Airborne Pesticides Research Articles

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.

Airborne Pesticides-Deep Diving into Sampling and Analysis.

The escalating utilization of pesticides has led to pronounced environmental contamination, posing a significant threat to agroecosystems. The extensive and persistent global application of these chemicals has been linked to a spectrum of acute and chronic human health concerns. This review paper focuses on the concentrations of airborne pesticides in both indoor and outdoor environments. The collection of diverse pesticide compounds from the atmosphere is examined, with a particular emphasis on active and passive air sampling techniques. Furthermore, a critical evaluation is conducted on the methodologies employed for the extraction and subsequent quantification of airborne pesticides. This analysis takes into consideration the complexities involved in ensuring accurate measurements, highlighting the advancements and limitations of current practices. By synthesizing these aspects, this review aims to foster a more comprehensive and informed comprehension of the intricate dynamics related to the presence and measurement of airborne pesticides. This, in turn, is poised to significantly contribute to the refinement of environmental monitoring strategies and the augmentation of precise risk assessments.

Airborne Pesticides from Agricultural Practices: A Critical Review of Pathways, Influencing Factors, and Human Health Implications.

This critical review examines the release of pesticides from agricultural practices into the air, with a focus on volatilization, and the factors influencing their dispersion. The review delves into the effects of airborne pesticides on human health and their contribution to anthropogenic air pollution. It highlights the necessity of interdisciplinary research encompassing science, technology, public policy, and agricultural practices to effectively mitigate the risks associated with pesticide volatilization and spray dispersion. The text acknowledges the need for more research to understand the fate and transport of airborne pesticides, develop innovative application technologies, improve predictive modeling and risk assessment, and adopt sustainable pest management strategies. Robust policies and regulations, supported by education, training, research, and development, are crucial to ensuring the safe and sustainable use of pesticides for human health and the environment. By providing valuable insights, this review aids researchers and practitioners in devising effective and sustainable solutions for safeguarding human health and the environment from the hazards of airborne pesticides.

Use of PLE-ATD-GC/MSMS for the Quantification of Airborne Pesticides in Active and Passive Samples and in Dust.

An analytical method coupling pressurized liquid extraction (PLE), pre-concentration by thermal desorption (ATD) and analysis by GC/MSMS was developed for the quantification of pesticides in air and dust near vineyards crops to evaluate potential exposure of residents living near these crops. PLE was done using acetonitrile and extracts were concentrated under fume hood to 1mL. 100μL of the extract was spiked in a Tenax TA tube and internal standards and N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide were added before thermal desorption at 300°C for 30min. GC/MSMS analysis was done in MRM mode and limits of quantification and limits of detection were determined for each matrix (passive air sample, active air sample and dust). The method was applied in the field and shows good sensitivity and accuracy.

Exposure to Airborne Pesticides and Its Residue in Blood Serum of Paddy Farmers in Malaysia.

Background: Pesticides manage pests and diseases in agriculture, but they harm the health of agricultural workers. Concentrations of thirteen pesticides were determined in personal air and blood serum of 85 paddy farmers and 85 non-farmers, thereafter associated with health symptoms. Method: Samples were analyzed using ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). Results: The median concentration of pesticides in personal air samples ranged from 10.69 to 188.49 ng/m3 for farmers and from 5.79 to 73.66 ng/m3 for non-farmers. The median concentration of pesticides in blood serum was from 58.27 to 210.12 ng/mL for farmers and 47.83 to 62.74 ng/mL for non-farmers. Concentration of eleven pesticides in personal air and twelve pesticides in blood serum were significantly higher in farmers than non-farmers (p < 0.05). All pesticides detected in personal air correlated significantly with concentration in the blood serum of farmers (p < 0.05). Health symptoms reported by farmers were dizziness (49.4%), nausea (47.1%), cough (35.3%), chest pain (30.6%), breathing difficulty (23.5%), sore throat (22.4%), vomiting (18.8%), phlegm (16.5%), and wheezing (15.3%). Concentration of pesticides in personal air, blood serum, and health symptoms were not significantly associated. Conclusion: Occupational exposure to pesticides significantly contaminates blood serum of farmers compared to non-farmers.

