Abstract

Anticoagulant rodenticides (ARs) have been used for decades for rodent control worldwide. Research on the exposure of the environment and accumulation of these active substances in biota has been focused on terrestrial food webs, but few data are available on the impact of ARs on aquatic systems and water organisms. To fill this gap, we analyzed liver samples of bream (Abramis brama) and co-located suspended particulate matter (SPM) from the German Environmental Specimen Bank (ESB). An appropriate method was developed for the determination of eight different ARs, including first- and second-generation ARs, in fish liver and SPM. Applying this method to bream liver samples from 17 and 18 sampling locations of the years 2011 and 2015, respectively, five ARs were found at levels above limits of quantifications (LOQs, 0.2 to 2 μg kg−1). For 2015, brodifacoum was detected in 88% of the samples with a maximum concentration of 12.5 μg kg−1. Moreover, difenacoum, bromadiolone, difethialone, and flocoumafen were detected in some samples above LOQ. In contrast, no first generation AR was detected in the ESB samples. In SPM, only bromadiolone could be detected in 56% of the samples at levels up to 9.24 μg kg−1. A temporal trend analysis of bream liver from two sampling locations over a period of up to 23 years revealed a significant trend for brodifacoum at one of the sampling locations.

Highlights

  • Since the introduction of warfarin as the first anticoagulant rodenticide on the US market in the late 1940s, rodent control worldwide has relied increasingly upon the use of these chemicals

  • We the applied this method in a spatial monitoring study for two time points for fish liver and one for suspended particulate matter (SPM) samples of the German Environmental Specimen Bank (ESB)

  • In order to optimize and merge available methods, and to secure the specificity of the method, the rodenticide analysis was performed on a UHPLC-chromatographic unit coupled to a high-resolution mass spectrometer operating at a resolution of 35,000

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Summary

Introduction

Since the introduction of warfarin as the first anticoagulant rodenticide on the US market in the late 1940s, rodent control worldwide has relied increasingly upon the use of these chemicals. Under the BPR, the approval of eight anticoagulants, i.e., warfarin, chlorophacinone, coumatetralyl, bromadiolone, difenacoum, brodifacoum, difethialone, and flocoumafen as active substances for the use in rodenticides, have just recently been renewed. The aim of this study was to assess the exposure of freshwater fish to anticoagulant rodenticides by analyzing levels of anticoagulants in fish tissues For this purpose, a highly sensitive and specific multimethod was developed to determine eight anticoagulants, which have been approved under the BPR for the use in rodenticides within the EU (cf Table 2). A highly sensitive and specific multimethod was developed to determine eight anticoagulants, which have been approved under the BPR for the use in rodenticides within the EU (cf Table 2) We the applied this method in a spatial monitoring study for two time points for fish liver and one for suspended particulate matter (SPM) samples of the German Environmental Specimen Bank (ESB). Selected liver samples from otters (Lutra lutra) were analyzed to characterize the bioaccumulation potential of ARs in fish-eating mammal species

Materials and methods
Method summary
Method development and method validation
Results and discussion
Compliance with ethical standards
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