Biological Monitoring Method for Urinary Neonicotinoid Insecticides Using LC-MS/MS and Its Application to Japanese Adults

• Published in: Journal of Occupational Health 2014-11, Vol.56 (6), p.461-468
• Main Authors: Ueyama, June, Nomura, Hiroshi, Kondo, Takaaki, Saito, Isao, Ito, Yuki, Osaka, Aya, Kamijima, Michihiro
• Format: Article
• Language: English
• Subjects: Acetonitriles; Adult; Biological monitoring; Chromatography, High Pressure Liquid - methods; Environmental Monitoring - methods; Female; Guanidines - urine; Humans; Imidazoles - urine; Insecticides - urine; Japan; LC‐MS/MS; Male; Methanol; Middle Aged; Neonicotinoid; Neonicotinoids; Nitro Compounds - urine; Occupational Exposure - analysis; Oxazines - urine; Pyridines - urine; Solid Phase Extraction - methods; Tandem Mass Spectrometry - methods; Thiamethoxam; Thiazines - urine; Thiazoles - urine; Urine
• ISSN: 1341-9145; 1348-9585; 1348-9585
• DOI: 10.1539/joh.14-0077-oa

[Abstract]: Biological Monitoring Method for Urinary Neonicotinoid Insecticides Using LC-MS/MS and Its Application to Japanese Adults: Jun UEYAMA, et al. Department of Pathophysiological Laboratory Sciences, Field of Radiological and Medical Laboratory Sciences, Nagoya University Graduate School of Medicine - [Objectives]: Agricultural use of neonicotinoid (NEO) insecticides has been increasing in recent years, but their biological monitoring methods have been scarcely reported. In this study, we developed and validated a rapid and sensitive method for quantifying urinary NEO concentrations using high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS). [Methods]: After phosphate-induced acidification of a urine sample, urinary NEOs were trapped by a solid-phase extraction column and eluted with methanol for acetamiprid, imidacloprid, thiacloprid, thiamethoxam, clothianidin and dinotefuran and with an acetonitrile and methanol solution (1:1, v/v) containing 5% NH3 for nitenpyram. A separation analysis was performed by LC-MS/MS within 10 minutes for the sample. This method was applied to first morning urine obtained from 52 Japanese (40.9 +- 10.5 years old, mean +- standard deviation) without occupational NEO exposure. [Results]: The linear dynamic ranges and their limit of quantification (LOQ, signal to noise ratio=10) levels were 0.3-20 or 50 μg// (r=0.998-0.999) and 0.05-0.36 μg//, respectively. The absolute recovery was 64-95%, and the intra- and inter-day precisions were less than 16.4% (relative standard deviation, %RSD). This method was successfully applied for analysis of NEOs in human urine samples obtained from 52 adults. The frequencies of individuals who showed more than LOD levels was above 90% for imidacloprid, thiamethoxam, clothianidin and dinotefuran, more than 50% for acetamiprid and thiacloprid and 29% for nitenpyram. [Conclusions]: These results indicated that our new method could be applied to biological monitoring of NEO exposure even at environmental exposure levels in Japanese adults without occupational spraying histories.