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目的利用改进的HLB小柱净化和高效液相色谱-串联质谱法(HPLCMS/MS)测定10种常见的邻苯二甲酸酯(PAEs)代谢物在婴幼儿人群尿液中的残留水平。方法征集了50例06月龄普通婴幼儿,通过问卷调查了婴儿的喂养方式,利用纸尿裤采集其尿液。尿液经β-葡萄糖醛酸酶酶解、HLB柱净化浓缩后,采用Hypersil Gold Phenyl色谱柱(1.9μm,100 mm×2.1 mm)分离,电喷雾电离质谱检测,同位素内标法定量。结果 10种邻苯二甲酸酯代谢物检出限(LOD)为0.060.16μg/L,在0.2~500μg/L线性范围内相关系数(R2)均大于0.99,5.0~50μg/L加标水平下回收率为82%~116%,相对标准偏差(RSD,n=5)为1.5%~12.2%;婴幼儿尿液中8种邻苯二甲酸酯代谢物检出率在98%以上,几何平均浓度(μg/L)从高到低依次为邻苯二甲酸单异丁酯(MiBP,10.35)、邻苯二甲酸单(5-羰基-2-己戊基)酯(MECPP,5.13)、邻苯二甲酸丁酯(MBP,4.53)、邻苯二甲酸乙酯(MEP,1.98)、邻苯二甲酸甲酯(MMP,1.69)、邻苯二甲酸(2-乙基己基)酯(MEHP,1.22)、邻苯二甲酸(2-乙基-5-羰基己基)酯(MEHHP,1.18)和邻苯二甲酸(2-乙基-5-氧己基)酯(MEOHP,0.99),邻苯二甲酸苄基酯(MBzP)和邻苯二甲酸单环己酯(MCHP)检出率较低(分别为28%和2%)。奶粉喂养可能是婴儿内分泌干扰物邻苯二甲酸二(2-乙基)己酯(DEHP,是MEHP、MEOHP、MEHHP和MECPP的母体化合物)和邻苯二甲酸丁基苄基酯(BBzP,是MBzP的母体化合物)暴露的主要途径之一。结论利用HLB柱净化-HPLC-MS/MS技术可准确测定婴儿尿液中10种长短链PAEs代谢物,可以进一步用于婴幼儿人群的PAEs暴露风险评估。
Abstract：Objective Monitoring infants' exposure to 10 phthalates by measuring their urinary metabolites using a modified high performance liquid chromatography tandemelectrospray ionization mass spectrometry( HPLC-ESI-MS/MS) method. Methods A total of 50 infants at 0-6 month-old were recruited and their urine samples were collected by commercial available gel diapers. After the urine expression,phthalates were hydrolyzed by β-glucuronidase,cleaned up by HLB cartridge,then these metabolites were measured by HPLC-ESI-MS/MS equipped with a Hypersil Gold Phenyl column. The target compounds were quantified by the stable isotope dilution technique. Results The limit of detection( LOD) was 0. 06-0. 16 μg/L with linear ranged 0. 2-500 μg/L. 8 of 10 phthalate metabolites could be detected with > 98% frequencies,from the high to low levels( geometric mean,μg/L) they were Mi BP( 10. 35),MECPP( 5. 13),MBP( 4. 53),MEP( 1. 98),MMP( 1. 69),MEHP( 1. 22),MEHHP( 1. 18) and MEOHP( 0. 99). MBz P and MCHP could be detected in very low frequencies of 28% and 2%,respectively. Formula feeding might be one of the major routes of infant exposure to DEHP( parent compound of MEHP,MEOHP,MEHHP and MECPP) and BBz P( parent compound of MBz P). Conclusion The modified HLB-HPLC-MS/MS method can be used for determination of PAEs metabolites in infant urine effectively,and it is valuable for monitoring the infant'exposure risk to PAEs.
[1]SCHETTLER T.Human exposure to phthalates via consumer products[J].Int J Androl,2006,29:134-139.
[2]HAUSER R.Phthalates and human health[J].Occup Environ Med,2005,62(11):806-818.
[3]CALAFAT A M,SLAKMAN A R,SILVA M J,et al.Automated solid phase extraction and quantitative analysis of human milk for 13 phthalate metabolites[J].J Chromatog B,2004,805(1):49-56.
[4]HINES E P,CALAFAT A M,SILVA M J,et al.Concentrations of phthalate metabolites in milk,urine,saliva,and serum of lactating North Carolina women[J].Environ Health Persp,2009,117(1):86-92.
[5]XUE H,CUI Z,ZHOU N,et al.Urinary phthalate metabolites and male reproductive function parameters in Chongqing general population,China[J].Int J Hyg Envir Heal,2014,217(2-3):271-278.
[6]JOENSEN U N,FREDERIKSEN H,JENSEN M B,et al.Phthalate excretion pattern and testicular function:a study of 881 healthy Danish men[J].Environ Health Persp,2012,120(10):1397-1403.