Passive Sampling as a Tool to Assess Atmospheric Pesticide Contamination Related to Vineyard Land Use

The massive use of pesticides in agriculture has led to widespread contamination of the environment, particularly the atmospheric compartment. Thirty-six pesticides, most used in viticulture, were monitored in ambient air using polyurethane foams as passive air samplers (PUF-PAS). Spatiotemporal data were collected from the samplers for 10 months (February–December 2013), using two different sampling times (1 and 2 months) at two different sites in a chateau vineyard in Gironde (France). A high-volume active air sampler was also deployed in June. Samples were extracted with dichloromethane using accelerated solvent extraction (ASE) (PUFs from both passive and active) or microwave-assisted extraction (MAE) (filters from active sampling). Extracts were analyzed by both gas and liquid chromatography coupled with tandem mass spectrometry. A total of 23 airborne pesticides were detected at least once. Concentrations in PUF exposed one month ranged from below the limits of quantification (LOQs) to 23,481 ng PUF−1. The highest concentrations were for folpet, boscalid, chlorpyrifos-methyl, and metalaxyl-m—23,481, 17,615, 3931, and 3324 ng PUF−1. Clear seasonal trends were observed for most of the pesticides detected, the highest levels (in the ng m−3 range or the µg PUF−1 range) being measured during their application period. Impregnation levels at both sites were heterogeneous, but the same pesticides were involved. Sampling rates (Rs) were also estimated using a high-volume active air sampler and varied significantly from one pesticide to another. These results provide preliminary information on the seasonality of pesticide concentrations in vineyard areas and evidence for the effectiveness of PUF-PAS to monitor pesticides in ambient air.

Pesticides: Undisputed Hazards for Environmental Health

Airborne pesticides are now disseminated over vast regions of the planet even where they were not spilled, remotely from its preceding source. Their deleterious effects have been sensed overwhelmingly increasing all along with the shifts provoked in the nature, fauna, and flora derangements’, regardless from where they come from either disseminated by air or water sources. They will insidiously, gently, or harshly impact the living beings (target and non-target organisms). Their effects will certainly be massive for those exposed and, consequently, at danger of death, extinction, or damage (grow retardation, physiological or behavioural shortages), the most vulnerable and susceptible individuals or species being quenched. The endocrine deleterious responses to adults as compared to the embryonic/fetal/neonatal responses have been described. Changes in the hormonal system development are often irreversible, in contrast to reversible changes induced by the exposure to transient hormones in adults. The toxic effects start as the pesticides get into the lungs or in the equivalent blood-water/air exchanging system. In mammals, birds and reptiles breathed air entering through the noses touch the sinus cavities, it irritates their fragile membranes as, in response, may lead to an inflammation as it also can occur topically. In the pesticides risk assessment, hormesis can have significant practical impact, because this concept assumes the existence of limits for doses higher than the hormetic ones; and its acceptance would therefore erroneously lead to modification in the current practice of cancer risk assessment. Thus, long run health advance may succeed by replacing hazardous pesticides by sustainable biopesticides and along with other non-poisoning methods.

Personal exposure assessment of pesticides in residents: The association between hand wipes and urinary biomarkers

