Widespread Pesticide Distribution in the European Atmosphere Questions their Degradability in Air.

Risk assessment of pesticide impacts on remote ecosystems makes use of model-estimated degradation in air. Recent studies suggest these degradation rates to be overestimated, questioning current pesticide regulation. Here, we investigated the concentrations of 76 pesticides in Europe at 29 rural, coastal, mountain, and polar sites during the agricultural application season. Overall, 58 pesticides were observed in the European atmosphere. Low spatial variation of 7 pesticides suggests continental-scale atmospheric dispersal. Based on concentrations in free tropospheric air and at Arctic sites, 22 pesticides were identified to be prone to long-range atmospheric transport, which included 15 substances approved for agricultural use in Europe and 7 banned ones. Comparison between concentrations at remote sites and those found at pesticide source areas suggests long atmospheric lifetimes of atrazine, cyprodinil, spiroxamine, tebuconazole, terbuthylazine, and thiacloprid. In general, our findings suggest that atmospheric transport and persistence of pesticides have been underestimated and that their risk assessment needs to be improved.

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

Pesticides 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.

Underestimation of Anthropogenic Bromoform Released into the Environment?

Bromoform (CHBr3) belongs to very-short-lived substances (VSLSs), which are important precursors of reactive bromine species (BrOx) contributing to tropospheric and stratospheric chemistry. To date, most models calculating bromine product emissions to the atmosphere only consider the natural production of CHBr3 from marine organisms such as macroalgae and phytoplankton. However, CHBr3 has many other anthropogenic sources (coastal industrial sites, desalination and wastewater plants, ballast waters, and seawater toilets) that may drastically increase the amounts emitted in the atmosphere. Here, we report the levels of CHBr3 released in water and air (according to real-time and offline measurements by proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) and gas chromatography with electron capture detection (GC-ECD)) in a highly industrialized area where 3 million cubic meters of chlorinated seawater is released each day, which were measured during six field campaigns (at sea and on land) distributed over 3 years. The highest levels found during this survey (which were correlated to the physical-chemical characteristics of the water, meteorological and hydrological conditions, salinity, and temperature gradients along the water column) reached 34.6 µg L-1 in water (100-10 000 times higher than reported natural levels) and 3.9 ppbv in the air (100 times higher than the maximum reported value to date). These findings suggest the need to undertake sampling and analysis campaigns as close as possible to chlorinated discharges, as anthropogenic CHBr3 sources from industrial discharges may be a missing factor in global flux estimates or organic bromine to the atmosphere.

Simulating the impact of volatilization on atmospheric concentrations of pesticides with the 3D chemistry-transport model CHIMERE: Method development and application to S-metolachlor and folpet.

A module to simulate the volatilization of pesticides from soils and plants was implemented in the air quality model CHIMERE in order to simulate spatiotemporal distribution of pesticide atmospheric concentrations. Pesticide applications are spatially distributed according to the quantities of pesticides sold per municipality in France (recorded in the French BNVD-S database) and are temporally distributed according to the application periods determined with enquiries. The model was applied to S-metolachlor and folpet. In the first stage of the study, pesticide emissions simulated by the CHIMERE and Volt'Air models are compared. In the second stage, measured concentrations of S-metolachlor and folpet from mid-April to the end of June are compared to the simulation results at the French and PACA (Southeastern region of France) scales. The model can reproduce the spatial distribution of S-metolachlor concentrations (spatial correlation over France of 0.79) with a bias ranging from -50 to 50% for most stations during the application period. The simulation of folpet concentrations remains challenging with a lack of correlation between model results and measurements, that could possibly be due to a lack of precision in the temporalization of applications.

Sprays and diffusers as indoor air fresheners: Exposure and health risk assessment based on measurements under realistic indoor conditions.

