Pesticide analysis in teas and chamomile by liquid chromatography and gas chromatography tandem mass spectrometry using a modified QuEChERS method: Validation and pilot survey in real samples

• Published in: Journal of Chromatography A 2012-12, Vol.1268, p.109-122
• Main Authors: Lozano, Ana, Rajski, Łukasz, Belmonte-Valles, Noelia, Uclés, Ana, Uclés, Samanta, Mezcua, Milagros, Fernández-Alba, Amadeo R.
• Format: Article
• Language: English
• Subjects: black tea; calcium chloride; chamomile; citrates; detection limit; European Union; fungicides; Gas chromatography; green tea; herbicides; insecticides; Liquid chromatography; magnesium sulfate; Mass spectrometry; maximum residue limits; QuEChERS; surveys; tandem mass spectrometry; Tea; Validation
• ISSN: 0021-9673
• DOI: 10.1016/j.chroma.2012.10.013

► A method for analysis of 86 pesticide residues in green, black, red teas and chamomile was validated. ► A modification of QuEChERS method was employed; calcium chloride in clean-up step. ► The method was applied to the real samples. ► Pesticides above EU maximum residue levels detected in real samples. ► Pesticides banned in EU detected in real samples. This paper presents the validation of a modified QuEChERS method in four matrices – green tea, red tea, black tea and chamomile. The experiments were carried out using blank samples spiked with a solution of 86 pesticides (insecticides, fungicides and herbicides) at four levels – 10, 25, 50 and 100μg/kg. The samples were extracted according to the citrate QuEChERS protocol; however, to reduce the amount of coextracted matrix compounds, calcium chloride was employed instead of magnesium sulphate in the clean-up step. The samples were analysed by LC–MS/MS and GC–MS/MS. Included in the scope of validation were: recovery, linearity, matrix effects, limits of detection and quantitation as well as intra-day and inter-day precision. The validated method was used in a real sample survey carried out on 75 samples purchased in ten different countries. In all matrices, recoveries of the majority of compounds were in the 70–120% range and were characterised by precision lower than 20%. In 85% of pesticide/matrix combinations the analytes can be detected quantitatively by the proposed method at the European Union Maximum Residue Level. The analysis of the real samples revealed that large number of teas and chamomiles sold in the European Union contain pesticides whose usage is not approved and also pesticides in concentrations above the EU MRLs.