Neonicotinoid contamination in wildflowers collected from citrus orchards in a northwestern Mediterranean Region (Spain) after tree foliar treatments.

Ground-cover vegetation attracts and harbors beneficial insects to the agrosystem, playing an important role in conservation biological control. Integrated pest management (IPM) program guidelines recommend the implantation of sowed or resident wild covers in perennial crops. Given the high-quality fruit requirements, even in IPM programs, insecticides can be required in citrus crops. This study presents, over a year, the levels of neonicotinoids (thiamethoxam and imidacloprid) in not-target ground-cover wildflowers growing spontaneously in citrus orchards after foliar treatment of citrus trees. The presence and persistence of these neonicotinoids in different wildflower species were studied. Concentrations of thiamethoxam and imidacloprid in whole wildflowers ranged from < method quantification limit (MQL) to 52.9 ng g-1 and from < MQL to 98.6 ng g-1, respectively. Thiamethoxam was more frequently detected than imidacloprid. Thiamethoxam and imidacloprid were detected up to 336 and 230 days after treatment, respectively. The highest detection frequencies (100%) and highest thiamethoxam and imidacloprid mean concentrations (26.0 ± 7.3 ng g-1 and 11.0 ± 10.6 ng g-1, respectively) occurred in wildflowers collected 9 days after the treatments. Since application, a clear decrease in the concentration of both compounds and differences in the accumulation depending on wildflower species were observed. Cross contamination was detected, indicating a transport from adjacent treated plots. Maintaining a cover crop in citrus orchards may lead to detrimental effects on non-target arthropods if these neonicotinoid compounds are used for pest control since they can entail a chronic exposure during at least 230 days for imidacloprid and 336 days for thiamethoxam.

Evaluation of Residue Levels of Imidacloprid and Thiamethoxam After Foliar Application to the Citrus Varieties Lane Late, Valencia Late, Rohde Summer, and Nules.

Neonicotinoids are used to protect citrus trees against pests. Dissipation and persistence of neonicotinoids in pollen and nectar of citrus trees after foliar applications and their potential exposure to pollinators have not been well characterized. Field studies were conducted using three orange and one mandarin varieties to compare the imidacloprid and thiamethoxam residue levels and their decline in pollen and nectar after treatments in pre-bloom close to flowering period and their persistence 1 yr after treatment. The possible risk to honeybees was assessed. In nectar, thiamethoxam and imidacloprid residues were between 61 and 99% lower than in pollen, depending on the citrus variety or/and the days after treatment when applied close to blooming. At the end of the flowering period, imidacloprid in pollen and nectar was not detected in the mandarin variety after treatment in pre-bloom, whereas for thiamethoxam, no residues were detected in nectar but 10 ng/g was detected in pollen. There were no quantifiable levels of residues for either neonicotinoids in pollen or nectar during the flowering period of the following year. Neonicotinoid residue levels and their decline in nectar and pollen in citrus depended on the timing of applications relative to flowering and on the citrus variety. The absence of neonicotinoid residues 1 yr out after foliar applications in all varieties assayed demonstrated that none of the neonicotinoids tested were persistent. The results could be different in other citrus varieties, and therefore, also the exposure assessment for managed pollinators.

Analysis of pesticide residues in honeybee (Apis mellifera L.) and in corbicular pollen. Exposure in citrus orchard with an integrated pest management system.

In the last years, the honeybee population is facing growing threats such as expansion of pathogens, incorrect use of phytosanitary products and environmental contaminants, loss or fragmentation of habitat, invasive species and climate change. The citrus cropping by Integrated Pest Management (IPM) in Spain combines strategies to reduce pest populations preventing environmental problems and reducing levels of damage by using chemicals only when it is strictly necessary. The goal of this study is to develop a simple analytical method to evaluate pesticide residue levels in honeybees and corbicular pollen when honeybees are exposed to plant protection products (PPPs) used in integrated pest management citrus orchards. The proposed method is based in an ultrasound assisted extraction procedure followed by a dispersive solid phase extraction (d-SPE) clean-up with alumina and LC-MS/MS pesticides determination. The method was validated in samples of honeybee and corbicular pollen for 10 pesticides commonly used in citrus orchards under IPM. This procedure was compared with QuEChERS methodologies for these matrices. The developed method was applied to determine pesticides in both matrices in a two -year study in citrus orchards.

Microflow liquid chromatography coupled to mass spectrometry--an approach to significantly increase sensitivity, decrease matrix effects, and reduce organic solvent usage in pesticide residue analysis.

This manuscript reports a new pesticide residue analysis method employing a microflow-liquid chromatography system coupled to a triple quadrupole mass spectrometer (microflow-LC-ESI-QqQ-MS). This uses an electrospray ionization source with a narrow tip emitter to generate smaller droplets. A validation study was undertaken to establish performance characteristics for this new approach on 90 pesticide residues, including their degradation products, in three commodities (tomato, pepper, and orange). The significant benefits of the microflow-LC-MS/MS-based method were a high sensitivity gain and a notable reduction in matrix effects delivered by a dilution of the sample (up to 30-fold); this is as a result of competition reduction between the matrix compounds and analytes for charge during ionization. Overall robustness and a capability to withstand long analytical runs using the microflow-LC-MS system have been demonstrated (for 100 consecutive injections without any maintenance being required). Quality controls based on the results of internal standards added at the samples' extraction, dilution, and injection steps were also satisfactory. The LOQ values were mostly 5 µg kg(-1) for almost all pesticide residues. Other benefits were a substantial reduction in solvent usage and waste disposal as well as a decrease in the run-time. The method was successfully applied in the routine analysis of 50 fruit and vegetable samples labeled as organically produced.