Heterogeneous reactivity of pesticides adsorbed on atmospheric particles : influence of environmental parameters on the kinetics

La contamination de l’environnement par les pesticides est ubiquiste et les preuves d’impacts sanitaires et environnementaux s’accumulent. Après application, une fraction des pesticides passe dans l’atmosphère où ils sont répartis entre les phases gazeuse, aqueuse et particulaire. La plupart des pesticides utilisés aujourd’hui sont semi-volatils et sont donc en partie adsorbés en surface de particules atmosphériques où ont lieu des réactions hétérogènes. La réactivité en phase gazeuse des pesticides est documentée contrairement à celle en phase particulaire qui est mal décrite. Ce travail expérimental a permis d’étudier l’influence de paramètres environnementaux (humidité relative, nature des particules, taux de recouvrement) sur la réactivité hétérogène de 8 pesticides (cyprodinil deltaméthrine difénoconazole fipronil oxadiazon pendiméthaline perméthrine tétraconazole). Ces composés étaient adsorbés sur des particules minérales (silices hydrophobe et hydrophile, sable d’Arizona) et ont été exposés aux principaux oxydants atmosphériques (ozone, radicaux hydroxyles (OH) et nitrates (NO3)). Les résultats ont montré que l’humidité relative, la nature des particules et le taux de recouvrement peuvent influencer les cinétiques de dégradation hétérogène par l’ozone et les radicaux OH. Ils ont aussi permis de mettre en évidence l’efficacité des radicaux NO3 pour la dégradation hétérogène des pesticides (temps de demi-vie hétérogène avec NO3 : 2 à 16 j contre 0,4 à >800 j avec l’ozone et 3 à >100 j avec OH). Ces résultats permettent une meilleure compréhension du devenir atmosphérique des pesticides et contribueront à la prédiction de la pollution de l’air par les pesticides.Environmental contamination by pesticides is ubiquitous and induces health and environmental impacts. Once applied, some of the pesticides reach the atmosphere, where they distribute between the aqueous, gaseous and particle phases. Most of the currently used pesticides are semi-volatiles and are therefore partially adsorbed on the atmospheric particle surfaces and undergo heterogeneous degradation reactions. If their reactivity in the gaseous phase is often known, their reactivity in the particle phase remains poorly described. This experimental work allowed studying the influence of environmental parameters (relative humidity, type of particles, pesticides surface concentration) on the reactivity of eight pesticides (cyprodinil, deltamethrin, difenoconazole, fipronil, oxadiazon, pendimethalin, permethrin, tetraconazole). They were adsorbed on mineral surfaces mimicking mineral aerosol particles (hydrophobic and hydrophilic silica, Arizona sand) to simulate atmospheric degradation by the mains atmospheric oxidants (ozone, hydroxyl radicals (OH) and nitrate radicals (NO3)). Results showed that relative humidity, particle type, and pesticide concentration can influence the heterogeneous degradation of pesticides with ozone and OH radicals. They also showed the efficiency of NO3 radicals for the atmospheric heterogeneous degradation of pesticides (half-lives in the particle phase from 2 to 16 d with NO3 compared to 0.4 to > 800 d with ozone and to 3 to > 100 d with OH). Results obtained allow a better understanding of the atmospheric fate of pesticides and will contribute to predict of atmospheric contamination

Heterogeneous atmospheric degradation of current-use pesticides by nitrate radicals

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Heterogeneous atmospheric degradation of pesticides by ozone: Influence of relative humidity and particle type

International audienceIn the atmosphere pesticides can be adsorbed on the surface of particles, depending on their physico-chemical properties. They can react with atmospheric oxidants such as ozone but parameters influencing the degradation kinetics are not clear enough. In this study the heterogeneous ozonolysis of eight commonly used pesticides (i.e., difenoconazole, tetraconazole, cyprodinil, fipronil, oxadiazon, pendimethalin, deltamethrin, and permethrin) adsorbed on hydrophobic and hydrophilic silicas, and Arizona dust at relative humidity ranging from 0% to 80% was investigated. Under experimental conditions, only cyprodinil, deltamethrin, permethrin and pendimethalin were degraded by ozone. Second-order kinetic constants calculated for the pesticides degraded by ozone ranged from (4.7 ± 0.4) × 10−20 cm3 molecule−1 s−1 (pendimethalin, hydrophobic silica, 55% RH) to (2.3 ± 0.4) × 10−17 cm3 molecule−1 s−1 (cyprodinil, Arizona dust, 0% RH). Results obtained can contribute to a better understanding of the atmospheric fate of pesticides in the particulate phase and show the importance of taking humidity and particle type into account for the determination of pesticides atmospheric half-lives

Heterogeneous degradation of pesticides by OH radicals in the atmosphere: Influence of humidity and particle type on the kinetics

