磁性氮掺杂石墨烯固相萃取环境水样中的4种有机氯污染物

引用本文: 陈林吉, 朱晁乐, 曹小吉, 周婷, 叶学敏, 莫卫民. 磁性氮掺杂石墨烯固相萃取环境水样中的4种有机氯污染物[J]. 分析化学, 2017, 45(5): 762-769. doi: 10.11895/j.issn.0253-3820.170016 shu

Citation: CHEN Lin-Ji, ZHU Chao-Le, CAO Xiao-Ji, ZHOU Ting, YE Xue-Min, MO Wei-Min. Magnetic Solid Phase Extraction with Fe₃O₄-Grafted Nitrogen- Doped Graphene for Determination of Four Organochlorine Contaminants in Environmental Water Samples[J]. Chinese Journal of Analytical Chemistry, 2017, 45(5): 762-769. doi: 10.11895/j.issn.0253-3820.170016 shu

磁性氮掺杂石墨烯固相萃取环境水样中的4种有机氯污染物

1.
浙江工业大学, 化学工程学院, 杭州 310014;
2.
浙江工业大学, 分析测试中心, 杭州 310014
基金项目:
本文系浙江省科技厅公益技术应用研究项目（Nos. 2017C33014，2014C03026）资助。

摘要: 采用化学共沉淀法成功合成了磁性氮掺杂石墨烯纳米材料，对其吸附性能进行了初步探讨。此磁性纳米材料对对氯间二甲苯酚的吸附不局限于均匀的单分子层吸附，吸附动力学符合准二级动力学模型。将其作为磁性固相吸附剂，通过对吸附剂用量、超声萃取时间、水样pH值、上样体积等条件的优化，建立了超声辅助磁性固相萃取-气相色谱/串联质谱同时测定环境水样中的三氯生（TCS）、对氯间二甲苯酚（PCMX）、六氯苯（HCB）和2，2'，4，4'，5，5'-六氯联苯（PCB-153） 4种有机氯污染物的方法。在优化条件下，将6.0 mg Fe₃O₄/N-G分散于100 mL水样中，调节水样至pH 5，超声萃取15 s，磁性分离，3 mL乙醇和2 mL二氯甲烷分步洗脱，洗脱液氮吹定容，进行气相色谱-质谱联用分析。4种有机污染物在0.1~10 μg/L范围内与峰面积呈良好的线性关系，相关系数为0.9983~0.9999，检出限（S/N=3）和定量限（S/N=10）分别为0.05~0.6 ng/L和0.4~2.4 ng/L，3个加标浓度水平的回收率为68.3%~103.4%，日内、日间测定的相对标准偏差分别为3.3%~6.9%和3.4%~9.4%（n=6）。本方法简单方便，易于操作，适用于环境水样中有机氯污染物的检测。

关键词:

English

Magnetic Solid Phase Extraction with Fe₃O₄-Grafted Nitrogen- Doped Graphene for Determination of Four Organochlorine Contaminants in Environmental Water Samples

1.
College of Chemical Engineering Science, Zhejiang University of Technology, Hangzhou 310014, China;
2.
Research Center of Analysis and Measurement, Zhejiang University of Technology, Hangzhou 310014, China
Received Date: 10 January 2017
Revised Date: 28 February 2017

Abstract: Fe₃O₄-grafted nitrogen-doped graphene (Fe₃O₄/N-G) nanomaterials were synthesized by chemical co-precipitation method, and its adsorption properties were discussed preliminarily. It was demonstrated that the adsorption of parachlormetaxylenol on Fe₃O₄/N-G was not limited to uniform monolayer adsorption and the adsorption kinetic followed the pseudo-second-order kinetic mode. Then, an ultrasound-assisted magnetic solid-phase extraction with Fe₃O₄/N-G as the magnetic adsorbent has been developed for the determination of four compounds including triclosan, chloroxylenol, hexachlorobenzene and 2,2',4,4',5,5'-hexachlorobiphenyl in environmental water samples, in combination with gas chromatography coupled to tandem mass spectrometry. Several factors related to extraction efficiencies, such as the amount of adsorbent, extraction time, sample pH and desorption conditions were investigated. The proposed preparation procedure was as follows: 6.0 mg of Fe₃O₄/N-G was dispersed into 100 mL of water sample under ultrasound. After 15 s, the Fe₃O₄/N-G carrying four compounds was separated from the water sample by an external magnetic field. Then, the targets were eluted from Fe₃O₄/N-G with 3 mL of ethanol and 2 mL of dichloromethane, sequentially. Finally, the eluent was dried under a mild stream of nitrogen and reconstituted with methanol and dichloromethane (1∶1, V/V) for the subsequent GC-MS/MS analysis. Under the optimized condition, an excellent linearity was observed in the range of 0.1-10 ng/L for the four compounds, with the correlation coefficients ranging from 0.9983 to 0.9999. The limits of detections (S/N=3) ranged from 0.05 to 0.6 ng/L and the limits of quantity (S/N=10) ranged from 0.2 to 2.4 ng/L. The mean recoveries at three spiked levels ranged from 68.2% to 99.6%. The relative standard deviations (RSDs) of intraday and interday were in the range of 3.3%-6.9% and 3.4%-9.4% (n=6), respectively. The proposed method was demonstrated to be simple and feasible for the trace analysis of antimicrobial agents and organochlorine contaminants in environmental water samples.

