Residue behavior of etoxazole under field conditions in Egypt and estimation of processing factors during the production of strawberry juice and purée.

The degradation under field conditions and the residue behavior of etoxazole during juicing and purée making was evaluated. Etoxazole residues were determined by HPLC-UV at six different Pre Harvest Intervals (PHIs) as to estimate the degradation of residue in fruits. Samples with significant residues were processed and residue were determined after juicing and purée making. The effect of washing was also estimated. Processing Factors (PFs) for etoxazole after each step were less than 1 and the PFs of the overall processes were lower than 0.85 for washing fruits, 0.13 for juice and 0.04 for purée. The studied processes could obviously reduce the pesticide residues that are present in the raw strawberries. Uncertainties in the use of the PFs were identified due to the potential formation of metabolites during the processes.

Development and validation of a new method for the simultaneous determination of PAHs and NDL-PCBs in fish by GC-SQ-MS.

A new method for the simultaneous determination of PAHs and NDL-PCBs in fish and fish products was developed and validated using a GC-SQ-MS system. The efficacy of different solvents for a quantitative extraction was studied, as was the efficacy of different sorbents for sample clean up. The developed method, which includes extraction by DCM and sample clean up by SPE using Isolute® SI cartridges, was statistically validated at two concentration levels by assessing: accuracy, precision, limit of quantification, limit of detection and matrix effect. The method was used for analysing fresh, frozen and smoked fish products from the Greek retail market. None of the samples examined showed results above the maximum limits set by EU regulations.

Residue, dissipation, and dietary intake evaluation of fenpyroximate acaricide in/on guava, orange, and eggplant under open field condition.

Fenpyroximate is a widely used acaricide applicable in many crops. In this study, the residue behavior of fenpyroximate on eggplant, orange, and guava was investigated. The chronic and acute dietary intake was calculated at several sampling points, and preharvest intervals (PHI) were proposed to ensure compliance with the existing maximum residue levels. A simple extraction protocol combined with ultrahigh-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was employed to quantify residue levels. The method was successfully validated according to the European Union (EU) guidelines, and a limit of quantification of 0.01 mg/kg was set. The dissipation patterns in all crops could be described by the first-order kinetics model with half-lives of 1.7, 2.2, and 1.9 days for eggplants, guavas, and oranges, respectively. The dietary risk assessment at the authorized or more critical application patterns was acceptable for the consumers. For oranges and eggplant, a PHI of 3 and 7 days, respectively, can be proposed; however, a proposal was not possible for guava due to the absence of maximum residue limits (MRLs) and quantitative residue findings at all sampling points tested. The current work not only contributes to the practical application of fenpyroximate related to residue management in dryland areas, such as Egypt, but can also be used to estimate the appropriate PHIs and support the authorization of plant protection products as supplementary information.

Retrospective cumulative dietary risk assessment of craniofacial alterations by residues of pesticides.

EFSA established cumulative assessment groups and conducted retrospective cumulative risk assessments for two types of craniofacial alterations (alterations due to abnormal skeletal development, head soft tissue alterations and brain neural tube defects) for 14 European populations of women in childbearing age. Cumulative acute exposure calculations were performed by probabilistic modelling using monitoring data collected by Member States in 2017, 2018 and 2019. A rigorous uncertainty analysis was performed using expert knowledge elicitation. Considering all sources of uncertainty, their dependencies and differences between populations, it was concluded with varying degrees of certainty that the MOET resulting from cumulative exposure is above 100 for the two types of craniofacial alterations. The threshold for regulatory consideration established by risk managers is therefore not exceeded. Considering the severity of the effects under consideration, it was also assessed whether the MOET is above 500. This was the case with varying levels of certainty for the head soft tissue alterations and brain neural tube defects. However, for the alterations due to abnormal skeletal development, it was found about as likely as not that the MOET is above 500 in most populations. For two populations, it was even found more likely that the MOET is below 500. These results were discussed in the light of the conservatism of the methodological approach.

Dissipation behavior and dietary risk assessment of pyridaben in open field strawberries and cucumber under Egyptian cultivation conditions.

Pyridaben, an inhibitor of mitochondrial electron transport at complex I, is authorized in Egypt as an insecticide/acaricide for strawberries and cucumbers; thus the investigation of residues in the final consumed product is essential as to ensure consumer safety and trade barriers. Therefore, residue trials were conducted according to the in force and more critical Good Agricultural Practices (GAPs) as to investigate the dissipation rate of the compound on both crops and the terminal residues in the final products. Results showed that the residue decline fits a first-order decay process with calculated half-lives of 1 and 6.4 days for cucumbers and strawberries, respectively. Dietary risk assessment was performed based on the risk quotients (RQ) method and the EFSA PRIMo model demonstrating that the dietary exposure to pyridaben residues from cucumber and strawberry consumption, applied either according to the in force or more critical GAPs, does not pose unacceptable health risk to Egyptian and European consumers.

Dissipation behavior of thiophanate-methyl in strawberry under open field condition in Egypt and consumer risk assessment.

