Bees and systemic insecticides (imidacloprid, fipronil) in pollen: subnano-quantification by HPLC/MS/MS and GC/MS

Environmental Fate and Ecological Effects of Pesticides 05/2007;
Source: OAI


Imidacloprid and fipronil are two insecticides acting on the central nervous system. They are used worldwide, from the mid nineties, especially for seed coating of crops. Concomitantly to their introduction and their increasing use in French fields, honeybee populations decreased. Bee problems are nowadays reported in other countries (also called disappearing disease, desplobación de las colmenas, trouble des abeilles, deperimento degli apiari or colony collapse disorder). Bee problems have certainly several origins. Contamination of pollen and nectar by such chemicals appeared as one of the most probable cause, since subletal effects and chronic intoxications were observed on bees, at very low concentrations. We developed fully validated methods to measure contamination in pollen (sunflower and maize) for imidacloprid (HPLC/MS/MS) and for fipronil and 3 of its derivatives (GC/MS). For imidacloprid LOD and LOQ are 0.3 and 1 ng/g, respectively. For fipronil and each derivative (fiprole), LOD and LOQ are 0.07 and 0.2 ng/g, respectively. The averaged level of imidacloprid in pollen was 2-3 ng/g, which is 20-30 times higher than the concentration inducing significant mortality by chronic intoxication. Fiproles were detected in 48% of pollens issuing from treated crops. Fipronil and its sulfone derivative represented 77% and 17% of contaminants, respectively. The averaged fiprole sum Σf was 0.3 - 0.4 ng/g, which is 30-40 times higher than the concentration inducing significant mortality of bees by chronic intoxication.

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    • "Based on the average mass of honey bee workers of 90 mg, concentrations in individual bees were calculated (Moritz and Southwick, 1992). The mean concentration of clothianidin for samples in which it was detected, 2.5 ng bee À1 was near the estimated LD 50 2.5 and 3.5 ng bee À1 , estimated by Bonmatin et al (2007) and Kamel (2010), respectively, but less than LD 50 s estimated by others (SI Table 4). For all other untransformed, NIs detected, concentrations found in bees were orders of magnitude less than LD 50 s (Table 2, SI Table 4). "
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    ABSTRACT: Neonicotinoid insecticides (NIs) and their transformation products were detected in honey, pollen and honey bees, (Apis mellifera) from hives located within 30 km of the City of Saskatoon, Saskatchewan, Canada. Clothianidin and thiamethoxam were the most frequently detected NIs, found in 68 and 75% of honey samples at mean concentrations of 8.2 and 17.2 ng g(-1) wet mass, (wm), respectively. Clothianidin was also found in >50% of samples of bees and pollen. Concentrations of clothianidin in bees exceed the LD50 in 2 of 28 samples, while for other NIs concentrations were typically 10-100-fold less than the oral LD50. Imidaclorpid was detected in ∼30% of samples of honey, but only 5% of pollen and concentrations were <LOD in bees. Transformation products of Imidaclorpid, imidaclorpid-Olefin and imidacloprid-5-Hydroxy were detected with greater frequency and at greater mean concentrations indicating a need for more focus on potential effects of these transformation products than the untransformed, active ingredient NIs. Results of an assessment of the potential dietary uptake of NIs from honey and pollen by bees over winter, during which worker bees live longer than in summer, suggested that, in some hives, consumption of honey and pollen during over-wintering might have adverse effects on bees.
    Chemosphere 02/2016; 144:2321-2328. DOI:10.1016/j.chemosphere.2015.10.135 · 3.34 Impact Factor
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    ABSTRACT: This review has brought some light on the direct, sublethal and indirect effects that systemic insecticides have on species populations and ecosystems. Some long-term impacts have been known for some time (e.g. carbofuran, phorate), but it is the rapid increase in the usage of neonicotinoids and other systemic products that poses a new challenge to the ecological risk assessment of agrochemicals. Indeed, current risk protocols, based on acute, short-term toxic affects are inadequate to cope with the chronic exposure and cumulative, delayed impacts of the new compounds. Awareness of the increasing contamination of the environment with active residues of these chemicals should help regulators and managers to implement new approaches for risk assessment of these substances.
    Insecticides - Development of Safer and More Effective Technologies, Edited by Stanislav Trdan, 01/2013: pages 365-414; InTech Open Science., ISBN: 980-953-307-514-8


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