Modified QuEChERS method for 24 plant growth regulators in grapes using LC-MS/MS

A multiresidue analytical method was developed for grapes for the following 24 plant growth regulators: 1-naphthylacetamide, 2,3,5-triiodobenzoic acid, 2,4,5-T, 2-naphthoxyacetic acid, 3-indolylacetic acid, 4-(3-indolyl)-butyric acid, 4-chlorophenoxyacetic acid, 4-nitrophenol, 6-benzylaminopurine, N6-isopentenyladenine, butralin, chlormequat chloride, chlorphonim-Cl, cloprop, forchlorfenuron, gibberellic acid 3, gibberellic acid 4, gibberellic acid 7, inabenfide, mepiquat chloride, paclobutrazol, prohydrojasmon, thidiazuron and uniconizole-P. The compounds were extracted from grape samples using an extraction method modified from the Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method. Liquid chromatography – tandem mass spectrometry was used for the detection and quantification of the compounds. Validation of the method was performed by using recovery studies at both intra-day and inter-day intervals, as well as by evaluation of the matrix effect, limit of quantification, trueness and precision. We used matrix-matched calibrations for the quantification of the compounds, which all resulted in determination coefficients (r2) higher than 0.995. The limit of quantification ranged from 0.1 to 5 ng/mL. Recovery studies using three spiking concentrations at varying levels showed recoveries of 70.2–112.6% and 67.5–101.8% at intra-day and inter-day intervals, respectively. Relative standard deviations were below 20% for the recovery studies. The extraction method were further validated by performing recovery study and matrix effect test in six different grape varieties from Taiwan and the United States and all resulted in comparable results. Application of the established method to 50 grape samples, resulted in the detection of chlormequat chloride and forchlorfenuron residues in the tested grapes. The results of the method validation and real sample analysis shows the extraction method is therefore suitable for routine monitoring of residue in grapes.