RESUMEN
OBJECTIVE: To develop a method for simultaneous detection of 4 kinds of bisphenol A analogs in human urine by high performance liquid chromatography and tandem quadrupole mass-spectrometry. METHODS: The urine samples were extracted by solid phase extraction( Bond Elut Plexa) after hydrolyzed using β-glucuronidase and sulfatase. The gradient elution was carried out with acetonitrile-water. The bisphenol A-d16 and tetrabromobisphenol A-d10 were used as internal standard substances to conduct the quantitative analysis using the combined mode of liquid chromatography-mass spectrometry and mass spectrometry with the negative electrospray ionization,and the multiple reaction monitoring scan mode. RESULTS: The linear range of all the 4 kinds of bisphenol A analogs( Bisphenol F, Bishpenol A,Tetrachlorobisphenol A and Tetrabromobisphenol A) in urine was found to be 0. 50-100. 00 μg / L, and the linear correlation coefficients were 0. 998 6,0. 999 1,0. 999 6 and 0. 999 7,respectively. The limits of detection were 0. 21,0. 25,0. 01 and 0. 14 μg / L. The recovery rate was 69. 2%-99. 9%. The relative standard deviations of within-run and between-run precisions were 5. 5%-22. 8% and 2. 4%-14. 4%,respectively. The samples could be kept for at least 7 days at room temperature. The method was applied to detect urine samples of 38 children and 20 medical workers and the results were statistically analyzed. The detection rates of bisphenol A, bisphenol F, tetrachlorobisphenol A and tetrabromobisphenol A for children group were 94. 7%,94. 7%,0. 0% and 34. 2%,respectively,and those of the medical workers group were 100. 0%,100. 0%,5. 0% and 75. 0%,respectively. CONCLUSION: The method is effective for the detection of 4 kinds of bisphenol A analogs in human urine with simple operation,high sensitivity and good selectivity.
RESUMEN
<p><b>OBJECTIVE</b>We aimed to establish a sensitive quantified method for the simultaneous determination of melamine and cyanuric acid residues in water and urine by hydrophilic interaction liquid chromatography coupled with electrospray tandem mass spectrometry (HILIC-ESI-MS/MS) with the pretreatment of hydrophilic functional silica gel and cation exchange resin mixed solid phase extraction column(MCT), and to investigate the melamine and cyanuric acid residues in 501 water and 216 urine from several province and city.</p><p><b>METHODS</b>About 100 ml water (or 10 ml urine) was adjusted to pH 3.0 with concentrated hydrochloric acid, and then mixed with the internal standard solution((15)N3-melamine and (15)N3-(13)C3 -cyanuric acid) and 100 ml acetonitrile (10 ml for urine). The solution was cleaned with MCT solid-phase extraction column, and eluted once by 3 ml methanol and twice by 2.5 ml methanol (containing 5% ammonia water). The effluent was collected and dried by N2 flow at 40 °C, and then diluted to 2 mmol/L ammonium acetate containing 90% volume fraction acetonitrile. The completely dissolved solution was then filtered with 0.22 µm organic membrane; and the filtrate was detected by high performance liquid chromatography-tandem mass spectrometry and quantified with internal standards. The repeatability and sensitivity of the assay were evaluated. Then we detected the melamine and cyanuric acid residues in 501 water and 216 urine samples collected from several province and city.</p><p><b>RESULTS</b>By the quantification of internal standard (15)N3-melamine and (15)N3-(13)C3-cyanuric acid, the melamine and cyanuric acid were linear in the range of 2.0-1000.0 µg/L with correlation coefficient of 0.9998 and 0.9997. The detection limits of the method were separately 0.4 ng/L (melamine) and 0.3 ng/L (cyanuric acid) for water, and 4.0 ng/L (melamine) and 3.0 ng/L (cyanuric acid) for urine. The average recovery rate was around 95.3%-100.1% with the relative standard deviation (RSD) was <4.02%. Out of the 501 water samples, melamine was detected out in 19.9% (100/501) and cyanuric acid was detected out in 5.2% (26/501). The content was around 0.03-5.00 g/L. Melamine or cyanuric acid was detected out in 24.5% of the urine samples (53/216), with the content around 0.01-1.00 g/L.</p><p><b>CONCLUSION</b>The established method of solid phase extraction-hydrophilic interaction liquid chromatography-electrospray tandem mass spectrometry can satisfy the requirement for detection of melamine and cyanuric acid residues in all sorts of water and urine. Meanwhile, the two substances widely existed in water and Chinese population.</p>