Gas- and particle-phase products from the photooxidation of acenaphthene and acenaphthylene by OH radicals

This work is focused on the gas-phase oxidation of acenaphthylene and acenaphthene by OH radicals and associated secondary organic aerosol (SOA) formation under low and high-NOx conditions. Experiments were carried out in an atmospheric simulation chamber using a proton transfer reaction time-of-flight-mass spectrometer (PTR-TOF-MS) and an aerosol time-of-flight-mass spectrometer (ATOFMS) to chemically characterize the gas- and particle-phase products, respectively. Due to the structures of these two aromatic compounds, the proposed chemical mechanisms exhibit some differences. In the case of acenaphthene, H-atom abstraction from the saturated cyclopenta-fused ring was found to be competitive with the OH-addition to the aromatic rings. During the photooxidation of acenaphthene using nitrous acid (HONO), aromatic ring-opening products such as indanone and indanone carbaldehyde, generated through OH addition to the aromatic ring, were formed in higher yields compared to low-NOx conditions. In the case of acenaphthylene, OH addition to the unsaturated cyclopenta-fused ring was strongly favored. Hence, ring-retaining species such as acenaphthenone and acenaphthenequinone, were identified as the main reaction products in both gas- and particle-phases, especially under high-NOx conditions. Subsequent SOA formation was observed in all experiments and SOA yields were determined under low/high-NOx conditions to be 0.61/0.46 and 0.68/0.55 from the OH-initiated oxidation of acenaphthylene and acenaphthene, respectively

Atmospheric organic vapors in two European pine forests measured by a Vocus PTR-TOF : insights into monoterpene and sesquiterpene oxidation processes

Atmospheric organic vapors play essential roles in the formation of secondary organic aerosol. Source identification of these vapors is thus fundamental to understanding their emission sources and chemical evolution in the atmosphere and their further impact on air quality and climate change. In this study, a Vocus proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF) was deployed in two forested environments, the Landes forest in southern France and the boreal forest in southern Finland, to measure atmospheric organic vapors, including both volatile organic compounds (VOCs) and their oxidation products. For the first time, we performed binned positive matrix factorization (binPMF) analysis on the complex mass spectra acquired with the Vocus PTR-TOF and identified various emission sources as well as oxidation processes in the atmosphere. Based on separate analysis of low- and high-mass ranges, 15 PMF factors in the Landes forest and nine PMF factors in the Finnish boreal forest were resolved, showing a high similarity between the two sites. Particularly, terpenes and various terpene reaction products were separated into individual PMF factors with varying oxidation degrees, such as lightly oxidized compounds from both monoterpene and sesquiterpene oxidation, monoterpene-derived organic nitrates, and monoterpene more oxidized compounds. Factors representing monoterpenes dominated the biogenic VOCs in both forests, with lower contributions from the isoprene factors and sesquiterpene factors. Factors of the lightly oxidized products, more oxidized products, and organic nitrates of monoterpenes/sesquiterpenes accounted for 8 %-12% of the measured gas-phase organic vapors in the two forests. Based on the interpretation of the results relating to oxidation processes, further insights were gained regarding monoterpene and sesquiterpene reactions. For example, a strong relative humidity (RH) dependence was found for the behavior of sesquiterpene lightly oxidized compounds. High concentrations of these compounds only occur at high RH; yet similar behavior was not observed for monoterpene oxidation products.Peer reviewe

Passive Sampling as a Tool to Assess Atmospheric Pesticide Contamination Related to Vineyard Land Use

The massive use of pesticides in agriculture has led to widespread contamination of the environment, particularly the atmospheric compartment. Thirty-six pesticides, most used in viticul-ture, were monitored in ambient air using polyurethane foams as passive air samplers (PUF-PAS). Spatiotemporal data were collected from the samplers for 10 months (February–December 2013), using two different sampling times (1 and 2 months) at two different sites in a chateau vineyard in Gironde (France). A high-volume active air sampler was also deployed in June. Samples were extracted with dichloromethane using accelerated solvent extraction (ASE) (PUFs from both passive and active) or microwave-assisted extraction (MAE) (filters from active sampling). Extracts were analyzed by both gas and liquid chromatography coupled with tandem mass spectrometry. A total of 23 airborne pesticides were detected at least once. Concentrations in PUF exposed one month ranged from below the limits of quantification (LOQs) to 23,481 ng PUF−1. The highest concentrations were for folpet, boscalid, chlorpyrifos-methyl, and metalaxyl-m—23,481, 17,615, 3931, and 3324 ng PUF−1. Clear seasonal trends were observed for most of the pesticides detected, the highest levels (in the ng m−3 range or the µg PUF−1 range) being measured during their application period. Impregnation levels at both sites were heterogeneous, but the same pesticides were involved. Sampling rates (Rs) were also estimated using a high-volume active air sampler and varied significantly from one pesticide to another. These results provide preliminary information on the seasonality of pesticide concentrations in vineyard areas and evidence for the effectiveness of PUF-PAS to monitor pesticides in ambient air. © 2022 by the authors. Licensee MDPI, Basel, Switzerland.COntinental To coastal Ecosystems: evolution, adaptability and governanc

