Use of an Efficient Measurement Uncertainty Approach To Compare Room Temperature and Cryogenic Sample Processing in the Analysis of Chemical Contaminants in Foods.

In this study, analytical results were compared when using different approaches to bulk food sample comminution, consisting of a vertical chopper (Blixer) at room temperature and dry ice cryogenic conditions, followed by further subsample processing (20 g) using liquid nitrogen cryogenic conditions (cryomill). Analysis of the 43 targeted spiked and incurred contaminants in a food mixture consisting of equal parts orange, apple, kale, salmon, and croaker involved quick, easy, cheap, effective, rugged, and safe (QuEChERS) with automated mini-column solid-phase extraction (known as ITSP) cleanup, followed by low-pressure gas chromatography-tandem mass spectrometry (LPGC-MS/MS). Different ambient Blixer test portion sizes of 20, 10, 5, 2, and 1 g were assessed, and for cryogenic Blixer conditions, a 0.5 g test portion was also tested. In the case of the cryomill, test portions were 2, 1, and 0.5 g and all subsamples in all cases entailed five replicates. Determined concentrations and precisions (CV) of the analytes were compared to assess possible differences in systematic and random forms of error. A quality control spike was made before each step in the procedures to isolate that individual step in the uncertainty measurements using the error propagation sum of squares approach. Results indicated that the uncertainty of the sample preparation and LPGC-MS/MS analysis steps were 2-7 and 11% CV, respectively, while uncertainties of sample processing ranged from 6% CV for the cryomill to 12% CV for the ambient Blixer conditions. The common use of internal standards reduced overall method uncertainty from 12-15 to 7-10% CV. For the analytes, matrix, conditions, and tools used in this study, the minimal test sample weight that gave satisfactory recoveries and precision was found to be 1 g in all cases.