Thiophanate methyl is a broad-spectrum benzimidazole fungicide extensively applied in pre- and post-harvest, for the control of a wide range of fruit and vegetable pathogens. In the current work, the residue behavior of thiophanate methyl after application on strawberries and an estimation of the consumer dietary exposure was performed. Supervised field trials were conducted in Egypt (Qaluobiya Governorate) as to investigate the residue dynamics and terminal residues at different PHIs of thiophanate methyl and its metabolite carbendazim in strawberries under Egyptian conditions. For the measurement of residues in fruits, a QuEChERS-based protocol coupled with LC-MS/MS was optimized and successfully validated at 0.01 mg kg-1. The half-life (t1/2) of thiophanate methyl in strawberries was estimated, and a dietary risk assessment was performed employing both FAO/WHO and EFSA approaches.

Investigation of the dissipation behaviour and exposure of spitotetramat, flonicamid, imidacloprid and pymetrozine in open field strawberries in Egypt.

The dissipation behaviour and the consumer risk assessment of spitotetramat, flonicamid, imidacloprid and pymetrozine in open field strawberries were studied. Insecticides were applied at the authorised levels and the more critical good agricultural practice regimes (GAP). The initial concentrations varied from 0.069 to 1.75 mg kg-1 depending on the compound, while the dissipation half-lives and terminal residues, 14 days from the last applications, were similar. After application according to the authorised pattern the half-lives were 2.8 days for flonicamid and 3.2 days for spitotetramat, imidacloprid and pymetrozine. The dietary risk assessment, performed using the hazard quotient and the EFSA PRIMo model showed no concern to consumer health with exposure values <2% of the acceptable daily intake (ADI) and <32% of the acute reference dose (ARfD) of each compound.

Magnitude of picoxystrobin residues in strawberry under Egyptian conditions: dissipation pattern and consumer risk assessment.

Picoxystrobin is a synthetic strobilurin fungicide widely used in Egypt to control downy and powdery mildews, a risk that is significant also in cultivating strawberries. In the ccurrent work, the safety to consumers from the use of picoxystrobin in strawberries along with its residue behaviour was studied. Supervised field trials were conducted to investigate the residue dynamics and terminal residues of picoxystrobin in strawberries under Egyptian conditions for several agricultural practices including worst-case scenarios. For the measurement of residues in fruit, a QuEChERS-based protocol coupled with LC-MS/MS was employed and successfully validated at 0.001 mg kg-1. A decline of picoxystrobin residues in fruit fitted a first-order decay process with a calculated t1/2 of 5.4 days with a significant degradation (79%) after 14 days. A consumer risk assessment was performed employing both FAO/WHO and EFSA approaches, in which no significant health risks after consumption of strawberries were identified.

A Pesticide Residues Insight on Honeybees, Bumblebees and Olive Oil after Pesticidal Applications against the Olive Fruit Fly Bactrocera oleae (Diptera: Tephritidae).

In 2017 and 2018, a field survey was initiated on Greek olive orchards to investigate the attractiveness of bait spray applications and the impact of cover and bait sprays applied against the olive fruit fly Bactrocera oleae (Diptera: Tephritidae), on the honeybee, Apis mellifera L. and bumblebees Bombus terrestris, by investigating the pesticides' residual prevalence. Bee colonies were evenly distributed in three sites located on coastal areas of Western Crete and visited almost weekly between July and October. Samples collected, were analyzed using existing or developed-optimized liquid and gas chromatographic methods. In bee samples, concentrations varied from 0.0013 to 2.3 mg/kg for dimethoate, from 0.0013-0.059 mg/kg for its metabolite omethoate, and from 0.0035 to 0.63 mg/kg regarding the pyrethroids, ß-cyfluthrin and λ-cyhalothrin. In one bee sample dimethoate concentration exceeded both acute oral and contact median lethal dose (LD50). Residue findings in bees, along with verified olive oil residues corroborated that those insecticides had been applied in the olive orchards and transferred to bees. The possibility of non-target effects of the bait sprays to the bees, as well as the impact of the contaminated olive to the bees are discussed.

Cumulative dietary risk assessment overarching different regulatory silos using a margin of exposure approach: A case study with three chemical silos.

Risk assessment of chemicals occurring in our diet is commonly performed for single chemicals without considering exposure to other chemicals. We performed a case study on risk assessment of combined dietary exposure to chemicals from different regulatory silos, i.e. pesticides (PPRs), persistent organic pollutants (POPs) and food additives (FAs). Chemicals were grouped into the cumulative assessment group (CAG) liver steatosis using a component-based approach. Based on literature, the CAG included 144 PPRs, 49 POPS and 7 FAs for which concentration data were available. For each silo, chronic combined dietary exposure was assessed for adults and children of nine European countries following the most commonly used exposure methodologies in Europe and by using a relative potency factor approach. For risk characterization, a Margin of Exposure (MOE) was calculated. To overarch the risk across silos, a normalised combined margin of exposure (nMOET) approach was proposed. This case study demonstrated that risk assessment of combined exposure to chemicals can be performed within regulatory silos. It also highlighted important differences in the conservatism of exposure scenarios, the derivation of point of departures and the subsequent acceptable MOEs between the silos. To overarch the risk despite these differences, a nMOET approach can be used.

