Photolytic degradation of commonly used pesticides adsorbed on silica particles.

The currently used pesticides are mostly semi-volatile organic compounds. As a result, a fraction of them can be adsorbed on atmospheric aerosol surface. Their atmospheric photolysis is poorly documented, and gaps persist in understanding their reactivity in the particle phase. Laboratory experiments were conducted to determine the photolysis rates of eight commonly used pesticides (i.e., cyprodinil, deltamethrin, difenoconazole, fipronil, oxadiazon, pendimethalin, permethrin, and tetraconazole) using a flow reactor. These pesticides were individually adsorbed on hydrophobic silica particles and exposed to a filtered xenon lamp to mimic atmospheric aerosols and sunlight irradiation, respectively. The estimated photolysis rate constants ranged from less than (3.4 ±â€¯0.3) × 10-7 s-1 (permethrin; >47.2 days) to (3.8 ±â€¯0.2) × 10-5 s-1 (Fipronil; 0.4 days), depending on the considered compound. Moreover, this study assessed the influence of pesticide mixtures on their photolysis rates, revealing that certain pesticides can act as photosensitizers, thereby enhancing the reactivity of permethrin and tetraconazole. This study underscores the importance of considering photolysis degradation when evaluating pesticide fate and reactivity, as it can be a predominant degradation pathway for some pesticides. This contributes to an enhanced understanding of their behavior in the atmosphere and their impact on air quality.

Quantification of monosaccharide anhydrides by gas chromatography/mass spectrometry in lichen samples.

Lichens are effective atmospheric bioindicators, and the bioaccumulation of pollutants is frequently measured in their tissues to assess contamination levels. Even though monosaccharide anhydrides are not directly considered as contaminants, Levoglucosan is a common tracer of biomass burning in atmospheric samples and measuring their accumulation in lichens could help to evaluate the main atmospheric pollution sources on a spatially resolved scale depending on the size of the sampling grid. In this work, a realiable analytical method to determine monosaccharide anhydrides in liches was developed. It is based on ASE extraction, solid phase extraction to clean the sample, and silylation derivatization before GC/MS analysis. The reliability and detection limits of the method were suited to the analysis of lichen samples, and additional quality tests achieved the validation of the method with lichen test matrix. Finally field samples were quantified and the results obtained were consistent with atmospheric levels.

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

Pesticides 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 ±â€¯0.61) × 10-13 cm3 molecule-1 s-1 (permethrin, hydrophobic silica, 30% RH) to (4.08 ±â€¯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.

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

In 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 ±â€¯0.4) × 10-20 cm3 molecule-1 s-1 (pendimethalin, hydrophobic silica, 55% RH) to (2.3 ±â€¯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.

The persistence of pesticides in atmospheric particulate phase: An emerging air quality issue.

The persistent organic pollutants (POPs) due to their physicochemical properties can be widely spread all over the globe; as such they represent a serious threat to both humans and wildlife. According to Stockholm convention out of 24 officially recognized POPs, 16 are pesticides. The atmospheric life times of pesticides, up to now were estimated based on their gas-phase reactivity. It has been only speculated that sorption to aerosol particles may increase significantly the half-lives of pesticides in the atmosphere. The results presented here challenge the current view of the half-lives of pesticides in the lower boundary layer of the atmosphere and their impact on air quality and human health. We demonstrate that semivolatile pesticides which are mostly adsorbed on atmospheric aerosol particles are very persistent with respect to the highly reactive hydroxyl radicals (OH) that is the self-cleaning agent of the atmosphere. The half-lives in particulate phase of difenoconazole, tetraconazole, fipronil, oxadiazon, deltamethrin, cyprodinil, permethrin, and pendimethalin are in order of several days and even higher than one month, implying that these pesticides can be transported over long distances, reaching the remote regions all over the world; hence these pesticides shall be further evaluated prior to be confirmed as POPs.

In-cloud multiphase behaviour of acetone in the troposphere: gas uptake, Henry's law equilibrium and aqueous phase photooxidation.

Acetone is ubiquitous in the troposphere. Several papers have focused in the past on its gas phase reactivity and its impact on tropospheric chemistry. However, acetone is also present in atmospheric water droplets where its behaviour is still relatively unknown. In this work, we present its gas/aqueous phase transfer and its aqueous phase photooxidation. The uptake coefficient of acetone on water droplets was measured between 268 and 281K (γ=0.7 x 10(-2)-1.4 x 10(-2)), using the droplet train technique coupled to a mass spectrometer. The mass accommodation coefficient α (derived from γ) was found in the range (1.0-3.0±0.25) x 10(-2). Henry's law constant of acetone was directly measured between 283 and 298K using a dynamic equilibrium system (H((298K))=(29±5)Matm(-1)), with the Van't Hoff expression lnH(T)=(5100±1100)/T-(13.4±3.9). A recommended value of H was suggested according to comparison with literature. The OH-oxidation of acetone in the aqueous phase was carried out at 298K, under two different pH conditions: at pH=2, and under unbuffered conditions. In both cases, the formation of methylglyoxal, formaldehyde, hydroxyacetone, acetic acid/acetate and formic acid/formate was observed. The formation of small amounts of four hydroperoxides was also detected, and one of them was identified as peroxyacetic acid. A drastic effect of pH was observed on the yields of formaldehyde, one hydroperoxide, and, (to a lesser extent) acetic acid/acetate. Based on the experimental observations, a chemical mechanism of OH-oxidation of acetone in the aqueous phase was proposed and discussed. Atmospheric implications of these findings were finally discussed.

Comparison of annual dry and wet deposition fluxes of selected pesticides in Strasbourg, France.

This work summarizes the results of a study of atmospheric wet and dry deposition fluxes of Deisopropyl-atrazine (DEA), Desethyl-atrazine (DET), Atrazine, Terbuthylazine, Alachlor, Metolachlor, Diflufenican, Fenoxaprop-p-ethyl, Iprodione, Isoproturon and Cymoxanil pesticides conducted in Strasbourg, France, from August 2000 through August 2001. The primary objective of this work was to calculate the total atmospheric pesticide deposition fluxes induced by atmospheric particles. To do this, a modified one-dimensional cloud water deposition model was used. All precipitation and deposition samples were collected at an urban forested park environment setting away from any direct point pesticide sources. The obtained deposition fluxes induced by atmospheric particles over a forested area showed that the dry deposition flux strongly contributes to the total deposition flux. The dry particle deposition fluxes are shown to contribute from 4% (DET) to 60% (cymoxanil) to the total deposition flux (wet+dry).

Development of an SPME-GC-MS/MS method for the determination of pesticides in rainwater: laboratory and field experiments.

A solid-phase microextraction -- coupled to a gas chromatography -- ion trap tandem mass spectrometry (SPME-GC-MS/MS) method was developed for the quantitative determination in rainwater of 8 pesticides amongst the most used in France and 3 triazines metabolites. The main factors affecting the SPME process were studied. Using a 3 mL sample, the method developed showed good linearity for concentrations ranging from 0.05 to 50 microgL(-1) with correlation coefficients between 0.997 and 0.9999 and relative standard deviations (% RSD) below 14%. The study of matrix effects showed that rainwater was too diluted to have any significant influence on the extraction efficiency. To validate the method, a field campaign was carried out on the rain events, which occurred in Strasbourg during a one-year period. The rain concentrations showed patterns of high pesticide concentrations during spring months, which were correlated to the spraying periods of most of these substances.