改进的固相萃取-气相色谱-质谱法测定复杂基质文具用品中6种邻苯二甲酸酯类化合物的含量  

Determination of 6Phthalate Ester Compounds in Stationery Supplies with Complex Matrix by Improved Gas Chromatography-Mass Spectrometry with Solid Phase Extraction

作　　者：马宇熙 房苗[2] 胡海 MA Yuxi;FANG Miao;HU Hai(Key Laboratory of Special Environment and Health Research in Xinjiang,Xinjiang Medical University,Urumqi 830054,China;Urumqi Centre for Disease Control and Prevention,Urumqi 830026,China)

机构地区：[1]新疆医科大学新疆特殊环境与健康研究重点实验室,乌鲁木齐830054 [2]乌鲁木齐市疾病预防控制中心,乌鲁木齐830026

出　　处：《理化检验（化学分册）》2023年第11期1241-1248,共8页Physical Testing and Chemical Analysis(Part B:Chemical Analysis)

基　　金：新疆特殊环境与健康研究重点实验室开放课题项目资助项目(SKL-SEHR-2021-10)。

摘　　要：提出了乙腈萃取-固相萃取柱净化-气相色谱-质谱法测定4种复杂基质文具用品(塑料书皮、包书膜、笔杆、尺子)中6种邻苯二甲酸酯类化合物[PAEs,包括邻苯二甲酸二丁酯(DBP)、邻苯二甲酸丁苄酯(BBP)、邻苯二甲酸二(2-乙基)己酯(DEHP)、邻苯二甲酸二异壬酯(DINP)、邻苯二甲酸二异癸酯(DIDP)、邻苯二甲酸二正辛酯(DNOP)]含量,并对方法的前处理条件,包括萃取剂(乙酸乙酯、二氯甲烷、体积比1∶1的正己烷-二氯甲烷混合溶液、正己烷、丙酮、四氢呋喃、甲苯、乙腈)、萃取温度(0,20,30,40℃)和萃取时间(10,20,30,40 min)等进行了优化。将样品剪成10 mm×10 mm的小片,分取0.2 g,加入乙腈5 mL,振荡20 min,于40℃超声萃取30 min,分取1 mL萃取液过活化好的固相萃取柱(Si/PSA SPE玻璃小柱),用10 mL乙腈洗脱柱子,收集洗脱液,氮吹至近干,用正己烷溶解残渣并定容至1 mL,气相色谱-质谱法分析,外标法定量。净化其他7种溶剂的萃取液时,先用5 mL正己烷淋洗,再用10 mL体积比2∶8的正己烷和乙酸乙酯混合溶液洗脱,其他步骤同乙腈的。各溶剂的萃取效果均采用实际样品中PAEs测定值以及加标回收率来评价。结果显示,乙腈对不同材质文具用品的适应性更强,40℃超声萃取30 min时萃取得到的PAEs更多且其测定值以及回收率更高(大于70.0%)。6种PAEs的质量浓度分别在0.2~10.0 mg·L^(-1)(DBP、BBP、DEHP和DNOP)和2.0~100.0 mg·L^(-1)(DINP和DIDP)内与对应的峰面积呈线性关系,检出限(3S/N)为0.003~0.05 mg·kg-1;加标回收率为74.1%~107%,测定值的相对标准偏差(n=6)为1.2%~5.1%。方法用于12份实际样品的分析,DNOP、DINP、DIDP均未检出,DBP、BBP和DEHP的检出总量未超过GB 21027-2020规定的限量。A method of gas chromatography-mass spectrometry with acetonitrile extraction and solid phase extraction column purification was proposed for the determination of 6phthalate ester compounds[PAEs,including dibutyl phthalate(DBP),benzyl butyl phthalate(BBP),di(2-ethyl)hexyl phthalate(DEHP),di-iso-nonyl phthalate(DINP),di-n-octyl phthalate(DNOP)and di-n-decyl phthalate(DIDP)]in 4stationery supplies(plastic book covers,book membranes,pen holders,rulers)with complex matrix,and the pretreatment conditions of the method,including extractant(ethyl acetate,dichloromethane,mixed solution of n-hexane and dichloromethane at volume ratio of 1∶1,n-hexane,acetone,tetrahydrofuran,toluene,acetonitrile),extraction temperature(0,20,30,40℃),and extraction time(10,20,30,40min)were optimized.The sample was cut into small pieces with the size of 10cm×10cm.An aliquot(0.2g)was taken and immersed into 5mL of acetonitrile,and the mixture was shaken for 20min,and extracted by ultrasound at 40℃for 30min.Then 1mL of the extract was taken and passed through the solid phase extraction column(Si/PSA SPE glass column)activated beforehand.The above column was eluted by 10mL of acetonitrile,and the eluate was collected,and blown to near dryness by nitrogen.The residue was dissolved by n-hexane,and made its volume up to 1mL.The resulting solution was analyzed by gas chromatography-mass spectrometry,with external standard method for quantification.When purifying the extract of the other 7solvents,5mL of n-hexane was used for rinsing,and 10mL of mixed solution composed of n-hexane and ethyl acetate at volume ratio of 2∶8.was used for elution.The other steps were the same as those of acetonitrile.The extraction effect of each solvent was evaluated using determined values of PAEs in actual samples and spiked recoveries.It was shown that acetonitrile had stronger adaptability to stationery supplies made of different materials.When ultrasonic extraction was made at 40℃for 30min,more PAEs were obtained,and their determined values and recoveries

关 键 词：气相色谱-质谱法 邻苯二甲酸酯类化合物 复杂基质 文具用品 前处理方法 优化 

分 类 号：O657.63[理学—分析化学]