Selecting mixtures on the basis of dietary exposure and hazard data: application to pesticide exposure in the European population in relation to steatosis.

Populations are exposed to mixtures of pesticides through their diet on a daily basis. The question of which substances should be assessed together remains a major challenge due to the complexity of the mixtures. In addition, the associated risk is difficult to characterise. The EuroMix project (European Test and Risk Assessment Strategies for Mixtures) has developed a strategy for mixture risk assessment. In particular, it has proposed a methodology that combines exposures and hazard information to identify relevant mixtures of chemicals belonging to any cumulative assessment group (CAG) to which the European population is exposed via food. For the purposes of this study, food consumption and pesticide residue data in food and drinking water were obtained from national surveys in nine European countries. Mixtures of pesticides were identified by a sparse non-negative matrix underestimation (SNMU) applied to the specific liver steatosis effect in children from 11 to 15 years of age, and in adults from 18 to 64 years of age in nine European countries. Exposures and mixtures of 144 pesticides were evaluated through four different scenarios: (1) chronic exposure with a merged concentration dataset in the adult population, (2) chronic exposure with country-specific concentration datasets in the adult population, (3) acute exposure with a merged concentration dataset in the adult population, and (4) chronic exposure with a merged concentration dataset in the paediatric population. The relative potency factors of each substance were calculated to express their potency relative to flusilazole, which was chosen as the reference compound. The selection of mixtures and the evaluation of exposures for each country were carried out using the Monte Carlo Risk Assessment (MCRA) software. Concerning chronic exposure, one mixture explained the largest proportion of the total variance for each country, while in acute exposure, several mixtures were often involved. The results showed that there were 15 main pesticides in the mixtures, with a high contribution of imazalil and dithiocarbamate. Since the concentrations provided by the different countries were merged in the scenario using merged concentration data, differences between countries result from differences in food consumption behaviours. These results support the approach that using merged concentration data to estimate exposures in Europe seems to be realistic, as foods are traded across European borders. The originality of the proposed approach was to start from a CAG and to integrate information from combined exposures to identify a refined list of mixtures with fewer components. As this approach was sensitive to the input data and required significant resources, efforts should continue regarding data collection and harmonisation among the different aspects within the pesticides regulatory framework, and to develop methods to group substances and mixtures to characterise the risk.

Residual degradation and toxicity of insecticides against Bactrocera oleae.

Field and lab trials took place in Crete (July to September 2016), concerning the residual degradation and toxicity of seven active ingredients applied as bait sprays against the olive fruit fly. Highest residues were recorded in olive leaves for dimethoate and phosmet (~ 60 mg/kg) immediately after application (day 1+), while a threefold and fivefold reduction was observed 1 week later, respectively. Residues of pyrethroids were determined at lower levels (< 10 mg/kg) but remained almost stable for a longer period of time. Finally, thiacloprid and spinosad residues were determined at 5.81 and 0.19 mg/kg respectively (day 1+), and rapidly decreased below the LOQ. Highest toxicity against the olive fruit fly was observed just right after the application of dimethoate (100%), a-cypermethrin (80%), and L-cyhalothrin (72.92%). Although the toxicity of dimethoate was significantly reduced 1 week after the application (80%) and then minimized, toxicity of pyrethroids remained almost stable (> 60%) for the first 2 weeks and then decreased to 30-40%, which remained stable up to the end of the study (8 weeks). Concerning phosmet, its toxicity ranged from 35 to 56% for 3 weeks with no significant reduction, while spinosad presented a lower toxicity profile (50% only for 1 week). The benefits of these results in the knowledge of insecticide residues and their toxicity against olive fruit fly can be used for improving olive fruit fly control.

Pesticide residues in honeybees, honey and bee pollen by LC-MS/MS screening: reported death incidents in honeybees.

The aim of this study was to investigate reported cases of honeybee death incidents with regard to the potential interrelation to the exposure to pesticides. Thus honeybee, bee pollen and honey samples from different areas of Greece were analyzed for the presence of pesticide residues. In this context an LC-ESI-MS/MS multiresidue method of total 115 analytes of different chemical classes such as neonicotinoids, organophosphates, triazoles, carbamates, dicarboximides and dinitroanilines in honeybee bodies, honey and bee pollen was developed and validated. The method presents good linearity over the ranges assayed with correlation coefficient values r(2)≥0.99, recoveries ranging for all matrices from 59 to 117% and precision (RSD%) values ranging from 4 to 27%. LOD and LOQ values ranged - for honeybees, honey and bee pollen - from 0.03 to 23.3 ng/g matrix weight and 0.1 up to 78 ng/g matrix weight, respectively. Therefore this method is sufficient to act as a monitoring tool for the determination of pesticide residues in cases of suspected honeybee poisoning incidents. From the analysis of the samples the presence of 14 active substances was observed in all matrices with concentrations ranging for honeybees from 0.3 to 81.5 ng/g, for bee pollen from 6.1 to 1273 ng/g and for honey one sample was positive to carbendazim at 1.6 ng/g. The latter confirmed the presence of such type of compounds in honeybee body and apicultural products.