A modified quick, easy, cheap, effective, rugged, and safe cleanup method followed by liquid chromatography-tandem mass spectrometry for the rapid analysis of perchlorate, bromate and hypophosphite in flour

A selective, sensitive and useful method, based on modified QuEChERS cleanup combined with liquid chromatography-tandem mass spectrometry (LC-MS/MS) in the negative-ion electrospray ionization (ESI−) mode, was developed and validated for the simultaneous determination of three inorganic anions including perchlorate (ClO4−), bromate (BrO3−) and hypophosphite (H2PO2−) in flour. The extraction parameters and LC-MS/MS conditions were optimized by single-factor experiment and sorbent combination in modified QuEChERS clean-up was optimized through response surface analysis. Three target analytes were separated on a normal-phase Phenomenex Luna Silica (2) column (150 mm × 2.0 mm, 5 μm, 100 Å) with the mobile phase of a mixture of 5 mmol/L ammonium acetate water solution and acetonitrile, detected by MS/MS under multiple reaction monitoring and quantified by external standard method. The developed method was validated in terms of the sensitivity, linearity, accuracy and precision, and matrix effect. The method showed a good linearity (R2 > 0.999) for all analytes in their respective concentration ranges. The ILOQs and MLOQs for perchlorate, bromate and hypophosphite were 0.1, 0.5, 5.0 μg/L and 2.0, 6.0, 60.0 μg/L, respectively. The average recoveries of three target analytes from the negative samples spiked at three different concentrations were in a range from 84.6% to 104.9%. The intra-day precision (n = 6) and inter-day precision (n = 5) of the target analytes were in the ranges of 2.9%-6.9% and 6.4%-8.2%. The matrix effect of this method was observed between 0.83 and 1.17 and was acceptable. The validated method was successfully applied to determine the concentrations of these inorganic anions in flour. Results found that perchlorate and hypophosphite were detected in 33 out of 50 and 7 out of 50 flour samples.