BackgroundResidential exposure to pesticides may occur via inhalation of airborne pesticides, direct skin contacts with pesticide-contaminated surfaces, and consumption of food containing pesticide residues. The aim was to study the association of dermal exposure to pesticides between the use and non-use periods, between farmer and non-farmer families and between dermal exposure and the excretion of metabolites from urine in residents living close to treated agricultural fields. MethodsIn total, 112 hand wipes and 206 spot urine samples were collected from 16 farmer and 38 non-farmer participants living within 50 m from an agricultural field in the Netherlands. The study took place from May 2016 to December 2017 during the use as well as the non-use periods of pesticides. Hand wipes were analysed for the parent compound and urines samples for the corresponding urinary metabolite of five applied pesticides: asulam, carbendazim (applied as thiophanate-methyl), chlorpropham, prochloraz and tebuconazole. Questionnaire data was used to study potential determinants of occurrence and levels of pesticides in hand wipes according to univariate and multivariate analysis. ResultsCarbendazim and tebuconazole concentrations in hand wipes were statistically significantly higher in the pesticide-use period compared to the non-use period. In addition, especially during the use periods, concentrations were statistically significantly higher in farmer families compared to non-farmer families. For asulam, chlorpropham and prochloraz, the frequency of non-detects was too high (57–85%) to be included in this analysis. The carbendazim contents in urine samples and hand wipes were correlated on the first and second day after taking the hand wipe, whereas chlorpropham was only observed to be related on the second day following the spray event. ConclusionsConcentrations in hand wipes were overall higher in pesticide use periods compared to non-use periods and higher in farmer families compared to non-farmer families. Only for carbendazim a strong correlation between concentrations in hand wipes and its main metabolite in urine was observed, indicating dermal exposure via contaminated indoor surfaces. We expect this to be related to the lower vapour pressure and longer environmental lifetime of carbendazim compared to the other pesticides studies.

Does polyacrylamide-based adjuvant actually reduce primary drift of airborne pesticides?

Atmospheric drift of pesticides sprayed outside treated fields may pose serious environmental and health concerns. Chemical adjuvants, among other techniques, reduce drift by modifying the physicochemical properties of the pesticide solution, which presumably produces larger droplets upon spraying that are less prone to drift. Previous studies, that have addressed the effect of adjuvants on drift reduction, mainly rely on measurements of droplet sedimentation while ignoring the presence of pesticides in the forms of small aerosols and vapor. Such forms are expected to be highly susceptible to atmospheric drift that may pose human health risk via inhalation exposure.The present study examines the effect of a polymer-based adjuvant on airborne-pesticide drift using active air sampling in two field campaigns. Surprisingly, these measurements indicate higher primary drift (PD) of airborne pesticides in the presence of adjuvant in the spraying solution. The results are further supported by comparing measured drifts to those calculated using a modified Gaussian puff dispersion model, which enabled to evaluate the impact of varying meteorological conditions during the field experiments. In addition, the adjuvant effect on droplet size distribution generated by common nozzles, was tested in a wind tunnel. The resulting size-distributions demonstrated that while the addition of adjuvant resulted in a desired shift of the volumetric distribution towards larger droplets, it also led to a significant increase in the number concentration of fine droplets. Such trends can explain how the addition of polymeric adjuvant can yield both, a reduction in sedimenting drift outside treated areas and an increase in airborne PD intensity, as observed in the present study. This study demonstrates the complex effect of chemical adjuvants and the urgent need to further explore and understand their environmental impact.

Comparison of the epiphyte Tillandsia bergeri and the XAD-resin based passive air sampler for monitoring airborne pesticides

The aim of this study was to assess if the epiphyte Tillandsia bergeri is feasible to be used as a biomonitor of pesticides in the air by comparing with the results of the artificial XAD-resin based passive air sampler (XAD-PAS). Biomonitors and XAD-PAS were deployed at 10 sites of Quequén Grande River watershed (Buenos Aires province, Argentina) during three exposure periods. Endosulfan was the main pesticide found in T. bergeri as well as in XAD-PAS, even after the ban was in effect. Higher endosulfan levels were observed during pesticide application period in XAD-PAS, while T. bergeri showed a decreasing trend during this period. Chlorpyrifos concentrations were in the same order than endosulfan in XAD-PAS, while T. bergeri showed significantly lower levels. Concentrations of legacy pesticides (hexachlorocyclohexanes, chlordanes, dieldrin, heptachlors) registered a low contribution to total pesticides analyzed both in T. bergeri and XAD-PAS, reflecting the past use of organochlorine pesticides in the region. Trifluralin showed the lowest concentrations in T. bergeri while XAD-PAS exhibited a higher proportion in some sites. Even both samplers showed that endosulfan was the most frequent pesticide found, environmental processes such as volatilization and photodegradation, as well as biological processes in T. bergeri have probably occurred and therefore pesticides accumulation was altered. Results demonstrate the importance of taking into account the type of sampling media when analyzing atmospheric pesticide composition. Nevertheless, the use of T. bergeri and XAD-PAS allowed discriminating efficiently the relative contribution of currently used pesticides versus legacy pesticides to air pollution.

