| Objective: To investigate the levels of 2-chlorophenol(2-CP), 2,4-dichlorophenol(2,4-DCP), 2,4,6-trichlorophenol(2,4,6-TCP)and pentachlorophenol(PCP) in source water and humans urine based on the community population from Guichi district,Chizhou, and evaluate the ecological risk of four chlorophenols in water environment preliminarily to provide reference for risk management.Methods: To establish the method for the simultaneous determination of 2-CP, 2,4-DCP,2,4,6-TCP and PCP in water and human urine by solid phase extraction-gas chromatography tandem mass spectrometry(SPE-GC/MS/MS) and liquid-liquid extraction(LLE)-GC-MS/MS, respectively. The source water samples were collected in the study for a total of 24 samples in May 2014, including Yangtze River water,reservoir water and river water. To construct the species sensitivity distribution curve,and evaluate potential ecological risk of four chlorophenols in source water according to the detection results of water samples. To select the two towns of Dunshang and Yinhui in accordance with the higher concentrations of PCP in source water and collect the first morning urine samples from the community residents in two towns in October 2014, the total of 498 participants(≥10 years old) were collected. This study selected the morning urine samples of 50 participants randomly, and the internal dose of four chlorophenols in urine of residents in long-term low-dose exposure were analyzed.Results:(1) The determination method of four chlorophenols was established by solid phase extraction-gas chromatography tandem mass spectrometry(SPE-GC/MS/MS).The linear range of 1.0~200.0μg/L with good linear relationship, the detection limit of method were 1.0~4.0 ng/L, the recoveries were 83.2%~108.8% and relative standard deviation(RSD) were 3.4%~8.7%.(2) The concentrations of 2-CP, 2,4-DCP, 2,4,6-TCP and PCP in source water ranged from 51.54~115.55ng/L, nd(<LOD,not detected)~51.42ng/L, nd~22.08 ng/L and 12.34~92.55ng/L, respectively, with the median concentration of 79.22ng/L, nd, 3.59ng/L and 19.46ng/L. The levels of 2-CP and PCP in river water,reservoir water and the Yangtze River water showed no statistical difference(P>0.05),the concentrations of 2,4-DCP and 2,4,6-TCP in Yangtze River water were higher than that of river water and reservoir water, with statistical difference(P<0.05).(3)The ecological risk of four chlorophenols to all the species from high to low was in the order of 2-CP>2,4,6-TCP>PCP≈2,4-DCP using the species sensitivity distribution method.The risk of four chlorophenols in each sampling site did not exceed the 5%threshold with the joint acute ms PAF being less than 1%.(4) To establish a method for the simultaneous determination of 2-CP, 2,4-DCP, 2,4,6-TCP and PCP in human urine by liquid-liquid extraction-gas chromatography coupled with tandem mass spectrometry(LLE-GC- MS/MS). Artificial simulation urine used as matrix of urine blank, good linear relationships were obtained in the range of 0.5~100μg/L, 0.5~100μg/L,0.5~100μg/L and 1.0~100μg/L for 2-CP, 2,4-DCP, 2,4,6-TCP and PCP, respectively. The correlation coefficients were above 0.999, The limits of detection ranged from 0.1μg/L to 0.3μg/L, Recoveries were between 88.8% and 118.2% with relative standard deviation in the range of 1.3% to 5.5%.(5)The urinary chlorophenols levels in 50 participants ranged from nd~1.06μg/L,0.57~1.08μg/L,0.68~1.45μg/L for 2-CP, 2,4-DCP and 2,4,6-TCP, respectively. PCP was not detected in all the samples. The median concentration of 2-CP, 2,4-DCP and 2,4,6-TCP was nd(<LOD), 0.65μg/L and 0.87μg/L,respectively.(6) The analysis result of affecting factors showed that age may affect the internal dose of 2,4,6-TCP, the high age group had a higher urinary 2,4,6-TCP concentration than the low age group. The effect of gender for urinary 2,4-DCP and2,4,6-TCP, and age for urinary 2,4-DCP had not been found.Conclusion:(1) The method was simple, sensitive and accurate to detect chlorophenols in source water and human urine. The concentrations of four chlorophenols in source water were far lower than the corresponding standard values of "Surface Water Environment Quality Standard"(GB 3838-2002).(2) The preliminary evaluation the ecological risk of four chlorophenols in source water, 2-CP showed low potential ecological risk, the others had no ecological risk. Four chlorophenols in each sampling site did not exceed the 5%threshold with the joint acute ms PAF being less than 1%.The others chlorophenols should been concerned except PCP.(3) The concentrations of urinary chlorophenols in 50 participants ranged from nd~1.06μg/L, 0.57~1.08μg/L,0.68~ 1.45μg/L for 2-CP, 2,4-DCP and 2,4,6-TCP, respectively. PCP was not detected in all the samples. The concentrations of 2,4-DCP and 2,4,6-TCP were consistent with the biological monitoring results of urinary chlorophenols from the United States and South Korea.(4) The high age group had a higher urinary 2,4,6-TCP concentration than the low age group and that could be related to the accumulation of chlorophenols in body after long-term low-dose exposure. |
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