Emilie Perraudin

Characterisation of tracers for aging of a-pinene secondary organic aerosol using liquid chromatography/negative ion electrospray ionisation mass spectrometry

Secondary organic aerosol (SOA) from the oxidation of a-pinene is a very complex and dynamic mixture containing products with a different chemical nature and physicochemical properties that are dependent on chemical evolution or aging processes. In this study, we focus on the chemical characterisation of major products that are formed upona-pineneozonolysisSOAandsubsequentagingthroughOH-initiatedreactionsintheabsenceofNOx,whichinclude known as well as unknown tracers. The mass spectrometric data obtained for selected unknown compounds that show an increasedrelativeabundanceuponagingareinterpreted indetailandtentativestructuresforthemareproposedtakinginto account their formation through photooxidation of a-pinene. Known tracers for a-pinene SOA aging that were identified include norpinic acid, 10-hydroxypinonic acid, diaterpenylic acid acetate, and diesters formed by esterification of pinic acidwithterpenylicacidor10-hydroxypinonicacid.Noveltracersfora-pineneSOAagingthatweretentativelyidentified include dinorpinic acid and 8-hydroxypinonic acid. In addition, reaction mechanisms are proposed to explain the formation of the observed a-pinene SOA tracers.

Photochemical Aging of Secondary Organic Aerosols Generated from the Photooxidation of Polycyclic Aromatic Hydrocarbons in the Gas-Phase

Aging processes of secondary organic aerosol (SOA) may be a source of oxygenated organic aerosols; however, the chemical processes involved remain unclear. In this study, we investigate photochemical aging of SOA produced by the gas-phase oxidation of naphthalene by hydroxyl radicals and acenaphthylene by ozone. We monitored the SOA composition using a high-resolution time-of-flight aerosol mass spectrometer. We initiated SOA aging with UV photolysis alone and with OH radicals in the presence or absence of light and at different NOx levels. For naphthalene, the organic composition of the particulate phase seems to be dominated by highly oxidized compounds such as carboxylic acids, and aging data may be consistent with diffusion limitations. For acenaphthylene, the fate of oxidized products and the moderately oxidized aerosol seem to indicate that functionalization reactions might be the main aging process were initiated by the cumulative effect of light and OH radicals.

Kinetics of the gas-phase reactions of chlorine atoms with naphthalene, acenaphthene, and acenaphthylene.

Reactions of polycyclic aromatic hydrocarbons (PAHs) with chlorine atoms may occur in specific areas such as coastal regions and the marine boundary layer. In this work, rate constants for the gas-phase reactions of naphthalene, acenaphthene, and acenaphthylene with chlorine atoms have been measured using the relative rate technique. Experiments were performed at room temperature (293 ± 2 K) and atmospheric pressure in an atmospheric simulation chamber using a proton-transfer reaction mass spectrometer (PTR-MS) to monitor the concentrations of PAHs and the reference compounds (acetone, methanol, 1,3,5-trimethylbenzene, and isoprene) as a function of time. The rate constants obtained in this work were (in units of cm(3) molecule(-1) s(-1)) (4.22 ± 0.46) × 10(-12), (3.01 ± 0.82) × 10(-10), and (4.69 ± 0.82) × 10(-10) for naphthalene, acenaphthene, and acenaphthylene, respectively. These are the first measurements of the rate constants for gas-phase reactions of Cl atoms with acenaphthene and acenaphthylene. The rate constant determined in this study for the reaction of naphthalene with Cl atoms is not in agreement with the only other previously reported value in the literature. The results are used to assess the potential role of chlorine atom reactions in the atmospheric oxidation of PAHs.

