Application of d-SPE before SPE and HPLC-FLD to Analyze Bisphenols in Human Breast Milk Samples

Abstract

In this study, we propose a simple, cost-effective, and sensitive high-performance liquid chromatography with fluorescence detection (HPLC-FLD) for the simultaneous determination of seven bisphenols (bisphenol F (BPF), bisphenol E (BPE), bisphenol B (BPB), BADGE (bisphenol A diglycidyl ether), BADGE∙2H2O, BADGE∙H2O, BADGE∙2HCl) in human breast milk samples. The dispersive solid phase extraction (d-SPE) coupled with solid phase extraction (SPE) procedure performed well for the majority of the analytes with recoveries in the range 57–88% and relative standard deviations (RSD%) of less than 9.4%. During the d-SPE stage, no significant matrix effect was observed thanks to the application of different pairs of salts such as zirconium-dioxide-based sorbents (Z-Sep or Z-Sep +) and primary secondary amine (PSA) or QuEChERS Enhanced Matrix Removal-Lipid (EMR-Lipid) and PSA. The method limits of quantification (mLOQs) for all investigated analytes were set at satisfactory low values in the range 171.89–235.11 ng mL−1. Analyte concentrations were determined as the average value from human breast milk matrix samples. The results show that the d-SPE/SPE procedure, especially with the application of EMR-Lipid and PSA, could be used for further bisphenol analyses in human breast milk samples.

Application of Solid Phase Extraction and High-Performance Liquid Chromatography with Fluorescence Detection to Analyze Bisphenol A Bis (2,3-Dihydroxypropyl) Ether (BADGE 2H2O), Bisphenol F (BPF), and Bisphenol E (BPE) in Human Urine Samples

“…Tuzimski and Szubartowski [ 34 ] described a method for the determination of selected bisphenols in human breast milk samples by a dispersive solid phase extraction before solid phase extraction procedure (d-SPE/SPE) and high-performance liquid chromatography coupled with fluorescence detector (HPLC-FLD). In comparison to the results published earlier [ 33 ], the authors proposed a method, which has advantages, as follows [ 34 ]: A 10–fold reduction in the sample volume (from 5 to 0.5 mL); Optimization of the d-SPE/SPE technique for the majority of analyzed bisphenols; Optimal recovery values obtained for all of the analytes in the range from 57 to 88% for seven bisphenols combined with a low matrix effect, ensuring the reliable identification and quantification of analytes; The sample volume of 0.5 mL enabled to combine several milk samples from one woman allowing the identification and quantitation of the analytes in biological samples using a sensitive fluorescence detector (FLD); Due to the use of HPLC-FLD it was possible to identify and quantify bisphenols in human milk samples. …”

“…A series of experiments were conducted applying HPLC-FLD system, which is less expensive than liquid chromatography coupled with mass spectrometry (LC-MS) or tandem mass spectrometry (LC-MS/MS). Bisphenol standards (see Table 2 ) were chromatographed in condition based on the previously published method applied for determination of selected bisphenols, after appropriate modification [ 33 , 34 ].…”

“…Z-Sep, Z-Sep+, and EMR-Lipid (enhanced matrix removal-lipid) removes fatty and more hydrophobic interferences of matrices [ 38 , 39 , 40 , 41 , 42 , 43 ]. Zirconium-based dispersive phases demonstrate the ability to extract more fatty non-polar interferences (e.g., lipids) and pigment than traditional PSA and octadecyl (C18) sorbents and, therefore, in many cases, greater analyte recovery and better reproducibility may be achieved [ 34 ].…”

“…The ratio of PSA to Z-SEP was chosen during optimization (on the basis of previous experiments [ 33 , 34 ]). Additionally, Z-Sep with PSA can remove some medicines, vitamins, and dietary supplements in urine.…”

“…Previous studies detected bisphenols in amniotic fluid, follicular fluid, placental tissue, sperm, cord blood, fetal serum, adipose tissue [ 27 , 28 , 29 , 30 , 31 ], and human breast milk samples [ 32 , 33 , 34 , 35 ].…”