Noncombustible air fresheners are indoor air emission sources of concern. The associated health risks should be better understood. Based on 15 products (4 sprays, 6 passive diffusers, and 5 active diffusers), the health risk assessment (HRA) approach was applied to a national use survey in France and to concentrations measured in an experimental house. The targeted substances included volatile organic compounds (VOCs), carbonyls, and fine particles (PM2.5 ). Mean-use and reasonable worst-case generic scenarios were designed. No situation of concern occurred regarding chronic exposure associated with the mean use. Under the reasonable worst-case scenarios, the chronic risk could exceed selected health reference standards, mainly for acrolein (average inhaled concentration (AIC) up to 3.5 µg/m3 ), benzene (AIC up to 4 µg/m3 ), and limonene (AIC up to 8 mg/m3 ). The acute exposure, defined as a 1-h exposure, could exceed selected health standards, primarily for acrolein (up to 23 µg/m3 ) and formaldehyde (up to approximately 370 µg/m3 ). Furthermore, the 1-h average PM2.5 concentration, including ultrafine particles, could exceed 100 µg/m3 , typically for sprays. These results suggest that the highest exposures should be reduced and, as such, that the emissions of the highest-emissivity products should be lowered.

Development and validation of a UPLC-MS/MS method for the quantification of isothiazolinones in the composition and emissions from consumer products.

Isothiazolinones, a family of biocides, are used as preservatives for their fungicidal, bactericidal, and algacidal properties. These compounds can be found in a wide range of consumer and building products, such as paints, varnishes, shampoos, and liquid detergents. A robust analytical UPLC-MS/MS method to identify and quantify seven isothiazolinones (MIT, CMI, BIT, MBIT, BBIT, OIT, and DCOIT) in consumer products and their emissions was developed and validated according to ISO/IEC 17025. The limits of detection (LODs) ranged from 0.14 µg L-1 (BIT) to 0.54 µg L-1 (CMI). The method was applied for the quantification of the seven isothiazolinones in four types of consumer products (i.e., cosmetics, air fresheners, cleaning products, and building products) and the indoor emissions from a paint. Matrix effects were observed for the shampoo (63-74%), the shower gel (67-84%), and the ceramic glass cleaner (53-57%). All isothiazolinones indicated by the manufacturer (i.e., MIT, CMI, BIT, OIT, and DCOIT) were detected in the products and successfully quantified by the UPLC-MS/MS method.

Monitoring of pesticides in ambient air: Prioritization of substances.

Despite the richness of data collected on pesticide concentrations in ambient air in France, knowledge on this topic remains partial and heterogeneous in the absence of specific regulations. The population exposure remains thus difficult to estimate; therefore it was necessary to define modalities for implementing national monitoring of pesticides in ambient air in metropolitan France and in the overseas territories. The objective of this work was to identify which active substances (a.s.) have to be monitored in priority. As part of a collective expertise, a group of multidisciplinary experts has developed a method to rank active substances authorised as plant protection products, biocides and antiparasitic agents, which were available on the French market in 2015. A 3-steps approach has been developed. The first step consisted of a theoretical approach based on a hierarchy of substances according to four criteria: (a) national uses, (b) emission potential to the air, (c) persistence in the air, and (d) chronic toxicity. The three first criteria give information on their potential to be present in the atmosphere, and the fourth criterion allows to consider their potential of hazard. The second step was an observational approach based on existing database on pesticide air measurements in France. In the third step, both approaches were combined using decision trees to select priority pesticides. Among the 1316 a.s. first identified from the EU Pesticides database, 90 were selected, among which 43 required metrological and/or analytical development. The experts recommended confirming the relevance of performing a longer term monitoring of these a. s. after a one-year exploratory campaign. The proposed method is reproduceable, transparent, easy to update (e.g. in the light of a change in product authorization), and can be adapted to other agricultural and geographical conditions, and objectives (e.g. monitoring of the ecotoxicological effects of pesticides).

Influence of pesticide concentration on their heterogeneous atmospheric degradation by ozone.

