环境空气细颗粒物中16种邻苯二甲酸酯类化合物的超高效液相色谱-串联质谱测定法

摘要/Abstract

摘要： 目的建立超声波提取-超高效液相色谱-串联质谱法同时检测环境空气细颗粒物（particulate matter,PM_2.5）中16种邻苯二甲酸酯类化合物（phthalate esters,PAEs）的快速检测方法。方法使用装有PM_2.5切割头的采样器收集样本至石英滤膜上,通过比较不同提取液的提取效率,选择适当的提取液对样品进行超声提取,对比3种色谱柱的分离效果及保留时间,对16种PAEs采用超高效液相色谱-串联质谱法进行检测,内标法定量,得到线性、检出限等指标,加入适量标准至石英滤膜,评价方法的回收率及精密度。结果 16种PAEs类化合物的线性范围在0.5~200 ng/mL的范围内均具有较好的线性关系,R值均>0.995 0;比较50%甲醇水溶液、50%乙腈水溶液、甲醇和乙腈4种提取溶液对加标后浓度为10、50、100 μg/L滤膜样品的提取效果,4种提取溶剂的平均加标回收率（n=3）分别为71.45%~126.8%、51.71%~124.40%、68.62%~210.3%和84.08%~110.28%。使用乙腈溶剂进行提取时,3次平行样本的加标回收率最稳定,16种PAEs的加标回收率均在80%~120%之间。使用T3色谱柱时,在15 min内16种PAEs全部分离,分离效果较好。方法精密度≤7.95%,检出限在0.001~0.077 ng/m³之间,加标回收率为83.8%~117.6%。采用本实验方法,对2021年11—12月采集的上海市室外同一采样点不同时期的PM_2.5样本（n=9）进行检测,共检出7种邻苯二甲酸酯类化合物,其中5种检出率为100%,分别为邻苯二甲酸二甲酯（dimethyl phthalate,DMP）（0.26~6.39 ng/m³）、邻苯二甲酸二乙酯（diethyl phthalate,DEP）（0.96~2.04 ng/m³）、邻苯二甲酸二异丁酯（diisobutyl phthalate,DiBP）（9.46~63.40 ng/m³）、邻苯二甲酸二丁酯（dibutyl phthalate,DBP）2.52~44.60 ng/m³和邻苯二甲酸二-2-乙基己酯[bis（2-ethylhexyl） phthalate,DEHP]（6.29~59.40 ng/m³）。结论该方法的加标回收率稳定,检出限低,准确度和灵敏度高;实验前处理步骤简单,分析时间短,可以用于PM_2.5中PAEs的检测。

关键词: 邻苯二甲酸酯, 大气细颗粒物, 超高效液相色谱-串联质谱, 超声提取

Abstract: Objective To establish a rapid detection method for 16 phthalate esters（PAEs） in ambient air fine particulate matter（PM_2.5） by ultrasonic extraction ultra high performance liquid chromatography-tandem mass spectrometry. Methods The samples were collected onto a quartz filter membrane by a sampler equipped with the PM_2.5 cutting head. By comparing the extraction efficiency of different extraction solutions,selecting the appropriate extraction solution for ultrasonic extraction of the sample,comparing the separation effect and retention time of three chromatographic columns,16 types of PAEs were detected using ultra high performance liquid chromatography tandem mass spectrometry,and quantified using internal standard method to obtain indicators such as linearity and detection limit. An appropriate amount of standard was added to the quartz filter membrane to evaluate the recovery rate and precision of the method. Results The linear range of 16 PAEs compounds was within the range of 0.5 to 200 ng/mL,and all had good linear relationships,with R>0.995 0. Comparing the extraction effects of 50% methanol aqueous solution,50% acetonitrile aqueous solution,methanol and acetonitrile on the samples with the concentration of 10,50,100 μg/L after spiked,the average recovery of standard addition（n=3） was 71.45%-126.8%,51.71%-124.40%,68.62%-210.3% and 84.08%-110.28%. When using acetonitrile solvent for extraction,the recovery rates of three parallel samples were the most stable,and the recovery rates of 16 PAEs were all between 80% and 120%.When using T3 chromatographic column,all 16 PAEs were separated within 15 minutes,and the separation effect was better. The method precision was ≤7.95%,the detection limit was between 0.001 and 0.077 ng/m³,and the recovery rate was 83.8%-117.6%. Using this method,PM_2.5 samples（n=9） collected from the same outdoor sampling point in Shanghai from November to December 2021 at different periods were detected. A total of 7 phthalate ester compounds were detected,of which 5 had a detection rate of 100%,namely dimethyl phthalate（DMP）（0.26-6.39 ng/m³）,diethyl phthalate（DEP）（0.96-2.04 ng/m³）,and diisobutyl phthalate（DiBP）（9.46-63.40 ng/m³）,dibutyl phthalate（DBP）（2.52-44.60 ng/m³） and di-2-ethylhexyl phthalate（DEHP）（6.29-59.40 ng/m³）. Conclusion The spiked recovery rate of this method is stable,the detection limit is low,and the accuracy and sensitivity are high. The pre experimental processing steps are simple and the analysis time is short,which can be used for the detection of phthalate esters in PM_2.5.

Key words: Phthalate esters, Atmospheric fine particulate matter, Ultra high performance liquid chromatography-tandem mass spectrometry, Ultrasound extraction

中图分类号:

R115

杨其帆, 蔡菁婷, 范惠莹. 环境空气细颗粒物中16种邻苯二甲酸酯类化合物的超高效液相色谱-串联质谱测定法. [J]职业与健康, 2023, 39(23): 3206-3211.

