The Study On Occurrence And Distribution Of Typical Pharmaceuticals And Personal Care Products (PPCPs) In Tianjin Urban Aqueous And Soil Environment And The Combined Estrogenic Effects

Pharmaceuticals and Personal Care Products as Pollutants (PPCPs) comprise a diverse collection of chemical substances, including any product used by individuals for personal health or cosmetic reasons or used by agribusiness to enhance growth or health of livestock. In this paper, fluoroquinolones, tetracyclines and sulfonamides were selected as traget compounds, considering that they are the the three most commonly used antibiotic groups in China. The combined estrogenic activity of binary mixtures of estrone, 17β-estradiol, estiol and 17α-ethynylestradiol at different equipotent concentrations were also tested.The simultaneous analysis method for multiple classes of antibiotics in water samples via solid phase extraction and liquid chromatography-tandem mass spectrometry were established and optimized. The limit of detection of target antibiotics were at the range of 0.4-3.2 ng/L, the recoveries were between 60% and 105%, and the relative standard deviation was less than 15%.This optimized analytical method were applied for the detection of fluoroquinolones, tetracyclines and sulfonamides in rivers, discharge river, wastewater treatment effluent, reclaimed water, drinking water resource and tap water.Thirteen target antibiotics were detected in the river, with the concentration of 3.0-1080.0 ng/L. Nine target antibiotics were detected in the discharge river, with the concentration of 4.7-448.4 ng/L. In the wastewater treatment effluent, twelve target antibiotics were determined, of which the contents were at the range between 43.0 ng/L and 486.0 ng/L. Nine target antibiotics were detected in the reclaimed water, with the concentration of 4.0-311.0 ng/L. None of the target antibiotics were detected in drinking water resource and tap water.Moreover, the simultaneous analysis method for multiple classes of antibiotics in soil samples via solid phase extraction and liquid chromatography-tandem mass spectrometry were established and optimized. The limit of detection of target antibiotics were at the range of 0.1-1.9μg/kg, the recoveries were between 56% and 97%, and the relative standard deviation was less than 20%.This optimized analytical method were applied for the detection of fluoroquinolones, tetracyclines and sulfonamides in soil samples collected from the irrigation area of Dagu discharge river and Beitang discharge river. The soil samples collected from the farmland and orchard near the Yvqiao reservoir were also analysed.Twelve target antibiotics were detected in the samples collected from the irrigation area of Dagu discharge river, the concentration were from 1.4μg/kg to114.8μg/kg. Nine target antibiotics were detected in the samples collected from the irrigation area of Beitang discharge river, with the concentration of 0.7-306.9μg/kg. All of the target antibiotics were detected in the samples collected from Yvqiao reservoir, with the concentration of 0.5-20343.2μg/kg.The procedure of recombined yeast estrogen screen were optimized by adjusting the sample reaction time to 2 h and set the color reaction time as 30 min.The parameters for cell proliferation assay using MCF-7 human breast cancer cells were optimized. The DMEM medium without phenol was selected as the solvent for analytical compounds. The fetal bovine serum treated by activated carbon / dextran was necessary for the proliferation test. The optimized pro-incubation time with DMEM medium without phenol was 7 d. The analytical reaction time was set as 48 h.The optimized recombined yeast estrogen screen and cell proliferation assay were applied for the test of combined estrogenic activity of binary mixtures of estrone, 17β-estradiol, estiol and 17α-thynylestradiol at different equipotent concentrations. Concentration addition model and independent action model were used to predict the combined estrogenic activity of binary mixtures. The results demonstrated that the prediction of concentration addition model was less deviated in the recombined yeast estrogen screen than the prediction of independent action model. However, the independent action model was better than concentration addition model in the cell proliferation assay.