Sources,Environmental And Human Exposure Of Typical Personal Care Products

Personal care products?PCPs?such as mildew preventives and preservatives are widely used in various household chemical products at relatively high content.During production and utilization,a large amount of PCPs find their way into various environmental media including water bodies,soil and indoor dust.These environmental media are closely related to human life,indirectly increasing the exposure risks of PCPs to human bodies.In addition,large quantities of PCPs are commonly used in production and living activities of human being,resulting in that a considerable amount of theses PCPs directly transfer into human bodies via breath,skin exposure and contaminated food.Presently,reported studies have revealed that the exposure of PCPs can pose different extents of detrimental effects to human health and the eco-environment.This study based on the target PCPs including methyl paraben?MP?,ethyl paraben?EP?,propyl paraben?PP?,butyl paraben?BP?,triclosan?TCS?,triclocarban?TCC?,Methylchloroisothiazolinone?CIT?,Methylisothiazolinone?MIT?,1,2-benzisothiazolin-one?BIT?,chlorophene?CP?,chloroxylenol?PCMX?,4-Chloro-3-cresol?BCP?,o-phenylphenol?OPP?,dichlorophene?DCP?,benzalkonium chloride(C₁₂BDMA,C₁₄BDMA and C₁₆BDMA).Solid phase extraction?SPE?,high performance liquid chromatography?HPLC?,HPLC tandem mass spectrometry?HPLC/MS/MS?and ultra-high performance liquid chromatography-quadrupole tandem time-of-flight?UPLC-QTOF-MS?were jointly applied to quanltative and quantitative analysis of the target PCPs in various household chemical products,environmental water bodies and human urine.The sources and environmental exposure of the PCPs were explored in terms of the concentration levels and distribution features of these compounds in household chemical products,and exposure to environmental water bodies and human urine.In addition,PCMX which presented relatively high exposure concentrations in both the environment and human bodies was chosen as a special target,to assess the human health risks of PCMX by means of establishing different exposure models in conjuction with external exposure internal exposure methods.This study gained the main resuls and insights as follows.?1?Ultrasonic extraction combined with HPLC were applied to develop 5 methods for quantification of 18 preservatives including MP,EP and so on in various household chemical products.The recoveries of standards of these methods were 92.0%-105.8%,with the relative standard deviations?RSDs?within 0.7%-5.2%,and the method detection limits were 0.3-3.0 mg/kg.SPE in combination with HPLC-MS/MS and UPLC-QTOF-MS were employed to develop 7 quantitative and confirmatory methods for analyzing 10 PCPs in environmental water bodies and 11 PCPs in human urine.After the optimization of working conditions and parameters of SPE,liquid chromatography and mass spectrometry,the recoveries of standards of the methods related to environmental bodies were 69.5%-112.0%,with RSDs of 1.7%-11.1%,and the method detection limits ranged from 0.03 to 1 ng/mL.The recoveries of standards of the methods corresponding to human urine were72.1%-125.2%?RSDs:3.3%-18.2%?,and the method detection limit were 0.002-0.02?g/L.Furthermore,by means of simulated metabolic pathways and constructed data reservoir of metabolites,the glucuronidation and sulfation metabolites of PCMX were rapidly and accurately screened and confirmed.?2?In all household chemical products,the additive proportion of MP was very high,and the detection rates of MP,PP,EP,BP and IBP were 47.0%,27.1%,2.9%,1.9%and0.6%,respectively with the average concentrations of 514 mg/kg,162 mg/kg,10.0 mg/kg,8.0 mg/kg and 0.6 mg/kg,respectively.MIT and CIT presented the highest use ratio in drip-washing household chemical products,with the detection rates of 50.6%and 39.6%,respectively,and the average concentrations were 19.3 mg/kg and 4.7 mg/kg,respectively.In addition,MIT showed the detection rate of 37.0%in baby products,with the average concentration of 16.6 mg/kg.TCS was mainly detected in hair shampoos and hand-washing products,with the detection rates of 24.6%and 9.1%in these two products,and the corresponding average concentrations were 106 mg/kg and 555 mg/kg,respectively.TCC was mainly found in toilet soaps with the detection rate of 17.6%,and the mean concentration was 654 mg/kg.The use rates of PCMX in