纺织学报 ›› 2021, Vol. 42 ›› Issue (05): 130-137.doi: 10.13475/j.fzxb.20200903508

• 染整与化学品 • 上一篇    下一篇

采用超声辅助-固相萃取气相色谱串联质谱法测定废棉中的增塑剂

铁建成1, 刘俊1,2, 贾丽霞1,2(), 藏蒙蒙1, 孙慧芹1, 朱鹏1   

  1. 1.新疆大学 纺织与服装学院, 新疆 乌鲁木齐 830046
    2.中华人民共和国乌鲁木齐海关, 新疆 乌鲁木齐 830063
  • 收稿日期:2020-09-15 修回日期:2021-02-06 出版日期:2021-05-15 发布日期:2021-05-20
  • 通讯作者: 贾丽霞
  • 作者简介:铁建成(1993—),男,硕士生。主要研究方向为纺织化学与分析。
  • 基金资助:
    新疆维吾尔自治区科技重大专项跨境纺织原料类固体废物鉴别及综合利用集成示范项目(2020A03002-2);乌鲁木齐海关总署项目(2019HK012);新疆大学自治区研究生教育创新计划项目(XJ2020G070)

Simultaneous determination of plasticizers in waste cotton by ultrasonic assisted solid phase extraction gas chromatography tandem mass spectrometry

TIE Jiancheng1, LIU Jun1,2, JIA Lixia1,2(), ZANG Mengmeng1, SUN Huiqin1, ZHU Peng1   

  1. 1. College of Textiles and Clothing, Xinjiang University, Urumqi, Xinjiang 830046, China
    2. Urumqi Customs District P.R. China, Urumqi, Xinjiang 830063, China
  • Received:2020-09-15 Revised:2021-02-06 Online:2021-05-15 Published:2021-05-20
  • Contact: JIA Lixia

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摘要：

为开发废棉中增塑剂的高效定量分析方法,建立了超声辅助-固相萃取气相色谱串联质谱的方法,用于对废棉中18种邻苯二甲酸酯和5种己二酸酯类增塑剂的定性及定量分析。以正己烷-二氯甲烷(体积比为4∶1)作为提取剂,提取液经Alumina-N固相萃取柱纯化,采用选择离子扫描模式,用外标法进行定量。结果表明:20种增塑剂在1~20 μg/mL,邻苯二甲酸二异庚酯、邻苯二甲酸二异壬酯、邻苯二甲酸二异癸酯在5~100 μg/mL的质量浓度范围内均呈现出良好的线性关系,检出限为0.084~1.748 μg/g,定量限为0.336~6.992 μg/g;在5、10和20 μg/mL加标水平下,23种增塑剂的回收率为83.3%~104.3%,日内及日间的相对标准偏差分别为1.9%~8.1%和1.6%~8.7%,满足检测要求。该方法操作简单、干扰小,可检测出废棉中邻苯二甲酸酯和己二酸酯类增塑剂的微量残留。

关键词: 超声辅助-固相萃取, 气相色谱串联质谱, 废棉, 邻苯二甲酸酯, 己二酸酯, 增塑剂

Abstract:

In order to develop an efficient quantitative analysis method for plasticizers in waste cotton, an ultrasound-assisted solid phase extraction gas chromatography tandem mass spectrometry (UE-SPE-GC/MS) method was established to simultaneously analyze 18 types of phthalates in waste cotton, using qualitative and quantitative analysis of formate and 5 adipate plasticizers. Using n-hexane-dichloromethane (volume ratio 4∶1) as the extractant, the extract was purified with an Alumina-N solid phase extraction column, using selective ion scanning mode and external standard method for qua.pngication. The results showed that 20 plasticizers demonstrate a good linear relationship in the concentration range of 1-20 μg/mL, DIHP, DINP and DIDP in the concentration range of 5-100 μg/mL), with the correlation coefficient being 0.990 7-0.999 6.The detection limit it is 0.084-1.748 μg/g, and the limit of qua.pngication is 0.336-6.992 μg/g. At the spiked levels of 5, 10 and 20 μg/mL, the recoveries of the 23 plasticizers were between 83.3%-104.3%, and the intraday and interday relative standard deviations were 1.9%-8.1% and 1.6%-8.7%, respectively, meeting the requirements of testing. The UE-SPE-GC/MS method is simple to operate and has little interference. It can accurately detect trace residues of phthalate and adipate plasticizers in waste cotton.