Développement et caractérisation d'un spectromètre laser infrarouge par différence de fréquences (application à la spectroscopie infrarouge à très haute résolution)

Les méthodes de détection et de caractérisation d'espèces moléculaires d'intérêt atmosphérique dans l'infrarouge se tournent de plus en plus vers l'utilisation de sources laser, monomodes, cw et accordables, complétant des outils tels que les spectromètres à transformée de Fourier (résolution spectrale limitée, source d'erreurs pour la détermination de paramètres moléculaires).Le spectromètre laser infrarouge à différence de fréquence que nous avons développé fonctionne au moyen de deux sources lasers solide (un Nd :YAG, 800 mW à 1064 nm, et une diode-laser à cavité externe, 10-50 mW à 805-885 nm) opérant dans l'infrarouge proche, focalisées au sein d'un cristal non-linéaire de LiNbO3 (PPLN). Il en résulte l'émission d'un faisceau laser à la fréquence égale à la différence des fréquences des faisceaux incidents. Celui-ci possède une largeur spectrale de 3.10-5 cm-1, est accordable de 1800 à 3100 cm-1 sur de petits intervalles spectraux de 0.5 à 1.0 cm-1 avec une puissance de quelques 0.1 microW et un rapport signal/bruit allant jusqu'à quelques milliers, permettant d'enregistrer rapidement (dans une minute environ) les profils et intensités de raies d'absorption avec grande précision. De plus, cet instrument est très compact (0.7.0.7 m2). Nous présentons l'instrument et sa caractérisation avec des raies de N2O, la détermination des intensités absolues de NO2 dans l'infrarouge (par intercalibration avec l'UV-visible) montrant des différences systématiques de 5 % par rapport à la base de données HITRAN 2004, ainsi que la première observation d'interférences collisionnelles dans la structure hyperfine de HI (un effet prédit il y a plus de 20 ans).For laboratory studies and field measurements of atmospheric molecules, single-mode tuneable lasers are more and more used, in order to complete other instruments such as Fourier-transform spectrometers because of their limitations (in particular spectral resolution and signal-to-noise ratio that have an important impact on the accurate determination of molecular line parameters).We report here the development and characterization of a compact tuneable continuous-wave infrared laser, based on difference-frequency generation (DFG) using quasi phase-matching in periodically poled LiNbO3 (PPLN). Several 0.1 microW of infrared radiation (tuneable in the 1800 à 3100 cm-1 range) are obtained using a diode-pumped Nd:YAG laser (output power about 800 mW at 1064 nm, linewidth 1 kHz) together with a tuneable external-cavity diode laser (output power about 10-50 mW in the 805-885 nm region, linewidth 1 MHz). Using this infrared DFG laser for absorption experiments of gas-phase molecules, both very high resolution (1 MHz) and a high signal-to-noise ratio (up to several 1000) can be achieved in measurement time of only a few minutes, as demonstrated using absorption spectra of N2O in different wavelength regions.Using this laser we have determined absolute intensities of infrared lines of NO2 (using a UV-visible set-up to measure the NO2 amounts) observing a systematic difference of about 5 % with respect to the HITRAN 2004 database. We have used the same laser for the first observation of collisional line-mixing between nuclear hyperfine components of HI lines (a phenomenon predicted over 20 years ago).ORSAY-PARIS 11-BU Sciences (914712101) / SudocSudocFranceF

Evaporation process of linalool droplet at high relative humidity using acoustic levitation

National audienc

Evaporation of biogenic organic particle using acoustic levitation

International audienc

Terpenes and their oxidation products in the French Landes forest : insights from Vocus PTR-TOF measurements

