A modified QuEChERS method for determination of organophosphate esters in milk by GC-MS

Organophosphate esters (OPEs) are substances that have been detected in several matrices due to their use as flame retardants and plasticizers. Human exposure to OPEs can cause endocrine disruption, hormonal problems, and reproductive disturbance. Ingestion of contaminated food can be a significant route of exposure to OPEs. Food can be contaminated by OPEs in the food chain, during cultivation, and by contact with plasticizers during the production chain of processed foods. In this study, a method for the determination of 10 OPEs in commercial bovine milk was developed. The procedure was based on QuEChERS extraction and gas chromatography coupled to mass spectrometry (GC-MS) analysis. QuEChERS modification included a freezing-out step after the extraction followed by the concentration of the entire acetonitrile phase before the clean-up step. Calibration linearity, matrix effects, recovery, and precision were evaluated. Significant matrix effects were observed, which could be compensated by the isotopically labeled internal standard quantification and matrix-matched calibration curves. Recoveries ranged from 77 to 105%, with a relative standard deviation ranging from 3 to 38%. The method detection limits (MDLs) were in the range of 0.031–6.7 ng mL−1, while the method quantification limits (MQLs) were within the range from 0.27 to 20 ng mL−1. The proposed method was successfully validated and applied to determine the concentrations of OPEs in bovine milk. The 2-ethylhexyl diphenyl phosphate (EHDPHP) was detected in the analyzed milk samples but at levels below the MQL.