Key words: ultrasonic assisted solid phase extraction, gas chromatography tandem mass spectrometry, waste cotton, phthalates, adipates, plasticizer

中图分类号: 

  • TP202

表1

23种增塑剂的保留时间及离子质荷比"

序号 化合物 CAS号 保留时间/
min		 定量离子
质荷比		 定性离子
质荷比
1 DEA 141-28-6 8.250 111 157、29、55
2 DEP 84-66-2 10.067 149 177、76、150
3 DIBA 141-04-8 10.714 129 57、185、41
4 DBA 105-99-7 11.440 129 185、111、41
5 DPrP 131-16-8 11.603 149 150、76、104
6 DIBP 84-69-5 12.554 149 57、104、150
7 DBP 84-74-2 13.622 149 150、104、76
8 DMEP 117-82-8 14.090 59 58、149、104
9 DPP 131-18-0 16.040 149 150、237、76
10 BMPP 146-50-9 17.629 149 85、43、251
11 BBOEA 141-18-4 17.861 57 56、85、45
12 DEEP 605-54-9 18.173 149 150、251、55
13 DNHP 84-75-3 18.721 149 104、233、251
14 BBP 85-68-7 18.835 149 91、206、104
15 DEHA 103-23-1 19.466 129 57、112、55
16 DIHP 41451-28-9 19.641~21.158 256 149、57、99
17 DCHP 84-61-7 21.226 149 167、150、55
18 DHP 3648-21-3 21.481 149 150、57、265
19 DEHP 117-81-7 21.610 149 167、57、70
20 DNOP 117-84-0 24.207 149 279、150、43
21 DINP 20548-62-3 24.576~25.503 293 149、127、57、
22 DIDP 26761-40-0 25.605~26.665 307 149、141、71、
23 DNP 84-76-4 26.845 149 293、71、57

图1

23种增塑剂标准品选择离子扫描总离子流色谱图"

图2

不同萃取溶剂对萃取效率影响"

图3

不同萃取时间对萃取效率的影响"

图4

样品提取液在固相萃取前和固相萃取后色谱图对比"

表2

23种增塑剂的线性相关系数、线性范围、检出限(LOD)和定量限(LOQ)"

化合物 回归方程 r 线性范围/(μg·mL-1) LOD/(μg·g-1) LOQ/(μg·g-1)
DEA y=82 420x+19 171 0.995 9 1~20 0.201 0.804
DEP y=511 008x-16 121 0.996 3 1~20 0.121 0.484
DIBA y=744 819x+145 000 0.998 4 1~20 0.203 0.812
DBA y=171 738x-101 345 0.998 9 1~20 0.192 0.768
DPrP y=775 135x+202 487 0.990 7 1~20 0.223 0.892
DIBP y=720 836x+83 739 0.999 6 1~20 0.113 0.452
DBP y=916 542x+71 567 0.993 4 1~20 0.130 0.52
DMEP y=317 517x-207 238 0.998 8 1~20 0.149 0.596
DPP y=947 408x-294 655 0.996 7 1~20 0.173 0.692
BMPP y=439 535x-257 273 0.998 1 1~20 0.153 0.612
BBOEA y=132 532x-171 820 0.998 0 1~20 0.097 0.388
DEEP y=765 154x-309 162 0.997 3 1~20 0.164 0.656
DNHP y=2E+06x+643 820 0.995 9 1~20 0.227 0.908
BBP y=485 434x-56 443 0.994 6 1~20 0.186 0.744
DEHA y=333 361x-191 226 0.997 9 1~20 0.172 0.688
DIHP y=104 740x-73 273 0.997 9 5~100 1.464 5.856
DCHP y=764 873x-304 698 0.997 1 1~20 0.196 0.784
DHP y=903 620x-498 051 0.998 4 1~20 0.084 0.336
DEHP y=610 048x-184 988 0.997 1 1~20 0.123 0.492
DNOP y=956 467x-721 251 0.998 2 1~20 0.114 0.456
DINP y=115 324x-144 526 0.997 9 5~100 1.423 5.692
DIDP y=58 518x+33 939 0.993 0 5~100 1.748 6.992
DNP y=832 901x-457 295 0.996 9 1~20 0.317 1.268