YANG Qifan, CAI Jingting, FAN Huiying. Ultra high performance liquid chromatography-tandem mass spectrometry determination of 16 phthalate esters in fine particulate matter in ambient air. [J]OCCUPATION AND HEALTH, 2023, 39(23): 3206-3211.

参考文献

[1] FENG Y X,FENG N X,ZENG L J,et al.Occurrence and human health risks of phthalates in indoor air of laboratories[J].Sci Total Environ,2020,707:135609.
[2] 余涵. 食品中的邻苯二甲酸酯来源及对人体危害[J].现代食品, 2021(19):41-43.
[3] 夏天,闵巍,詹铭.儿童尿液中5种邻苯二甲酸酯代谢物的固相萃取-超高液相色谱-串联质谱测定法[J].职业与健康,2020,36(7):890-893.
[4] RAMZI A,GIREESHKUMAR T,RAHMAN K H,et al.Phthalic acid esters-A grave ecological hazard in Cochin estuary,India[J].Mar Pollut Bull,2020,152:110899.
[5] 杨文韬,匡武,郑西强.邻苯二甲酸酯类化合物在环境中的污染现状及生态风险研究进展[J].环境保护与循环经济,2020,40(2):34-40,60.
[6] 袁泉. 基于黑龙江大学站研究城市大气邻苯二甲酸酯污染特征[D].哈尔滨:黑龙江大学,2019.
[7] 刘正丹,白文娟,刘俊玲,等.武汉市居民住宅室内空气颗粒物中邻苯二甲酸酯污染状况[J].公共卫生与预防医学,2020,31(4):36-40.
[8] 黄伟,淡默,舒木水,等.空气中邻苯二甲酸酯分布特征与人群暴露研究进展[J].环境与职业医学,2019,36(4):345-354.
[9] BENJAMIN S,MASAI E,KAMIMURA N,et al.Phthalates impact human health:Epidemiological evidences and plausible mechanism of action[J].J Hazard Mater,2017,340:360-383.
[10] 宫雅雯,李圆龙,崔彤,等.邻苯二甲酸酯对男性(雄性)生殖毒性的研究进展[J].中国计划生育学杂志,2021,29(3):629-634.
[11] 于召龙,柳超,田纪伟.邻苯二甲酸二丁酯生殖及发育毒性的研究进展[J].职业与健康,2020,36(18):2582-2585.
[12] 刘国敏. 我国邻苯二甲酸酯环境污染现状及对女性(雌性)生殖健康的危害[J].职业卫生与应急救援,2020,38(3):320-324.
[13] 曹龙,张朝升,陈秋丽,等.邻苯二甲酸酯的环境污染和生态行为及毒理效应研究进展[J].生态毒理学报,2018,13(2):34-46.
[14] CHENG Z,LI H H,WANG H S,et al.Dietary exposure and human risk assessment of phthalate esters based on total diet study in Cambodia[J].Environ Res,2016,150:423-430.
[15] PU S Y,HAMID N,REN Y W,et al.Effects of phthalate acid esters on zebrafish larvae:Development and skeletal morphogenesis[J].Chemosphere,2020,246:125808.
[16] 王琼,董小艳,杨璐璐,等.基于北京市大气PM_2.5中9种元素的环境健康风险评价[J].环境卫生学杂志,2018,8(3):197-203.
[17] 卜素贝. 邻苯二甲酸酯空气污染特性及与颗粒物关联研究[D].哈尔滨:哈尔滨工业大学,2018.
[18] 曹亚强,顾雯,崔倩,等.北京市朝阳区采暖期和非采暖期PM_2.5中四种邻苯二甲酸酯的污染特征及健康风险[J].环境卫生学杂志,2022, 12(2):95-101.
[19] 刘正丹,汪耀,韩清,等.超声提取-气相色谱-质谱法测定空气颗粒物中邻苯二甲酸酯类化合物[J].中国卫生检验杂志,2020,30(16):1927-1931.
[20] 张玉美,张明洪,李红梅,等.食品级塑料包装袋中16种塑化剂的3种前处理方法研究[J].职业与健康,2018,34(1):32-35,39.
[21] 戴玄吏,李丹,章霖之,等.微波萃取/气质联用法测定细颗粒物(PM_2.5)中邻苯二甲酸酯类化合物[J].分析测试学报,2014,33(3):349-353.
[22] 崔永博,白莉,李春辉,等.室内空气邻苯二甲酸酯的污染危害及检测方法研究进展[J].北方建筑,2020,5(5):35-39.
[23] 张续,韩林学,邱天,等.改进的UPLC-MS/MS法测定尿中12种邻苯二甲酸酯代谢物[J].环境卫生学杂志,2022,12(1):56-63.
[24] 薛蕊. 食品中邻苯二甲酸酯类塑化剂的检测技术研究进展[J].现代食品,2021(18):134-136.
[25] 苗萌,李佳,张静怡,等.饮品中邻苯二甲酸酯类物质的检测技术进展[J].分析试验室,2021,40(11):1358-1364.
[26] 王肖红,胡小键,张海婧,等.大气PM_2.5中15种邻苯二甲酸酯的超声提取-超高效液相色谱串联质谱测定法[J].环境与健康杂志,2015, 32(1):49-53.