hand-washing and disinfection products were relatively high,with the detection rates of 20.6%and 12.5%,respectively,and the corresponding mean concentrations were 500 mg/kg and 4130 mg/kg,respectively.?3?The concentration ranges of PCMX,OPP and BCP in the water samples collected from the Guangzhou reach of the Pearl River were 1731-14141.7 ng/L,12.5-126.3 ng/L and0.1-0.6 ng/L,with the geometric mean concentrations of 2610.1 ng/L,74.0 ng/L and 0.4ng/L,respectively.The concentration ranges of C₁₂BDMA?C₁₄BDMA and C₁₆BDMA were3.6-46.7 ng/L,1.1-26.1 ng/L and not detected to 6.3 ng/L,with the geometric mean concentrations of 20.0 ng/L,10.6 ng/L and 1.0 ng/L,respectively.The detection rate of C₁₆BDMA was 66.7%,with the geometric mean concentration of 1.0 ng/L.The concentration range of BIT was 2.3-9.8 ng/L,with the geometric mean concentration of 4.0ng/L.Thus it can be concluded that various PCPs are ubiquitous in the aquatic environment,and the relatively high pollution levels of PCMX should be brought to the forefront.These results show that various PCPs were ubiquitously present in the environmental water bodies,and some PCPs including PCMX presented relatively high pollution level and might impact the aquatic environment.?4?The concentration range of PCMX in human urine was 0.5-5453?g/L,with the geometric mean concentrations of 28.5?g/L and 24.2?g/L in the urine of pregnant women and children,respectively,and the geometric mean concentrations in 2015 were lower than those in 2017.The detection rates of OPP and BCP were>40%,with the highest concentrations of 4.0?g/L and 3.9?g/L,respectively.Among the 6 PCPs involving parabens,MP showed the detection rate of 100%,with the highest concentration of 192.9?g/L;and the detection rates of EP,PP and TCS were higher than 70%,with the highest concentrations of 150.4?g/L,168.3?g/L and 22.7?g/L,respectively;while BP and TCC showed relatively lower detection rates within the range of 25.0-66.6%,and their highest concentrations were 3.42?g/L and 4.36?g/L,respectively.The average concentrations and the highest concentrations of the 6 PCPs in the urine of pregnant women were higher than those of children.The geometric mean concentrations of the 6 PCPs in the urine of pregnant women and children presented insignificant differences between 2015 and 2017.Therefore,the exposure of PCPs to human bodies were ubiquitous,and the exposed quantities migh be dependent on exposure periods and populations.?5?This study assessed the exposure risks of the disinfectants and hand-washing proeducts in which PCMX was used as the effective constituent.Based on the simulation of using disinfectants,the highest chronic exposure quantity was 2.7×10^-2mg/kg/day with the MOE of simulated scene<100,indicating that the environment of the simulated scene was relatively safe for pregnant women and children.However,the exposure to children in closed environment should be taken into account seriously.In the exposure test of hand-washing simulation,the concentrations of PCMX in the urine of 6 subjects generally kept unchanged in the 5 days prior to simulation.Whereas during the 5 days when the subjects washed hands with hand-washing products containing PCMX,the concentrations of PCMX increased significantly,reaching up to 688?g/L.In addition,when the subjects stopped using the hand-washing products,the concentrations of PCMX were decreased to the lowest within 48 hours.On the other hand,the increasing extents and decreasing rates of PCMX varied among different subjects.In terms of the calculation of summit values,the highest daily intake of PCMX for the subjects was 22.9?g/kg/day,which was significantly lower than the percutaneous stimulation NOEL value?18 mg/kg/day?.Furthermore,the concentrations of PCDX in urine showed some correlations with those of 8-OHdG,but the concentration variation of 8-OHdG was insignificant.As a result,in this study,the exposure of PCMX in human bodies could not trigger DNA oxidative damage which leads to variation of 8-OHdG concentrations.On the basis of the currently available toxilogical data of PCMX,the final assessment results indicate that utilization of floor disinfectants and hand-washing products under rational conditions is safe.Nevertheless,futher in-depth investigation and exploration are warranted in terms of the human health risks triggered by long-term exposure of PCMX and synergistic effects of PCMX and other PCPs.