[7]MEEKER J D,FERGUSON K K.Urinary phthalate metabolites are associated with decreased serum testosterone in men,women,and children from NHANES 2011-2012[J].J Clin Endocr Metab,2014,99(11):4346-4352.
[8]LIU L,XIA T,GUO L,et al.Expressing urine from a gel disposable diaper for biomonitoring using phthalates as an example[J].J Expo Sci Env Epid,2012,22(6):625-631.
[9]LIU L,BAO H,FENG L,et al.Phthalates exposure of Chinese reproductive age couples and its effect on male semen quality,a primary study[J].Environ Int,2012,42(1):78-83.
[10]FREDERIKSEN H,SKAKKEBAEK N E,ANDERSSON A M.Metabolism of phthalates in humans[J].Mol Nutr Food Res,2007,51(7):899-911.
[11]MATTHIAS W,JRGEN A.Phthalates:metabolismand exposure[J].Int J Androl,2008,31(2):131-138.
[12]YAGHJYAN L,CARLSSON N P,GHITA G L,et al.Associations of individual characteristics and lifestyle factors with metabolism of di-2-ethylhexyl phthalate in NHANES 2001-2012[J].Environ Res,2016,149:23-31.
[13]朱效宁,金玉娥,邬春华,等.某地区2岁幼儿的邻苯二甲酸酯暴露水平及其影响因素[J].环境与职业医学,2013,30(6):405-410.
[14]GONG M,WESCHLER C J,LIU L,et al.Phthalate metabolites in urine samples from Beijing children and correlations with phthalate levels in their handwipes[J].Indoor Air,2015,25(6):572-581.
[15]CALLESEN M,BEKG,WESCHLER C J,et al.Phthalate metabolites in urine and asthma,allergic rhinoconjunctivitis and atopic dermatitis in preschool children[J].Int J Hyg Envir Heal,2014,217(6):645-652.
[16]KASPER-SONNENBERG M,KOCH H M,WITTSIEPE J,et al.Levels of phthalate metabolites in urine among mother-child-pairs—results from the Duisburg birth cohort study,Germany[J].Int J Hyg Envir Heal,2012,215(3):373-382.
[17]HEFFERNAN A L,THOMPSON K,EAGLESHAM G,et al.Rapid,automated online SPE-LC-QTRAPMS/MS method for the simultaneous analysis of 14phthalate metabolites and 5 bisphenol analogues in human urine[J].Talanta,2016,151:224-233.
[18]朱效宁,汪国权,周志俊,等.尿中13种邻苯二甲酸酯代谢物的高效液相色谱串联质谱测定法[J].环境与职业医学,2015,32(3):265-270.
[19]高慧,许媛媛,孙丽,等.高效液相色谱-串联质谱法同时测定人尿液中7种邻苯二甲酸酯代谢物[J].色谱,2015,33(6):622-627.
[20]胡小键,张淼,徐肖雅,等.液相色谱-质谱/质谱法测定尿中11种邻苯二甲酸酯代谢物[J].卫生研究,2012,41(1):109-112.
[21]VLEZ M P,ARBUCKLE T E,FRASER W D.Female exposure to phenols and phthalates and time to pregnancy:the Maternal-Infant Research on Environmental Chemicals(MIREC)Study[J].Fertil Steril,2015,103(4):1011-1020.
[22]JOENSEN U N,JΦRGENSEN N,MELDGAARD M,et al.Associations of Filaggrin gene loss-of-function variants with urinary phthalate metabolites and testicular function in young Danish men[J].Environ Health Persp,2014,122(4):345-350.
[23]HUANG P,TSAI C,LIANG W,et al.Age and gender differences in urinary levels of eleven phthalate metabolites in general taiwanese population after a DEHP episode[J].PLo S One,2015,10(7):e133782.
[24]KASPER-SONNENBERG M,KOCH H M,WITTSIEPE J,et al.Phthalate metabolites and bisphenol A in urines from German school-aged children:results of the Duisburg Birth Cohort and Bochum Cohort Studies[J].Int J Hyg Envir Heal,2014,217(8):830-838.
[25]代娟娟,杨科峰,蒋磷蕾,等.固相萃取-高效液相色谱法测定儿童尿液中的邻苯二甲酸酯代谢物[J].上海交通大学学报(农业科学版),2014(4):82-87.
[26]林兴桃,王小逸,夏定国,等.固相萃取-高效液相色谱法测定人体尿液中邻苯二甲酸酯及其代谢物[J].分析化学,2011,39(6):877-881.
基本信息:
DOI：10.19813/j.cnki.weishengyanjiu.2017.04.023
中图分类号:R994.6
引用信息:
[1]王恒,刘良坡,申河清.HLB固相萃取-高效液相色谱串联质谱法测定婴幼儿尿液中邻苯二甲酸酯代谢物[J].卫生研究,2017,46(04):650-657.DOI:10.19813/j.cnki.weishengyanjiu.2017.04.023.
基金信息:
浙江省自然科学基金(No.LY14B070005)
2017-02-06
2017
2017-05-18
2017-05-18
2017
1
2017-07-30
2017-07-30