A fraction of the atmospheric pesticides can be adsorbed on particles surface according to their physicochemical properties. After adsorption, pesticides can undergo heterogeneous reactivity with atmospheric oxidants such as ozone, but the influence of the pesticide surface coating (i.e., the percentage of the particle surface covered by pesticide molecules) on the degradation kinetics is not well-understood. To estimate the importance of this phenomenon, the influence of the surface coating level in pesticides on the heterogeneous ozonolysis of cyprodinil, deltamethrin, permethrin, and pendimethalin adsorbed on hydrophobic and hydrophilic silicas was investigated. Surface coating level varied from 0.3% to 15% of a monolayer. Generally, the increase of the surface coating level induced a slower degradation of the pesticides above 1%-3% of a monolayer. This decrease was attributed to a shielding effect. More aggregates of pesticides form with increasing surface coating leading to lower accessibility for ozone to the adsorbed pesticide molecules. Moreover, it was observed that the particle type could play a role in the influence of the surface coating level on the degradation rates. Results obtained will contribute to a better understanding of the atmospheric fate of pesticides and semi-volatile organic compounds in the particulate phase and show the importance of working with consistent surface coating level in order to compare the obtained degradation constants.

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.

Occurrence and speciation of chlorination byproducts in marine waters and sediments of a semi-enclosed bay exposed to industrial chlorinated effluents.

Chlorination of seawater is one of the most effective technologies for industrial biofouling control. However, chlorination leads to the formation of halogenated chlorination byproducts (CBPs) associated with potential risks to environmental and human health. The present study investigated the occurrence and distribution of CBPs in the Gulf of Fos, a semi-enclosed bay where chlorinated effluents of multiple industrial plants are discharged. Seawater samples (surface and bottom) were collected at 24 sampling stations, with some near industrial outlets and others dispersed throughout the bay. Sediment samples were also collected at 10 sampling stations. Physicochemical parameters including water temperature, pH, salinity, bromide content, and free and total residual oxidant were determined. Several chemical classes of CBPs including trihalomethanes, haloacetic acids, haloacetonitriles, trihaloacetaldehydes, and halophenols were analyzed. Bromoform was the most abundant CBP in seawater, and it was detected at most of the sampling stations of the bay with highest concentrations occurring near the industrial effluent outlets. Dibromoacetic acid was the second most abundant CBP at most of the sites followed by dibromoacetonitrile. Other detected CBPs included tribromoacetic acid, bromochloroacetonitrile, and bromal hydrate. To our knowledge, the concentration of the latter CBP was reported here for the first time in the context of industrial seawater chlorination. In sediments, two bromine-containing halophenols (2-chloro-4-bromophenol and 2,4,6-tribromophenol) were detected at two sampling stations. Ecotoxicological assays and risk assessment studies based on the detected environmental concentrations are warranted to elucidate the impacts of marine CBP contamination.

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.

Products and mechanisms of the heterogeneous reactions of ozone with commonly used pyrethroids in the atmosphere.

The heterogeneous reactions of gas-phase ozone and two pyrethroid pesticides, deltamethrin and permethrin, which are the most frequently applied insecticides today, has been investigated. Tentative identifications of heterogeneous ozonolysis products of both pesticides reveal that the reaction mechanisms differ and are mainly influenced by the presence of the cyano moiety at the α-position of deltamethrin (pyrethroid type II). The mechanism study also suggests the important role of water. Finally, several of the degradation products emerged from the ozonolysis of deltamethrin and permethrin may pose further health and environmental hazard due to their higher toxicity, such as phosgene for permethrin, and bromophosgene, 3-phenoxybenzaldehyde (3-PBA) and fulminic acid for deltamethrin. The results obtained in this study can contribute to better describe the atmospheric fate of pesticides in the particle phase.

Formation of indoor nitrous acid (HONO) by light-induced NO2 heterogeneous reactions with white wall paint.

