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. 2023 Aug 30;71(34):12657-12667.
doi: 10.1021/acs.jafc.3c02250. Epub 2023 Aug 16.

Analysis of Pesticide Levels in Honey and Pollen from Irish Honey Bee Colonies Using a Modified Dutch Mini-Luke Method with Gas and Liquid Chromatography-Tandem Mass Spectrometry Detection

Marcela A Díaz  1 , Darren P O'Connell  1 , Seana Jordan  2 , Catriona O'Connor  2 , Paul Martin  2 , Julia C Jones  1 , Jim Garvey  2
Affiliations

Analysis of Pesticide Levels in Honey and Pollen from Irish Honey Bee Colonies Using a Modified Dutch Mini-Luke Method with Gas and Liquid Chromatography-Tandem Mass Spectrometry Detection

Marcela A Díaz et al. J Agric Food Chem. .

Abstract

Determining the levels of agrochemicals, such as pesticides, that honey bees are exposed to is critical for understanding what stress factors may be contributing to colony declines. Although several pesticide detection methods are available for honey, limited work has been conducted to adapt these methods for pollen. Here, we address this gap by modifying the Dutch mini-Luke extraction method (NL method) for pesticide analysis in honey and pollen from throughout the island of Ireland. The NL method was modified to enable detection in small-sized samples and validated for both pollen and honey matrices. The modified NL method combined with liquid and gas chromatography-tandem mass spectrometry gave consistent results in terms of accuracy and precision measured by recovery experiments and was successfully applied in the analysis of a range of pesticide residues. The modified NL method developed here provides a key tool for detecting pesticides in honey bee colony resources and the environment more broadly.

Keywords: Dutch mini-Luke extraction; GC-MS/MS; UHPLC-MS; honey; honey bee; pesticide detection; pollen.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Chromatogram of propargite detected in honey. The chromatogram exhibits two pairs of transitions (T), T1 (left):135.1 → 107.1 m/z and T2 (right): 135.1 → 77.0 m/z. The retention time for propargite was set at 27.692 min. The ratio of the two transitions observed in the sample (top pair) falls within the acceptable tolerance range, and both, the parent and product ion peak shape, resemble those presented by the calibration standard (bottom pair) at the second level (20 μg/kg). This confirms the presence of the compound propargite in the sample.
Figure 2
Figure 2
Recovery data for 180 pesticides analyzed by GC-MS/MS and 166 compounds analyzed by UHPLC-MS. Two different concentration levels were evaluated: 10 μg/kg (*) and 100 μg/kg (**). The abbreviations GC and LC represent GC-MS/MS and UHPLC-MS, respectively. The ESI operating mode is shown as ESI+ for positive mode, and ESI– for negative mode. The data is presented as a percentage of compounds per percentage of recovery, categorized into six ranges from <60 to >140%.
Figure 3
Figure 3
Effect of the matrices, honey and pollen, on the signal response of 180 pesticides analyzed by GC-MS/MS. The data is presented as a percentage of compounds per percentage within each percentage range of matrix effect, categorized into six ranges from < −20 to >20%.
Figure 4
Figure 4
Percentage of positive samples of pollen and honey collected across the island of Ireland.
See this image and copyright information in PMC

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