16 O have been recorded, at room temperature and for five pressures between 0.2 and 1 atm, in the very intense ν 3 band. As recently done for CO, this was achieved using a high resolution (0.005 cm −1 ) Fourier transform spectrometer together with a specially designed cell. With the latter, set to a path length of about 20 μm, the absorption by extremely intense lines is measured under appropriate (non saturating transmission) absorption conditions, regardless of the gas pressure. The recorded spectra have been adjusted one-by-one using Voigt line-shapes in order to retrieve the line positions and the Lorentz widths for the P (40) to R (40) lines. The results show that accurate self-broadening coefficients γ are obtained but that experimental uncertainties forbid any reliable determinations of the pressure-induced shifts δ due to the fact that they are about two order of magnitude smaller than γ . The present values of γ show the limited accuracy of previous determinations for the exact same lines. They are in very good agreement with those in the HITRAN database if the latter, which are for a speed-dependent Voigt profile, are properly corrected to correspond to a Voigt profile.

Absorption spectra of pure 12 C 16 O have been recorded, at room temperature and for various pressures, in the very intense 1←0 band. This was made using a high-resolution (0.005 cm −1 ) Fourier transform spectrometer together with a specially designed cell that enables one to adapt the optical path from a few μm up to several mm. Thanks to the latter, absorption by extremely intense lines is measured for the first time under adapted (non saturating transmission) absorbance conditions, even for a pure gas pressure near 1 atm. The recorded spectra, obtained for a path length of about 130 μm, have been adjusted using Voigt line-shapes in order to retrieve the unperturbed line positions, and the self-broadening and -shifting parameters induced by pressure for the P (20) to R (19) lines. Our results for the line widths confirm the expected very small and undetected influence of vibration on the broadening and demonstrate the inaccuracy of previous high-resolution measurements made under extremely strong absorption conditions. Similarly, our study provides the first accurate self-induced line shifts for the 1←0 band.

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 (

In this study we provide a first estimate of the aethalometer multiple scattering correction Cref for mineral dust aerosols. The Cref at 450 and 660 nm was obtained from the direct comparison of aethalometer data (Magee Sci. AE31) with the absorption coefficient calculated as the difference between the extinction and scattering coefficients measured by a CAPS PMex and a nephelometer at 450 nm and the absorption coefficient from a MAAP (Multi-Angle Absorption Photometer) at 660 nm. Measurements were performed on seven dust aerosol samples generated in the laboratory by the mechanical shaking of natural parent soils issued from different source regions worldwide. The single scattering albedo (SSA) at 450 and 660 nm and the size distribution of the aerosols were also measured. Cref for mineral dust varies between 1.81 and 2.56 for a SSA of 0.85–0.96 at 450 nm and between 1.75 and 2.28 for a SSA of 0.98–0.99 at 660 nm. The calculated mean Cref for dust is 2.09 (± 0.22) at 450 nm and 1.92 (± 0.17) at 660 nm. With this new Cref the dust absorption coefficient by aethalometer is about 2 % (450 nm) and 11 % (660 nm) higher than that obtained by using Cref = 2.14, usually assumed in the literature. This difference induces up to 3 % change in the dust SSA. The Cref seems independent of the particle fine and coarse size fractions, and so the obtained Cref can be applied to dust both close to sources and following transport. Additional experiments performed with pure kaolinite mineral and polluted ambient aerosols indicate a Cref of 2.49 (± 0.02) and 2.32 (± 0.01) at 450 and 660 nm (SSA = 0.96–0.97) for kaolinite, and a Cref of 2.32 (± 0.36) at 450 nm and 2.32 (± 0.35) at 660 nm for pollution aerosols (SSA = 0.62–0.87 at 450 nm and 0.42–0.76 at 660 nm).

This paper presents new laboratory measurements of the mass absorption efficiency (MAE) between 375 and 850 nm for mineral dust of different origin in two size classes: PM10.6 (mass fraction of particles of aerodynamic diameter lower than 10.6 µm) and PM2.5 (mass fraction of particles of aerodynamic diameter lower than 2.5 µm). Experiments have been performed in the CESAM simulation chamber using generated mineral dust from natural parent soils, and optical and gravimetric analyses. Results show that the MAE values are lower for the PM10.6 mass fraction (range 37–135 × 10−3 m2 g−1 at 375 nm) than for the PM2.5 (range 95–711 × 10−3 m2 g−1 at 375 nm), and decrease with increasing wavelength as λ-AAE, where Angstrom Absorption Exponent (AAE) averages between 3.3–3.5, regardless of size. The size-independence of AAE suggests that, for a given size distribution, the possible variation of dust composition with size would not affect significantly the spectral behavior of shortwave absorption. Because of its high atmospheric concentration, light-absorption by mineral dust can be competitive to black and brown carbon even during atmospheric transport over heavy polluted regions, when dust concentrations are significantly lower than at emission. The AAE values of mineral dust are higher than for black carbon (~ 1), but in the same range as light-absorbing organic (brown) carbon. As a result, depending on the environment, there can be some ambiguity in apportioning the AAOD based on spectral dependence, which is relevant to the development of remote sensing of light-absorption aerosols from space, and their assimilation in climate models. We suggest that the sample-to-sample variability in our dataset of MAE values is related to regional differences of the mineralogical composition of the parent soils. Particularly in the PM2.5 fraction, we found a strong linear correlation between the dust light-absorption properties and elemental iron rather than the iron oxide fraction, which could ease the application and the validation of climate models that now start to include the representation of the dust composition, as well as for remote sensing of dust absorption in the UV-VIS spectral region.

In this study we present the first results from laboratory chamber experiments newly designed to investigate the longwave optical properties of mineral dust. Extinction spectra in the 2–16 µm range have been measured in situ (T = 293 K, RH