表3

23种增塑剂的平均加标回收率和相对标准偏差(RSD)"

化合物 添加水平/
(μg·mL-1)		 回收率/% RSD(n=6)/% 化合物 添加水平/
(μg·mL-1)		 回收率/% RSD(n=6)/%
日内 日间 日内 日间 日内 日间 日内 日间
DEA 5 97.7 97.9 3.3 2.7 DNHP 5 98.0 98.3 2.1 4.3
10 95.5 95.1 4.0 3.4
10 90.0 91.1 5.4 5.5
20 96.2 95.4 4.5 4.6
20 92.8 93.8 3.8 3.7
DEP 5 92.4 92.1 2.1 3.0 BBP
5 104.3 103.3 2.2 2.7
10 95.5 95.0 4.1 3.2
10 98.4 98.9 4.5 2.9
20 98.9 97.4 3.5 3.5
20 101.2 99.6 3.5 3.0
DIBA 5 100.8 100.9 2.8 1.6 DEHA
5 100.1 99.9 5.9 3.9
10 83.3 83.4 3.5 3.7
10 89.1 87.3 3.3 5.5
20 87.9 88.2 3.4 2.7
20 91.0 89.1 3.6 4.6
DBA 5 101.4 99.3 3.2 4.6 DIHP
25 94.0 93.9 4.7 4.5
10 87.6 87.5 2.3 2.9
50 86.8 85.5 7.3 8.2
20 92.9 92.3 2.9 3.6
DPrP 5 103.1 101.9 1.9 1.9 DCHP 100 90.2 89.8 8.1 8.1
10 100.3 100.3 3.5 3.5
5 100.3 97.9 3.8 4.6
20 98.8 98.4 4.3 3.6
10 101.3 99.7 3.0 3.2
DIBP 5 91.8 94.0 4.8 4.6 DHP
20 98.5 97.8 3.6 4.3
10 93.8 94.7 4.9 4.1
5 93.3 92.5 2.6 4.9
20 94.6 94.2 2.3 2.7
10 90.9 91.6 3.6 4.1
DBP 5 95.8 94.2 2.6 2.0 DEHP
20 99.1 97.9 4.4 3.3
10 94.1 90.4 3.2 5.2
5 98.6 99.4 7.2 6.3
20 90.0 89.6 7.5 8.7
10 91.4 89.8 5.3 5.4
DMEP 5 88.7 88.2 3.8 2.5 DNOP
20 95.9 95.7 4.5 4.4
10 90.7 89.5 4.6 4.0
5 86.0 85.5 3.8 3.6
20 89.4 88.0 4.8 4.8
DPP 5 101.9 99.6 4.5 5.0 DINP 10 85.1 85.6 4.5 4.3
10 90.6 89.9 4.9 5.4
20 87.0 87.3 5.8 5.3
20 98.2 97.5 3.7 4.4
25 95.4 92.5 5.1 5.4
BMPP 5 85.9 86.1 5.3 4.2 DIDP
50 89.3 88.7 4.5 3.7
10 87.3 86.7 5.4 3.1
100 86.5 85.8 5.0 6.0
20 86.8 87.1 5.9 5.7
25 88.6 87.5 4.6 4.8
BBOEA 5 102.0 102.1 2.2 1.8 DNP
50 84.8 85.2 6.5 6.9
10 98.7 98.41 5.7 4.1
100 86.0 84.9 7.2 6.6
20 101.0 100.5 2.9 3.1
5 94.5 94.9 5.4 4.7
DEEP 5 89.1 88.2 7.5 3.6
10 92.7 92.2 3.5 4.0
10 90.4 89.9 3.4 2.8
20 91.5 91.2 5.9 4.7
20 92.5 91.0 4.6 4.3
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