RESEARCH PAPER Evaluation of on-line concentration coupled to liquid chromatography tandem mass spectrometry for the quantification of neonicotinoids and fipronil in surface water and tap water Juan Manuel Montiel-León 1 & Sung Vo Duy 1 & Gabriel Munoz 1 & Marc Amyot 2 & Sébastien Sauvé 1 Received: 9 November 2017 /Revised: 29 January 2018 /Accepted: 9 February 2018 # Springer-Verlag GmbH Germany, part of Springer Nature 2018 Abstract A study was initiated to investigate a fast and reliable method for the determination of selected systemic insecticides in water matrixes and to evaluate potential sources of bias in their analysis. Acetamiprid, clothianidin, desnitro-imidacloprid, dinotefuran, fipronil, imidacloprid, nitenpyram, thiacloprid, and thiamethoxam were amenable to analysis via on-line sample enrichment hyphenated to ultra-high-performance liquid chromatography tandem mass spectrometry. The selection of on-line solid-phase extraction parameters was dictated by a multicriterion desirability approach. A 2-mL on-line injection volume with a 1500 μL min -1 loading flow rate met the objectives sought in terms of chromatographic requirements, extraction efficiency, sensitivity, and precision. A total analysis time of 8 min per sample was obtained with method limits of detection in the range of 0.1–5 ng L -1 for the scope of targeted analytes. Automation at the sample concentration step yielded intraday and interday precisions in the range of 1–23 and 2–26%, respectively. Factors that could affect the whole method accuracy were further evaluated in matrix-specific experiments. The impact of the initial filtration step on analyte recovery was evaluated in ultra-pure water, tap water, and surface water. Out of the nine membranes tested, glass fiber filters and polyester filters appeared as the most appropriate materials. Sample storage stability was also investigated across the three matrix types; the targeted analytes displayed suitable stability during 28 days at either 4 °C or - 20 °C, with little deviations (± 10%) with respect to the initial T 0 concentration. Method applicability was demonstrated in a range of tap water and surface water samples from the province of Québec, Canada. Results from the present survey indicated a predominance of thiamethoxam (< 0.5–10 and 3–61 ng L -1 in tap water and river water, respectively), clothianidin (< 0.5–6 and 2–88 ng L -1 in tap water and river water, respectively), and imidacloprid (< 0.1–1 and 0.8–38 ng L -1 in tap water and river water, respectively) among the targeted analytes. Keywords Systemic pesticides . Neonicotinoids . On-line solid-phase extraction . Water analysis . Filtration . Storage stability Introduction Pesticides have been widely used for disease control, house- hold pest eradication, and agricultural pest management. Nitromethylene heterocyclic compounds were developed in the 1970s, and their specific modes of action immediately aroused the interest of the agricultural industry, imidacloprid being the first synthesized neonicotinoid [1, 2]. Neonicotinoid insecticides share a common mode of action, affecting the central nervous system playing the role of nico- tinic acetylcholine receptor (nAChR) agonist [1]. Another sys- temic insecticide of concern is fipronil, a GABA-gated chlo- ride channel blocker pertaining to group 2B (phenylpyrazoles) of the latter classification [3]. Non-target organisms may be affected by such insecticides, including domesticated insect pollinators such as western honey bees (Apis mellifera) and wild pollinators such as bumblebees (e.g., Bombus impatiens) [4, 5]. Neonicotinoid exposure may affect the health status of apiaries, contributing to a decline in brood production and total adult numbers—a syndrome otherwise known as colony Electronic supplementary material The online version of this article (https://doi.org/10.1007/s00216-018-0957-2) contains supplementary material, which is available to authorized users. * Sébastien Sauvé sebastien.sauve@umontreal.ca 1 Département de Chimie, Université de Montréal, Pavillon Roger-Gaudry, 2900 Edouard-Montpetit, Montréal, Québec H3C 3J7, Canada 2 GRIL, Département de Sciences Biologiques, Université de Montréal, Pavillon Marie-Victorin 90, Avenue Vincent-d’Indy, Montréal, Québec H2V 2S9, Canada Analytical and Bioanalytical Chemistry https://doi.org/10.1007/s00216-018-0957-2