Evaluation of sampling adsorbents and validation of a LC-HRMS method for determination of 28 airborne pesticides

A new strategy for sampling, using a low-volume sampler, and determination of airborne pesticides by liquid chromatography coupled to high-resolution mass spectrometry (UHPLC-HRMS) has been developed. The trapping efficiency of three adsorbents (sandwich PUF-XAD2-PUF; XAD-2 and XAD-4) was tested for 33 currently used pesticides and the first adsorbent (PUF-XAD2-PUF) was selected because it presented the highest retention capacity without breakthrough. Selected PUF-XAD2-PUF had the following design: 5 g of Amberlite XAD-2 sandwiched between two cylinders of PUF (6.87 cm3, height: 1.4 cm, diameter: 2.5 cm). A validation of the analytical methodology that includes microwave extraction with ethyl acetate, and determination by UHPLC-HRMS was employed. The method showed recoveries ranging from 75% to 120% with quantification limits in the range of 32.2–129.0 pg m−3 when 155 m3 were sampled. This analytical strategy was applied to 15 air samples collected in a rural area of Valencia Region (Spain). Ten polar pesticides, namely acetamiprid, carbendazim, carbofuran, imidacloprid, iprovalicarb, metalaxyl, myclobutanil, pirimicarb, pyrimethanil and terbuthylazine were detected in air samples with concentrations ranging from 411.16 pg m−3 (imidacloprid) to 11011.45 pg m−3 (pyrimethanil).

Strategies for reducing airborne pesticides under tropical conditions.

Brazil is currently one of the largest pesticide consumers worldwide. However, a lack of scientific information regarding airborne pollution is still an issue, with tragic consequences to human health and the environment. To reduce pollution of the lower air layers, where pesticide spraying occurs, green barriers that filter the air could be an effective mitigation procedure. Modifying pulverization habits, by pulverizing in the late afternoon instead of in the morning could also reduce pesticide volatilization, while other recommendations with the purpose of lowering the pesticide amounts currently applied are likewise pursued. Data obtained about volatilization have demonstrated that, in order to reduce air pollution risks, one of the most effective preventive strategies is to ban products with high vapor pressure. Global/local stakeholders need to assume the responsibility to find the best way to reduce airborne pesticide pollution, which has increasingly shown disastrous effects as major poisons to human health and the environment.

Selection of sampling adsorbents and optimisation and validation of a GC-MS/MS method for airborne pesticides

ABSTRACTA methodology for the sampling and determination of airborne pesticides has been developed. The trapping efficiency of three adsorbents, namely XAD-2,XAD-4 and a sandwich sorbent (PUF-XAD2-PUF), was tested for 34 pesticides and the latter was selected because it presented the highest retention capacity without breakthrough. Pesticides were determined by gas chromatography coupled to an ion trap mass spectrometer in tandem. The method showed recoveries ranging from 70% to 120% with limits of quantification in the range of 16.1–322.6 pg m−3 when 155 m3 were sampled. This analytical strategy was applied to 10 indoor air samples collected in dwellings from the Valencian Region. Six pesticides, namely diphenylamine, pyrimethanil, bifenthrin, lambda-cyhalothrin, permethrin and cypermethrin were detected in indoor samples with concentrations ranging from 1.46 to 22.02 ng m−3.