The capabilities of the recently developed Vocus proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF) are reported for the first time based on ambient measurements. With the deployment of the Vocus PTR-TOF, we present an overview of the observed gas-phase (oxygenated) molecules in the French Landes forest during summertime 2018 and gain insights into the atmospheric oxidation of terpenes, which are emitted in large quantities in the atmosphere and play important roles in secondary organic aerosol production. Due to the greatly improved detection efficiency compared to conventional PTR instruments, the Vocus PTR-TOF identifies a large number of gas-phase signals with elemental composition categories including CH, CHO, CHN, CHS, CHON, CHOS, and others. Multiple hydrocarbons are detected, with carbon numbers up to 20. Particularly, we report the first direct observations of low-volatility diterpenes in the ambient air. The diurnal cycle of diterpenes is similar to that of monoterpenes and sesquiterpenes but contrary to that of isoprene. Various types of terpene reaction products and intermediates are also characterized. Generally, the more oxidized products from terpene oxidations show a broad peak in the day due to the strong photochemical effects, while the less oxygenated products peak in the early morning and/or in the evening. To evaluate the importance of different formation pathways in terpene chemistry, the reaction rates of terpenes with main oxidants (i.e., hydroxyl radical, OH; ozone, O3; and nitrate radical, NO3) are calculated. For the less oxidized non-nitrate monoterpene oxidation products, their morning and evening peaks have contributions from both O3- and OH-initiated monoterpene oxidation. For the monoterpene-derived organic nitrates, oxidations by O3, OH, and NO3 radicals all contribute to their formation, with their relative roles varying considerably over the course of the day. Through a detailed analysis of terpene chemistry, this study demonstrates the capability of the Vocus PTR-TOF in the detection of a wide range of oxidized reaction products in ambient and remote conditions, which highlights its importance in investigating atmospheric oxidation processes.The capabilities of the recently developed Vocus proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF) are reported for the first time based on ambient measurements. With the deployment of the Vocus PTR-TOF, we present an overview of the observed gas-phase (oxygenated) molecules in the French Landes forest during summertime 2018 and gain insights into the atmospheric oxidation of terpenes, which are emitted in large quantities in the atmosphere and play important roles in secondary organic aerosol production. Due to the greatly improved detection efficiency compared to conventional PTR instruments, the Vocus PTR-TOF identifies a large number of gas-phase signals with elemental composition categories including CH, CHO, CHN, CHS, CHON, CHOS, and others. Multiple hydrocarbons are detected, with carbon numbers up to 20. Particularly, we report the first direct observations of low-volatility diterpenes in the ambient air. The diurnal cycle of diterpenes is similar to that of monoterpenes and sesquiterpenes but contrary to that of isoprene. Various types of terpene reaction products and intermediates are also characterized. Generally, the more oxidized products from terpene oxidations show a broad peak in the day due to the strong photochemical effects, while the less oxygenated products peak in the early morning and/or in the evening. To evaluate the importance of different formation pathways in terpene chemistry, the reaction rates of terpenes with main oxidants (i.e., hydroxyl radical, OH; ozone, O-3; and nitrate radical, NO3) are calculated. For the less oxidized non-nitrate monoterpene oxidation products, their morning and evening peaks have contributions from both O-3(-) and OH- initiated monoterpene oxidation. For the monoterpene-derived organic nitrates, oxidations by O-3, OH, and NO3 radicals all contribute to their formation, with their relative roles varying considerably over the course of the day. Through a detailed analysis of terpene chemistry, this study demonstrates the capability of the Vocus PTR-TOF in the detection of a wide range of oxidized reaction products in ambient and remote conditions, which highlights its importance in investigating atmospheric oxidation processes.Peer reviewe

Simulation of organic aerosol, its precursors, and related oxidants in the Landes pine forest in southwestern France: accounting for domain-specific land use and physical conditions

International audienceOrganic aerosol (OA) still remains one of the most difficult components of the atmospheric aerosols to simulate, given the multitude of its precursors, the uncertainty in its formation pathways, and the lack of measurements of its detailed composition. The LANDEX (LANDes Experiment) project, during its intensive field campaign in summer 2017, gives us the opportunity to compare biogenic secondary OA (BSOA) and its precursors and oxidants obtained within and above the Landes forest canopy to simulations performed with CHIMERE, a state-of-the-art regional chemistry transport model. The Landes forest is situated in the southwestern part of France and is one of the largest anthropized forests in Europe (1×106 ha). The majority of the forest is comprised of maritime pine trees, which are strong terpenoid emitters, providing a large potential for BSOA formation. In order to simulate OA buildup in this area, a specific model configuration setup adapted to the local peculiarities was necessary. As the forest is nonhomogeneous, with interstitial agricultural fields, high-resolution 1 km simulations over the forest area were performed. Biogenic volatile organic compound (BVOC) emissions were predicted by MEGAN, but specific land cover information needed to be used and was thus chosen from the comparison of several high-resolution land cover databases. Moreover, the tree species distribution needed to be updated for the specific conditions of the Landes forest. In order to understand the canopy effect in the forest, canopy effects on vertical diffusivity, winds, and radiation were implemented in the model in a simplified way. The refined simulations show a redistribution of BVOCs with a decrease in isoprene and an increase in terpenoid emissions with respect to the standard case, both of which are in line with observations. Corresponding changes to simulated BSOA sources are tracked. Very low nighttime ozone, sometimes near zero, remains overestimated in all simulations. This has implications for the nighttime oxidant budget, including NO3. Despite careful treatment of physical conditions, simulated BSOA is overestimated in the most refined simulation. Simulations are also compared to air quality sites surrounding the Landes forest, reporting a more realistic simulation in these stations in the most refined test case. Finally, the importance of the sea breeze system, which also impacts species concentrations inside the forest, is made evident