Development of an analytical method for the determination of more than 300 pesticides and metabolites in the particulate and gaseous phase of ambient air.

Pesticides can enter the atmosphere during spraying or after application, resulting in environmental or human exposure. The study describes the optimisation and validation of analytical methods for the determination of more than 300 pesticides in the particulate and gaseous phases of the air. Pesticides were sampled with high-volume air samplers on glass-fibre filters (GFFs) and glass columns filled with polyurethane foam (PUF) and XAD-2 resin. Comparing different extraction methods, a QuEChERS extraction with acetonitrile was selected for the GFFs. For the PUF/XAD-2 columns, a cold-column extraction with dichloromethane was used. Instrumental determination was performed using liquid chromatography/electrospray ionisation-time-of-flight mass spectrometry (LC/ESI-QTOF) and gas chromatography/electron impact ionisation-tandem mass spectrometry (GC/EI-MS/MS). Recovery experiments showed recovery rates between 70 and 120% for 263 compounds on the GFFs and 75 compounds on the PUF/XAD-2 columns. Semi-quantitative determination was performed for 39 compounds on the GFFs and 110 compounds on the PUF/XAD-2 columns. Finally, 27 compounds on the GFFs and 138 compounds on the PUF/XAD-2 columns could be determined only qualitatively. For the determination of the PUF/XAD-2 samples, signal suppression (LC) or signal enhancement (GC) due to matrix effects were determined. Method quantification limits of the optimised methods ranged from 30 to 240 pg/m3 for the target compounds on the GFFs, and from 8 to 60 pg/m3 on the PUF/XAD-2 columns. The applicability of the method was demonstrated by means of environmental air samples from an agricultural area in the Netherlands.

Occurrence and distribution of pesticides and transformation products in ambient air in two European agricultural areas.

Pesticides present a significant risk for both humans and the environment. However, quantitative data for a broad range of airborne pesticides in agricultural areas are missing. During or after the application, pesticides can reach the atmosphere and partition between the particulate and gaseous phase. As part of the EU project SPRINT, weekly ambient air samples were collected from two agricultural areas in Portugal (vineyard) and the Netherlands (potatoes, onions, and sugarbeet) between April 2021 and June 2022 using high-volume air samplers. The samples were analysed for 329 pesticides, of which 99 were detected. The most frequently detected compounds included the fungicides folpet, fenpropidin and mandipropamid, the insecticide chlorpyrifos-methyl, the herbicide terbuthylazine, and the metabolite prothioconazole-desthio, which were found with detection frequencies between 40 and 57 %. Pesticide concentrations ranged between 0.003 ng/m3 and 10 ng/m3. Remarkably, 97 % of the samples contained at least one pesticide and in 95 % of the samples, pesticide mixtures were present. The calculated particle phase fractions correlated with the octanol-air partitioning coefficient for most of the investigated compounds. Furthermore, calculated daily inhalation rates for individual pesticides and pesticide mixtures were far below the Acceptable Daily Intake (ADI) with a margin of exposure (MOE) of >1000 for the highest calculated daily inhalation rate for a child. However, as this value only includes pesticide intake from food and drinking water and considering that 91 % of the detected pesticides are associated with potential adverse human health effects. These findings highlight the broad range of airborne pesticides in agricultural areas and the need for quantitative data to include the intake of mixtures of highly hazardous pesticides by inhalation in human risk assessment.

Collection of human and environmental data on pesticide use in Europe and Argentina: Field study protocol for the SPRINT project.

Current farm systems rely on the use of Plant Protection Products (PPP) to secure high productivity and control threats to the quality of the crops. However, PPP use may have considerable impacts on human health and the environment. A study protocol is presented aiming to determine the occurrence and levels of PPP residues in plants (crops), animals (livestock), humans and other non-target species (ecosystem representatives) for exposure modelling and impact assessment. To achieve this, we designed a cross-sectional study to compare conventional and organic farm systems across Europe. Environmental and biological samples were/are being/will be collected during the 2021 growing season, at 10 case study sites in Europe covering a range of climate zones and crops. An additional study site in Argentina will inform the impact of PPP use on growing soybean which is an important European protein-source in animal feed. We will study the impact of PPP mixtures using an integrated risk assessment methodology. The fate of PPP in environmental media (soil, water and air) and in the homes of farmers will be monitored. This will be complemented by biomonitoring to estimate PPP uptake by humans and farm animals (cow, goat, sheep and chicken), and by collection of samples from non-target species (earthworms, fish, aquatic and terrestrial macroinvertebrates, bats, and farm cats). We will use data on PPP residues in environmental and biological matrices to estimate exposures by modelling. These exposure estimates together with health and toxicity data will be used to predict the impact of PPP use on environment, plant, animal and human health. The outcome of this study will then be integrated with socio-economic information leading to an overall assessment used to identify transition pathways towards more sustainable plant protection and inform decision makers, practitioners and other stakeholders regarding farming practices and land use policy.