Validation and Simultaneous Monitoring of 311 Pesticide Residues in Loamy Sand Agricultural Soils by LC-MS/MS and GC-MS/MS, Combined with QuEChERS-Based Extraction.

Soil can be contaminated by pesticide residues through agricultural practices, by direct application or through spray-drift in cultivations. The dissipation of those chemicals in the soil may pose risks to the environment and human health. A simple and sensitive multi-residue analytical method was optimized and validated for the simultaneous determination of 311 active substances of pesticides in agricultural soils. The method involves sample preparation with QuEChERS-based extraction, and determination of the analytes with a combination of GC-MS/MS and LC-MS/MS techniques. Calibration plots were linear for both detectors over the range of five concentration levels, using matrix-matched calibration standards. The obtained recoveries from fortified-soil samples ranged from 70 to 119% and from 72.6 to 119% for GC-MS/MS and LC-MS/MS, respectively, while precision values were <20% in all cases. As regards the matrix effect (ME), signal suppression was observed in the liquid chromatography (LC)-amenable compounds, which was further estimated to be negligible. The gas chromatography (GC)-amenable compounds showed enhancement in the chromatographic response estimated as medium or strong ME. The calibrated limit of quantification (LOQ) value was 0.01 µg g-1 dry weight for most of the analytes, while the corresponding calculated limit of determination (LOD) value was 0.003 µg g-1 d.w. The proposed method was subsequently applied to agricultural soils from Greece, and positive determinations were obtained, among which were non-authorized compounds. The results indicate that the developed multi-residue method is fit for the purpose of analyzing low levels of pesticides in soil, according to EU requirements.

Τemporal Variation in Pesticide Residues in Citrus Fruits from Chios, Greece, before and after the Development of an Integrated Pest Management Strategy (IPMS): A Five-Year Study (LIFE13 ENV GR/000414).

The temporal variation in pesticide residues in Kampos, of Chios Island, in Greece, was determined between June 2014 and October 2019. Monitoring of residues took place before and after the development of an Integrated Pest Management Strategy (IPMS) for the sustainable control of the Mediterranean fruit fly (medfly) based on mass trapping with the non-toxic and environmentally friendly attractant Biodelear. A total of 1252 samples of citrus fruits, collected from 12 experimental citrus orchards, were analyzed for the presence of 353 active substances and metabolites of pesticides. A modified QuEChERS method and sensitive chromatographic techniques were used. During preparatory monitoring for the project, the most frequently detected pesticides were the insecticides chlorpyrifos, deltamethrin and spirotetramat; the fungicides propamocarb, dimethomorph and mepanipyrim; and the synergist piperonyl butoxide. The implementation of the IPMS to address medfly resulted in a dramatic reduction in the pesticides detected in citrus fruits during confirmatory monitoring, with no detectable residues-which may cause serious problems to human health-in any of the samples analyzed at the end of the project, thus enhancing consumer safety.

Do pesticides promote or hinder sustainability in agriculture? The challenge of sustainable use of pesticides in modern agriculture.

Sustainable agriculture aims to meet the food needs of the growing world population while ensuring minimal impact on the environment and humans as well as productivity. Although pesticides represent the backbone of the agri-food sector in its endeavor to secure food production their application is perceived by many as an obstacle towards the achievement of sustainability; the main concerns are linked with their adverse effects on human health and the environment. Τhis review aims to present the status of chemical plant protection and provide insights into the use of pesticides within the context of sustainable agriculture. It mainly focuses on the strengthened legislation frameworks, which especially in the European Union and the United States of America ensure the placement in the market of pesticides with acceptable toxicological and environmental profiles without compromising crop production. Furthermore, the implementation of Integrated Pest Management principles plays a key role in the sustainable use of pesticides. The stringent regulatory requirements have resulted in the dramatic increase of the associated effort and costs in pesticide research and development (R&D) of improved products. Nevertheless, the investment of leading agrochemical companies in the R&D of new pesticides remains high. All the above set the ground for the sustainable use of pesticides in crop production while their successful application remains a challenge.

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.

Effect of wheat species (Triticum aestivum vs T. spelta), farming system (organic vs conventional) and flour type (wholegrain vs white) on composition of wheat flour - Results of a retail survey in the UK and Germany - 3. Pesticide residue content.

Wheat is a major component of the Northern European diet and contributes significantly to dietary pesticide exposure. Here we report results of a 2-year retail survey, which compared pesticide residues in organic and conventional, whole-grain and white, common and Spelt wheat flour brands available in the UK and Germany. Pesticide residues were detected significantly more frequently in conventional (87%) than organic (25%) flour samples. Chlormequat, a plant growth regulator, was the most frequently detected compound. Total concentrations of pesticide residues were (a) ~4 times higher in conventional than organic, (b) ~100% higher in common than Spelt wheat flour and (c) ~110% higher in conventional whole-grain than white flour samples, but (d) not significantly different in organic whole-grain and white flour. Results suggest that the use of organic wheat products allows increased whole-grain cereal consumption in line with nutritional recommendations, without an increase in dietary pesticide intake.