Comprehensive analysis of airborne pesticides using hard cap espresso extraction-liquid chromatography-high-resolution mass spectrometry

A hard cap espresso extraction procedure has been developed to recover airborne pesticides in particulate matter trapped in filters. This extraction step was made for 20s at 72°C and 19bar using 50mL of 20% (v/v) acetonitrile in water. After that, based on NaCl salting out, extracts were concentrated 22 times and analysed by ultra-high performance liquid chromatography – high resolution mass spectrometry. 35 pesticides were evaluated, as a proof of concept, being validated the whole methodology and compared the extraction method with that based on microwave assisted extraction for 20min. In short, the method avoids cross-contamination of samples, it is relatively fast and consumes only 10mL acetonitrile and 8g NaCl per sample; thus, offering a low cost and green alternatively to available methods based on pressurized solvent extraction or microwave-assisted treatment.

Primary and secondary pesticide drift profiles from a peach orchard

Atmospheric drift is considered a major loss path of pesticide from target areas, but there is still a large gap of knowledge regarding this complex phenomenon. Pesticide drift may occur during application (Primary drift) and after it (Secondary drift). The present study focuses on primary and secondary drift from ground applications in peach orchard (tree height of 3 m), under Mediterranean climate. Detailed and prolonged vertical drift profiles at close proximity to orchard are presented, together with detailed measurements of key meteorological parameters. The effect of volatility on drift was also studied by simultaneously applying two pesticides that differ in their volatility.Drifting airborne pesticides were detected both during and after applications at sampling distances of 7 and 20 m away from orchard edge. Concentrations ranged between hundreds ng m−3 to a few μg m−3 and showed clear decrease with time and with upwind conditions. Almost no decline in concentrations with height was observed up to thrice canopy height (i.e., 10 m). These homogeneous profiles indicate strong mixing near orchard and are in line with the unstable atmospheric conditions that prevailed during measurements. While air concentrations during pesticide application were higher than after it, overall pesticide load drifted from the orchard during primary and secondary drift are comparable.To the best of our knowledge this is the first work to show such large vertical dispersion and long duration of secondary drift following ground application in orchards. The obtained information indicates that secondary drift should not be neglected in exposure and environmental impact estimations.

Risk assessment of airborne pesticides in a Mediterranean region of Spain

A risk assessment strategy based on the quantitative target analysis and semi-quantitative retrospective screening determination of pesticides in PM10 has been developed. The proposed methodology was applied to 345 real samples from nine stations of a Mediterranean area in Spain, and the risk was assessed for adult, children and infants. Forty pesticides were detected with average concentrations ranging from 8 to 30,000pgm−3. Each station showed its specific pesticide profile, which is linked to the different types of crops around each station. For adults, children and infants the estimated chronic inhalation risk, expressed as Hazard Quotient (HQ), was <1 for all pesticides. The cumulative exposure for organophosphates, neonicotinoids, benzimidazoles, carbamates, micro-organism and triazoles pesticides (HI, Hazard Index) were <1 for the three groups of populations assessed. For infants, the cancer risk estimated for the detected pesticides classified as possible and potential carcinogens were lower than 1.0 E-06, except for carbendazim and hexythiazox.

Estimating drift of airborne pesticides during orchard spraying using active Open Path FTIR

The use of pesticides is important to ensure food security around the world. Unfortunately, exposure to pesticides is harmful to human health and the environment. This study suggests using active Open Path Fourier Transform Infra-Red (OP-FTIR) spectroscopy for monitoring and characterizing pesticide spray drift, which is one of the transfer mechanisms that lead to inhalation exposure to pesticides. Experiments were conducted in a research farm with two fungicides (Impulse and Bogiron), which were sprayed in the recommended concentration of ∼0.1%w in water, using a tractor-mounted air-assisted sprayer. The ability to detect and characterize the pesticide spray drift was tested in three types of environments: fallow field, young orchard, and mature orchard. During all spraying experiments the spectral signature of the organic phase of the pesticide solution was identified. Additionally, after estimating the droplets' size distribution using water sensitive papers, the OP-FTIR measurements enabled the estimation of the droplets load in the line of sight.

