One sampler to see it all: The use of APIStrips for beehive characterization and pesticide residue evaluation based on mass spectrometry

Abstract

Environmental monitoring is crucial for assessing the overall state of the ecosystems in terms of contaminant impact and chemical landscape. The use of honey bee (Apis mellifera) colonies considerably eases the sampling activities, as honey bees are exposed to a wide range of substances that are transported and accumulated within the beehives. In this work, combining low-resolution and high-resolution mass spectrometry, the APIStrip passive sampler has been employed to evaluate the presence of pesticide residues and the overall characterization of beehive environments. A total of 180 APIStrips have been deployed in 10 Danish apiaries, located in different landscapes, during a five-month sampling period. The targeted methodology for pesticide analysis was based on gas and liquid chromatography coupled with triple quadrupole mass spectrometry, covering 430 pesticide residues. A total of 29 pesticide residues were identified (fluopyram and azoxystrobin being the most frequently detected), with remarkable differences in the pesticide load between apiaries. For its part, the use of non-targeted approaches through liquid chromatography coupled with an Orbitrap mass spectrometer allowed the detection of unknown compounds that were specific of certain environments. Natural products such as eupatilin and gnaphaliin, which are derived from plant sources, were present exclusively in one of the apiaries. Additionally, the detection of drimane sesquiterpenoids, including compounds potentially originating from the Aspergillus genus, suggests the capability of APIStrips to early detect fungal contamination within beehives. This dual approach of low- and high-resolution mass spectrometry maximizes the analytical potential of APIStrips as a tool capable of detecting a wide range of substances with implications for both agricultural practices and ecological health.