Gaseous nitrogen dioxide (NO2) represents an oxidant that is present in relatively high concentrations in various indoor settings. Remarkably increased NO2 levels up to 1.5 ppm are associated with homes using gas stoves. The heterogeneous reactions of NO2 with adsorbed water on surfaces lead to the generation of nitrous acid (HONO). Here, we present a HONO source induced by heterogeneous reactions of NO2 with selected indoor paint surfaces in the presence of light (300 nm<λ<400 nm). We demonstrate that the formation of HONO is much more pronounced at elevated relative humidity. In the presence of light (5.5 W m(-2)), an increase of HONO production rate of up to 8.6·10(9) molecules cm(-2) s(-1) was observed at [NO2]=60 ppb and 50% relative humidity (RH). At higher light intensity of 10.6 (W m(-2)), the HONO production rate increased to 2.1·10(10) molecules cm(-2) s(-1). A high NO2 to HONO conversion yield of up to 84% was observed. This result strongly suggests that a light-driven process of indoor HONO production is operational. This work highlights the potential of paint surfaces to generate HONO within indoor environments by light-induced NO2 heterogeneous reactions.

Transfluthrin indoor air concentration and inhalation exposure during application of electric vaporizers.

Different household insecticide applications via two electric vaporizers emitting transfluthrin were realized in a full-scale experimental room under controlled air exchange rate conditions. On-line high-time resolved measurements of the gas-phase concentrations of the active substance during and immediately after the spreading periods were performed with a High Sensitivity Proton-Transfer-Reaction Mass Spectrometer (HS-PTR-MS). Experimental and modelled data from the ConsExpo 4.0 software were also compared to evaluate the sources of differences. Different application scenarios were also compared. Averaged inhaled concentrations over 1h, 1week, and 5months were estimated to be 8.3, 1.8, and 1.8µg.m(-3), respectively. Corresponding margins of exposures range from 1000 to 10,000, claiming for the absence of effect. Dermal and dust ingestion pathways, although roughly estimated, seems being non-negligible. This claims for a more in-depth integrated risk assessment.

Use of the HS-PTR-MS for online measurements of pyrethroids during indoor insecticide treatments.

A high-sensitivity proton transfer reaction mass spectrometer (HS-PTR-MS) has been used to study the temporal evolution of pesticide concentrations in indoor environments. Because of the high time variability of the indoor air concentrations during household pesticide applications, the use of this online high time resolution instrument is found relevant. Four pyrethroid pesticides of the latest generation that are commonly found in electric vaporizer refills, namely, transfluthrin, empenthrin, tetramethrin, and prallethrin, were considered. A controlled pesticide generation system was settled and coupled to a HS-PTR-MS analyzer, and a calibration procedure based on the fragmentation patterns of the protonated molecules was performed. To illustrate the functionality of the method, measurements of the concentration-time profiles of transfluthrin contained in an electric vaporizer were carried out in a full-scale environmental room under air exchange rate-controlled conditions. This study demonstrates that the HS-PTR-MS technique can provide online and high time-resolved measurements of semi-volatile organic compounds such as pyrethroid insecticides.

Influence of metal salts on the photodegradation of imazapyr, an imidazolinone pesticide.

The behaviour of imazapyr (2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid), a broad spectrum herbicide of the imidazolinone family, has been studied under UV radiation in the presence of metal salts. Complexation interactions between imazapyr and metal ions decreased imazapyr photolysis. A chemometric study compared the photodegradation of imazapyr in aqueous solutions in the presence of Na+, Ca2+ or Cu2+ and their concomitant anionic species (Cl-, NO3-) at various pesticide/metal ion molar ratios. The study showed the major role of metal ions in the degradation of imazapyr and its main photoproducts. The molecules were strongly stabilised on complexation with metal ions, leading to an increase in persistence of the pesticide.

Photochemical degradation of imazamox in aqueous solution: influence of metal ions and anionic species on the ultraviolet photolysis.

Imazamox [5-methoxymethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) nicotinic acid] is one of the later pesticides of the imidazolinone family. The fate of imazamox has been studied upon UV irradiation. The degradation of a 10 mg L(-1) imazamox solution leads to pyridine derivatives, which remain in solution for 50-100 h. Most of the photoproducts occurring during the photodegradation have been characterized by means of liquid chromatography coupled with mass spectrometry. The degradation scheme is very similar to that observed for the analogous imazapyr pesticide [2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) nicotinic acid]. Nevertheless, imazamox shows a greater stability than imazapyr. More, complexation interactions between imazamox and metal ions such as Cu2+ or Ca2+ increase the persistence of the pesticide.