Utilization of long duration high-volume sampling coupled to SPME-GC-MS/MS for the assessment of airborne pesticides variability in an urban area (Strasbourg, France) during agricultural application

ABSTRACTAtmospheric samples have been collected between 14 March and 12 September 2012 on a 2-week basis (15 days of sampling and exchange of traps each 7 days) in Strasbourg (east of France) for the analysis of 43 pesticides. Samples (particle and gas phases) were separately extracted using Accelerated Solvent Extraction (ASE) and pre-concentrated by Solid Phase Micro-Extraction (SPME) before analysis by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). Four SPME consecutive injections at distinct temperatures were made in order to increase the sensitivity of detection for the all monitored pesticides. Currently used detected pesticides can be grouped in four classes; those used in maize crops (acetochlor, benoxacor, dicamba, s-metolachlor, pendimethalin, and bromoxynil), in cereal crops (benoxacor, chlorothalonil, fenpropimorph, and propiconazole), in vineyards (tebuconazole), and as herbicides for orchards, meadows of green spaces (2,4-MCPA, trichlopyr). This is in accordance with the diversity of crops found in the Alsace region and trends observed are in accordance with the period of application of these pesticides. Variations observed permit also to demonstrate that the long time sampling duration used in this study is efficient to visualize temporal variations of airborne pesticides concentrations. Then, long time high-volume sampling could be a simple method permitting atmospheric survey of atmospheric contamination without any long analysis time and consequently low cost.

Airborne organophosphate pesticides drift in Mediterranean climate: The importance of secondary drift

Abstract Pesticide application is a short-term air-pollution episode with near and far field effects due to atmospheric drift. In order to better evaluate resulting air concentrations in nearby communities following pesticide application, measurements of airborne pesticides were conducted at ∼70 m from field edge. This was done following three different application events of the organophosphate pesticide Chlorpyrifos in a persimmon orchard. Complementary information on larger spatial scale was obtained using CALPUFF modeling in which application and meteorological data was used to better evaluate dispersion patterns. Measurements indicated high airborne concentrations during application hours (few μg m −3 for 8 h average), which dropped to tens of ng m −3 in the following days. Measured atmospheric concentrations show that secondary drift (i.e., post-application drift) involves significant loads of pesticides and hence should not be ignored in exposure considerations. Furthermore, CALPUFF modeling revealed the complex dispersion pattern when weak winds prevailed, and showed that during the 24 h after application air concentrations reached levels above the hourly Texas effect screening level (0.1 μg m −3 ). Interestingly, weak winds on the night after application resulted in a secondary peak in measured and modeled air concentrations. Long exposure time (when secondary drift is considered) and concentrations measured following such common air-assisted orchard application, suggest pesticide drift may have health repercussions that are currently unknown, and emphasize the need for further epidemiological studies.

Combined target and post-run target strategy for a comprehensive analysis of pesticides in ambient air using liquid chromatography-Orbitrap high resolution mass spectrometry

A comprehensive strategy for the analysis of current airborne pesticides has been developed using liquid chromatography coupled to high resolution mass spectrometry. The methodology includes both quantitative target analysis and post-run target screening analysis. The quantitative method was validated after a previous statistical optimisation of the main factors governing the ion source ionization and a study of the single-stage Orbitrap fragmentation through the HCD cell. The quantitative method presented recoveries ranging from 73 to 116%, with precision (RSD) lower than 20%, for the 35 substances in the scope of the target method. The full-scan accurate mass data were acquired with a resolving power of 50000 FWHM (scan speed, 2Hz), and alternating two acquisition events, ESI+ without fragmentation and ESI+ with fragmentation. The method-LOQ was 6.5pgm−3 for most of the target pesticides. For post-target screening a customized theoretical database, that included pesticides, metabolites and other substances such as emerging flame retardants was built up. For identification, accurate exact mass with less than 5ppm, and some diagnostic ions including isotopes and/or fragments were used.The strategy was applied to ten samples collected in a rural area of Valencia (Spain). Four pesticides, namely carbendazim, metalaxyl, myclobutanil and terbuthylazine, were detected in concentrations from 16pgm−3 to 174pgm−3. Some pesticides and metabolites (endothal, fenfuram, terbuthylazine-2-OH), in addition to two flame retardants were tentatively identified in the post-run target screening analysis.