A new approach for studying aqueous phase OH kinetics: application of Teflon waveguides

Bimolecular rate coefficients for the reactions of the hydroxyl radical, OH, with methanol, ethanol, tetrahydrofuran, dimethylmalonate [CH3OC(O)CH2C(O)OCH3], dimethylsuccinate [CH3OC(O)CH2CH2C(O)OCH3], dimethylcarbonate [CH3OC(O)OCH3] and diethylcarbonate [CH3CH2OC(O)OCH2CH3] in aqueous solutions have been measured using a novel experimental approach. The centrepiece of the new experimental technique reported in this work is a Teflon AF 2400 liquid core waveguide. The physical properties of the Teflon AF 2400 liquid core waveguide allow for the construction of a micro-flowtube reaction photolysis cell with an extremely low volume and a very long optical pathway. Such a reaction system allows for a very sensitive detection of chemical transients in the aqueous phase. The micro-flowtube experiments involved competition kinetics of the OH radical with the organic reactant of interest and an SCN− anion, (kOH+SCN− = 1.29 × 1010 M−1 s−1). The (SCN)−2 anion was detected using UV-visible spectroscopy following a medium pressure mercury lamp photolysis (λ ≥ 366 nm) of H2O/H2O2/reactant/KSCN mixtures. All experiments were carried out at room temperature. Measured rate coefficients for the reaction of the OH radical with methanol, ethanol, tetrahydrofuran, dimethylmalonate, dimethylsuccinate, dimethylcarbonate and diethylcarbonate are (units are 108 M−1 s−1): kOH+methanol = 13 ± 4, kOH+ethanol = 19 ± 5, kOH+THF = 38 ± 10, kOH+dimethylmalonate = 2.7 ± 0.9, kOH+dimethylsuccinate = 5.3 ± 2.9, kOH+dimethylcarbonate = 0.51 ± 0.22, kOH+diethylcarbonate = 7.9 ± 3.2. Uncertainties in the above expressions are ±2σ and represent precision only. The reported rate coefficients for the reactions of OH with ethanol, methanol and THF agree very well with the currently recommended values. To date, there is no kinetic data reported in the literature for the OH radical reaction with dimethylmalonate, dimethylsuccinate, dimethylcarbonate and diethylcarbonate. The reaction mechanism is briefly discussed as a function of bond energies.

Gas- and Particle-Phase Products from the Chlorine-Initiated Oxidation of Polycyclic Aromatic Hydrocarbons

The chlorine atom (Cl)-initiated oxidation of three polycyclic aromatic hydrocarbons (PAHs; namely, naphthalene, acenaphthylene, and acenaphthene) was investigated. Experiments were performed in an atmospheric simulation chamber using a proton transfer reaction time-of-flight mass spectrometer (TOF-MS) and an aerosol TOF-MS to characterize the oxidation products in the gas and particle phases, respectively. The major products identified from the reaction of Cl atoms with naphthalene were phthalic anhydride and chloronaphthalene, indicating that H atom abstraction and Cl addition reaction pathways are both important. Acenaphthenone was the principal product arising from reaction of Cl with acenaphthene, while 1,8-naphthalic anhydride, acenaphthenone, acenaphthenequinone, and chloroacenaphthenone were all identified as products of acenaphthylene oxidation, confirming that the cylcopenta-fused ring controls the reactivity of these PAHs toward Cl atoms. Possible reaction mechanisms are proposed for the formation of these products, and favored pathways have been suggested. Large yields of secondary organic aerosol (SOA) were also observed in all experiments, and the major products were found to undergo significant partitioning to the particle-phase. This work suggests that Cl-initiated oxidation could play an important role in SOA formation from PAHs under specific atmospheric conditions where the Cl atom concentration is high, such as the marine boundary layer.

Speciation of organic fraction does matter for source apportionment. Part 1: A one-year campaign in Grenoble (France)