Fipronil in eggs. Is LC-MS/MS the only option? A comparison study of LC-MS/MS and GC-ECD for the analysis of fipronil.

Fipronil is a broad-spectrum insecticide belonging to the phenylpyrazole chemical family, classified by the U.S. EPA as a group C (possible human) carcinogen. It is highly toxic to crustaceans, insects and zooplankton as well as to termites, rabbits and certain groups of gallinaceous birds. In European Union and Greece, fipronil is authorized only for the control of termites and cockroaches and not as a plant protection product or as a veterinary drug. The definition of residue of fipronil comprises of the sum of fipronil and its sulfone metabolite expressed as fipronil and is set at 5 µg kg-1. In this study, a sensitive and reliable modified QuEChERS method, proposed by the European Reference Laboratory for animal origin products, has been validated and applied to the residue analysis of fipronil and its metabolites (sulfone and desulfinyl) in chicken eggs and other egg products by LC-MS/MS and GC-ECD analysis. The two analytical systems performed almost equally concerning validation process and with regard to the analysis of real samples, results from both systems were in agreement: out of 11 samples analysed, 4 samples showed measurable residues of fipronil sulfone with 3 samples exceeding the MRL limit.

Determination of Eight Sulfonylurea Herbicide Residues by LC/MS/MS Using a Sample Separation Technique with Ethyl Acetate.

Background: Sulfonylureas are an important group of systemic herbicides mainly used for the control of weeds in cereals and other crops in early growth stages of their cultivations. Sulfonylureas are characterized by their broad spectrum weed control and their good crop selectivity. Objective: In the present study, the determination of eight sulfonylureas has been tested in wheat flour by applying the SweEt multiresidue method modified for dry products. Method: The method involves sample preparation with extraction with ethyl acetate (EEA) and determination of the analytes with LC/MS/MS-electrospray ionization. Its performance was compared with the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. Both methods were validated in three fortification levels according to European Union requirements. Results: The proposed method gave acceptable results as far as validation criteria are concerned, while QuEChERS did not result in successful recoveries in the lowest validation level, which is equal to the respective maximum residue limits (MRLs). Conclusions: The obtained results showed that the tested method showed good separation, sensitivity, linearity, precision, and accuracy for quantitative and qualitative analysis of sulfonylurea herbicides in cereals at low levels, as required by legislation. The analytical techniques were successfully applied to different samples of cereals, and no residues were determined above the reporting limit, as established at the lowest concentration level of each analyte being validated with acceptable accuracy. Highlights: Low recoveries for QuEChERS in the concentrations equal to the MRL. Acceptable recoveries for the EEA method in all fortification levels. Correlation coefficients above 0.99. Positive findings only with EEA in real samples.

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.

Determination of benzoylurea insecticide residues in tomatoes by high-performance liquid chromatography with ultraviolet-diode array and atmospheric pressure chemical ionization-mass spectrometry detection.

A simple and sensitive method using high-performance liquid chromatography/ mass spectrometry (LC/MS) was developed and validated for simultaneous determination of 5 benzoylurea insecticides-diflubenzuron, triflumuron, teflubenzuron, lufenuron, and flufenoxuron-in tomatoes. Residues were successfully separated on a C18 column by methanol-water isocratic elution. Detection was carried out by an ultraviolet diode array detector (UV-DAD) coupled with a quadrupole mass spectrometer, using atmospheric pressure chemical ionization (APCI) in negative-ion mode. The main ions were the deprotonated molecules [M-H]- for triflumuron, and the anions formed by elimination of hydrofluoric acid [M-H-HF]- for diflubenzuron and flufenoxuron, and [M-2H-HF] for lufenuron and teflubenzuron. The calibration plots were linear for both detectors over the range 0.05 to 10 microg/mL, and the method presented good quality parameters. The limits of detection for standard solutions were 0.008-0.01 mg/L (equivalent to 0.08-0.1 ng injected) for both detectors, and the limits of quantification (LOQs) were approximately 10 times lower than national maximum residue levels (MRLs). Depending on the compound and the detector, the LOQ values ranged from 0.2 to 0.4 ng injected. The optimum LC-UV-DAD/APCI-MS conditions were applied to the analysis of benzoylureas in tomatoes. The obtained recoveries from fortified tomato samples (50 g), extracted with ethyl acetate and purified by solid-phase extraction on silica sorbent, were 88-100 and 92.9-105% for the UV-DAD and MS detectors, respectively, with precision values (relative standard deviations) of 2.9-11 and 3.7-14%, respectively. The method was applied to 12 tomato samples from local markets, and diflubenzuron and lufenuron were detected in only one sample at concentrations lower than the MRLs. The results indicate that the developed LC/MS method is accurate, precise, and sensitive for quantitative and qualitative analysis at low levels of benzoylureas required by legislation.