International audiencePesticides can be adsorbed on the surface of atmospheric aerosol, depending on their physicochemical properties. They can be degraded by atmospheric oxidants such as OH radicals but the influence of some environmental parameters on the degradation kinetics, especially relative humidity and particle surface type, is not well understood. Heterogeneous degradation by OH radicals of eight commonly used pesticides (i.e., difenoconazole, tetraconazole, cyprodinil, fipronil, oxadiazon, pendimethalin, deltamethrin, and permethrin) adsorbed on hydrophobic and hydrophilic silicas at a relative humidity ranging from 0% to 70% was studied. Under experimental conditions, only cyprodinil, deltamethrin, permethrin, and pendimethalin were degraded by OH radical in atmospheric relevant concentration. Second-order kinetic constants calculated for the pesticides degraded by OH radicals ranged from (1.93 ± 0.61) × 10−13 cm3 molecule−1 s−1 (permethrin, hydrophobic silica, 30% RH) to (4.08 ± 0.27) × 10−12 cm3 molecule−1 s−1 (pendimethalin, hydrophilic silica, 0% RH). Results obtained can contribute to improve the understanding of the atmospheric fate of pesticides and other semi-volatile organic compounds in the particulate phase and they highlight the importance of taking humidity and particle type into account for the determination of pesticides atmospheric half-lives

Influence of pesticide concentration on their heterogeneous atmospheric degradation by ozone

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Ozonolysis of Oleic Acid Aerosol Revisited: Multiphase Chemical Kinetics and Reaction Mechanisms

The chemical processing of organic aerosol particles is important for atmospheric chemistry, climate, and public health. The heterogeneous oxidation of oleic acid particles by ozone is one of the most frequently investigated model systems. The available kinetic data span a wide range of particle size and ozone concentration and are obtained with different experimental techniques including electrodynamic balance (EDB), optical tweezers, environmental chamber, and aerosol flow tube reactors using mass spectrometry and Raman spectroscopy as detection methods. Existing kinetic and mechanistic analyses, however, reveal systematic differences and inconsistencies that are a matter of ongoing debate. We developed and applied an inverse modeling approach using a kinetic multilayer model (KM-SUB) and Monte Carlo-based global optimization algorithms to 11 literature data sets and an additional new set of EDB data. We were able to reconcile most experimental data with consistent sets of multiphase chemical kinetic parameters. For a unique determination of these parameters, however, further experiments with simultaneous measurement of multiple observables at specific, insightful reaction conditions are required. We tested three different reaction mechanisms and conclude that secondary chemistry involving Criegee intermediates appears crucial to resolve the discrepancies found in earlier studies. Primary ozone chemistry occurs close to the particle surface and secondary reactions seem to dominate in the particle bulk, involving OH formation and radical chain reactions.ISSN:2472-345

Influence of pesticide mixture on their heterogeneous atmospheric degradation by ozone and OH radicals

International audiencePesticides in the atmosphere can exist in both gaseous and particulate phases due to their semi-volatile properties. They can undergo degradation when exposed to atmospheric oxidants like ozone and hydroxyl radicals. The majority of studies on the atmospheric reactivity of pesticides study them in combination, without considering potential mixture effects that could induce uncertainties in the results. Therefore, this study aims to address this gap, through laboratory studies using a flow reactor, and by evaluating the degradation kinetics of pendimethalin mixed with folpet, tebuconazole, and S-metolachlor, which were simultaneously adsorbed on hydrophobic silica particles that mimic atmospheric aerosols. The comparison with other mixtures, including pendimethalin, from the literature has shown similar reactivity with ozone and hydroxyl radicals, indicating that the degradation kinetics of pesticides is independent of the mixture. Moreover, the degradation rates of the four pesticides under study indicate that they are not or slightly degraded by ozone, with half-lives ranging from 29 days to over 800 days. In contrast, when exposed to hydroxyl radicals, tebuconazole exhibited the fastest reactivity, with a half-life of 4 days, while pendimethalin had a half-life of 17 days

Heterogeneous atmospheric degradation of pesticides by ozone: Influence of relative humidity and particle type

International audienceIn the atmosphere pesticides can be adsorbed on the surface of particles, depending on their physico-chemical properties. They can react with atmospheric oxidants such as ozone but parameters influencing the degradation kinetics are not clear enough. In this study the heterogeneous ozonolysis of eight commonly used pesticides (i.e., difenoconazole, tetraconazole, cyprodinil, fipronil, oxadiazon, pendimethalin, deltamethrin, and permethrin) adsorbed on hydrophobic and hydrophilic silicas, and Arizona dust at relative humidity ranging from 0% to 80% was investigated. Under experimental conditions, only cyprodinil, deltamethrin, permethrin and pendimethalin were degraded by ozone. Second-order kinetic constants calculated for the pesticides degraded by ozone ranged from (4.7 ± 0.4) × 10−20 cm3 molecule−1 s−1 (pendimethalin, hydrophobic silica, 55% RH) to (2.3 ± 0.4) × 10−17 cm3 molecule−1 s−1 (cyprodinil, Arizona dust, 0% RH). Results obtained can contribute to a better understanding of the atmospheric fate of pesticides in the particulate phase and show the importance of taking humidity and particle type into account for the determination of pesticides atmospheric half-lives