PM10 source apportionment was performed by positive matrix factorization (PMF) using specific primary and secondary organic molecular markers on samples collected over a one year period (2013) at an urban station in Grenoble (France). The results provided a 9-factor optimum solution, including sources rarely apportioned in the literature, such as two types of primary biogenic organic aerosols (fungal spores and plant debris), as well as specific biogenic and anthropogenic secondary organic aerosols (SOA). These sources were identified thanks to the use of key organic markers, namely, polyols, odd number higher alkanes, and several SOA markers related to the oxidation of isoprene, α-pinene, toluene and polycyclic aromatic hydrocarbons (PAHs). Primary and secondary biogenic contributions together accounted for at least 68% of the total organic carbon (OC) in the summer, while anthropogenic primary and secondary sources represented at least 71% of OC during wintertime. A very significant contribution of anthropogenic SOA was estimated in the winter during an intense PM pollution event (PM10>50μgm-3 for several days; 18% of PM10 and 42% of OC). Specific meteorological conditions with a stagnation of pollutants over 10days and possibly Fenton-like chemistry and self-amplification cycle of SOA formation could explain such high anthropogenic SOA concentrations during this period. Finally, PMF outputs were also used to investigate the origins of humic-like substances (HuLiS), which represented 16% of OC on an annual average basis. The results indicated that HuLiS were mainly associated with biomass burning (22%), secondary inorganic (22%), mineral dust (15%) and biogenic SOA (14%) factors. This study is probably the first to state that HuLiS are significantly associated with mineral dust.

Observation of nighttime new particle formation over the French Landes forest

Improving the understanding of processes related to atmospheric particle sources is essential to better assess future climate. Especially, how biogenic volatile organic compounds (BVOCs) are involved in new particle formation (NPF) is still unclear, highlighting the need for field studies in sites that have not yet been explored. Weakly anthropised, mostly composed of maritime pines (known as strong monoterpene emitters), vast and under the influence of sea spray inputs, the Landes forest (located in the southwestern part of France) is a suitable ecosystem to explore these questions. The aim of the present work was to investigate for the first time NPF in the Landes forest, and to identify the conditions for NPF. During a field campaign conducted in July 2015, clear NPF was observed during nighttime, at a high frequency rate (37.5%), whereas only two daytime episodes were observed. Growth rates during NPF events were in the range 9.0-15.7nmh-1, and nucleation rates (J10) in the range 0.8-8 particles cm3s-1, typically in the range of reported values from rural sites. Nocturnal NPF started at sunset, lagging the reductions of temperature and ozone concentration as well as the increase of relative humidity, atmospheric stability and monoterpene concentration. We established that NPF occurred during more stratified atmosphere episodes, reflecting that NPF is more influenced by local processes at the Landes forest site (Bilos). Concentration of the sum of monoterpenes, here mainly α- and β-pinene, was observed to be maximal during NPF episodes. On the contrary, ozone concentration was lower, which may indicate a larger consumption during nights where NPF episodes occur. Results strongly suggest the contribution of BVOC oxidation to nocturnal NPF, in both nucleation and the growth stages.

Speciation of organic fractions does matter for aerosol source apportionment. Part 2: Intensive short-term campaign in the Paris area (France)

The present study aimed at performing PM10 source apportionment, using positive matrix factorization (PMF), based on filter samples collected every 4h at a sub-urban station in the Paris region (France) during a PM pollution event in March 2015 (PM10>50μgm-3 for several consecutive days). The PMF model allowed to deconvolve 11 source factors. The use of specific primary and secondary organic molecular markers favoured the determination of common sources such as biomass burning and primary traffic emissions, as well as 2 specific biogenic SOA (marine+isoprene) and 3 anthropogenic SOA (nitro-PAHs+oxy-PAHs+phenolic compounds oxidation) factors. This study is probably the first one to report the use of methylnitrocatechol isomers as well as 1-nitropyrene to apportion secondary OA linked to biomass burning emissions and primary traffic emissions, respectively. Secondary organic carbon (SOC) fractions were found to account for 47% of the total OC. The use of organic molecular markers allowed the identification of 41% of the total SOC composed of anthropogenic SOA (namely, oxy-PAHs, nitro-PAHs and phenolic compounds oxidation, representing 15%, 9%, 11% of the total OC, respectively) and biogenic SOA (marine+isoprene) (6% in total). Results obtained also showed that 35% of the total SOC originated from anthropogenic sources and especially PAH SOA (oxy-PAHs+nitro-PAHs), accounting for 24% of the total SOC, highlighting its significant contribution in urban influenced environments. Anthropogenic SOA related to nitro-PAHs and phenolic compounds exhibited a clear diurnal pattern with high concentrations during the night indicating the prominent role of night-time chemistry but with different chemical processes involved.