我国人群有机磷阻燃剂暴露评估及其健康风险

Exposure Assessment and Health Risk of Organophosphate Flame Retardants in General Population in China

有机磷阻燃剂的使用量呈现不断增加的趋势,但目前对我国人群有机磷阻燃剂的暴露特征及其健康风险研究甚少。为评估有机磷阻燃剂的暴露水平,本研究采集了全国8个城市中共600名普通成年人的尿液样本,用LC-MS-MS检测了11种有机磷酸酯代谢产物的浓度。研究表明,11种代谢产物均在尿液当中检出,磷酸二(2-氯乙基)酯(BCEP)的检出率及检出浓度最高,我国人群尿液样品中有机磷酸酯代谢产物浓度及组成特征呈现区域性差异,8个城市的总浓度范围在5.80~26.28 ng·mL^(-1)之间,深圳市以磷酸二丁酯(DnBP)为主要检出物质,其余地区以BCEP为主要检出物质,芳香类有机磷酸酯的代谢产物在深圳市的浓度比例高于其他7个城市。对8个城市检出率>60%的6种有机磷酸酯代谢产物尿液浓度数据的归一化处理表明,2-乙基-5-羟基己基二苯基磷酸酯(5-OH-EHDPP)、4-羟基苯基二苯基磷酸酯(4-OH-TPHP)、磷酸二(2-氯乙基)酯(BCEP)、磷酸二(1,3-二氯异丙基)酯(BDCIPP)、磷酸二丁酯(DnBP)和磷酸二苯酯(DPHP)的全国浓度几何均值分别为(0.03±2.75)、(0.08±2.77)、(4.78±2.77)、(0.12±2.77)、(0.83±2.77)和(0.25±2.75)ng·mL^(-1)。根据流行病学调查数据,计算得到以血液总胆固醇升高为终点的基准剂量为0.21 ng·mL^(-1)(5-OH-EHDPP)及0.93 ng·mL^(-1)(4-OH-TPHP),我国人群暴露EHDPP和TPHP导致血液总胆固醇浓度升高的健康风险分别为2.72%和0.80%。

With increasing production of organophosphate flame retardants(OPFRs),a few studies focused on their human exposure and health risks in population in China.In this study,we collected 600 urinary samples from general population across eight cities in China,and the urinary concentrations of 11 metabolites of OPFRs were detected using LC-MS-MS.The 11 metabolites were all detected in urinary samples,and bis(2-chloroethyl)phosphate(BCEP)showed the highest detection frequency and concentration.Concentrations and the composition of urinary OPFRs metabolites showed obvious differences across regions,with the total concentration ranging from 5.80 to 26.28 ng·mL^(-1).Di-n-butyl phosphate(DnBP)was the major metabolite in Shenzhen,while BCEP was the major in the other cities.The contribution of the metabolites of aryl-organophosphate to the total concentration in Shenzhen was higher than that in other cities.The geometric mean concentrations for 6 metabolites at national level were estimated by normalization method,including 2-ethyl-5-hydroxyhexyl diphenyl phosphate(5-OH-EHDPP),4-hydroxyphenyl diphenyl phosphate(4-OH-TPHP),bis(2-chloroethyl)phosphate(BCEP),bis(l,3-dichloro-2-propyl)phosphate(BDCIPP),di-n-butyl phosphate(DnBP)and diphenyl phosphate(DPHP),of which detection frequencies were more than 60%.Their geometric means were(0.03±2.75),(0.08±2.77),(4.78±2.77),(0.12±2.77),(0.83±2.77)and(0.25±2.75)ng·mL^(-1),respectively.Based on the results of an epidemiological study on the association between urinary concentration of 5-OH-EHDPP and 4-OH-TPHP with the elevated blood total cholesterol,BMDL 5(lower limit of the 95%confidence interval for benchmark dose with benchmark response of 5%)was calculated to be 0.21 ng·mL^(-1) for 5-OH-EHDPP and 0.93 ng·mL^(-1) for 4-OH-TPHP.Thus,the probability of the elevated blood total cholesterol level among Chinese population due to exposure to EHDPP and TPHP were 2.72%and 0.80%,respectively.