Key words:

1. [1]
  1 Crinnion W J. Altern. Med. Rev., 2010, 15(2):101-109
2. [2]
  Guo Q, Yan J, Wen J J, Hu Y Y, Chen Y B, Wu W J. Sci. Total. Environ., 2016, 571:1304-1311
3. [3]
  Shao D D, Sheng G D, Chen C L, Wang X K, Nagatsub M. Chemosphere, 2010, 79 (7):679-685
4. [4]
  Liu P, Zhang D J, Zhan J H. J. Phys. Chem. A, 2010, 114(50):13122-13128 5 GB 3838-2002, Environmental Quality Standards for Surface Water. National Standards of the People's Republic of China 地表水环境质量标准. 中华人民共和国国家标准. GB3838-2002
5. [5]
  GB 5749-2006, Standards for Dringing Water Quality. National Standards of the People's Republic of China 生活饮用水卫生标准. 中华人民共和国国家标准. GB 5749-2006
6. [6]
  HJ 715-2014, Water Quality-Determination of Polychorinated Biphenyls(PCBs)-Gas Chromatography Mass Spectrometry. The State Environmental Protection Standard of the People's Republic of China 水质-多氯联苯的测定-气相色谱-质谱法. 中华人民共和国国家环境保护标准. HJ 715-2014
7. [7]
  SHAO Yang, YANG Guo-Sheng, LIU Wei-Hua, MA Ling-Ling, LUO Min, HAN Shen, XU Dian-Dou. Chinese J. Anal. Chem., 2016, 44(5):698-706 邵阳, 杨国胜, 刘韦华, 马玲玲, 罗敏, 韩深, 徐殿斗. 分析化学, 2016, 44(5):698-706
8. [8]
  Han Q, Wang Z H, Xia J F, Xia L H, Chen S, Zhang X Q, Ding M Y. J. Sep. Sci., 2013, 36(21-22):3586-3591
9. [9]
  Chen M J, Liu Y T, Lin C W, Ponnusamy V K, Jen J F. Anal. Chim. Acta, 2013, 767(5):81-87
10. [10]
  Luo Y B, Li X, Jiang X Y, Cai B D, Zhu F P, Zhang H F, Chen Z G, Pang Y Q, Feng Y Q. J. Chromatogr. A, 2015, 1406:1-9
11. [11]
  Sun T, Yang J, Li L J, Wang X Z, Li X W, Jin Y R. Chromatographia, 2016, 79(5):345-353
12. [12]
  Wang X, Liu B, Lu Q P, Qu Q S. J. Chromatogr. A, 2014, 1362(44):1-15
13. [13]
  Xiao R, Zhang X T, Zhang X N,Niu J H, Lu M H, Liu X H, Cai Z W. Talanta, 2017, 166:262-267
14. [14]
  Menezes H C, de Barcelos S M R, Macedo D F D, Purceno A D, Machado B F, Teixeira A P C, Lago R M, Serp P, Cardeal Z L. Anal. Chim. Acta, 2015, 873:51-56
15. [15]
  PENG San, GUO Hui-Lin, KANG Xiao-Feng. Acta Phys. Chim. Sci., 2014, 30(9):1778-1786 彭三, 郭慧林, 亢晓峰. 物理化学学报, 2014, 30(9):1778-1786
16. [16]
  Qu S, Wang J, Kong J L, Yang P Y, Chen G. Talanta, 2007, 71(3):1096-1102
17. [17]
  Cao X J,Shen L X, Ye X M, Zhang F F, Chen J Y, Mo W M. Analyst, 2014, 139(8):1938-1944
18. [18]
  Wang W N, Li Y P, Wu Q H, Wang C, Zang X H, Wang Z, Anal. Methods, 2012, 4(3):766-772
19. [19]
  Ma Z Y, Guan Y P, Liu H Z. J. Polym. Sci. A, 2005, 43(15):3433-3439
20. [20]
  LIU Wan-Yi, YANG Lu-Ze, YU Meng, LIU Miao. Chinese J. Anal. Chem., 2016, 44(5):707-715 刘宛宜, 杨璐泽, 于萌, 刘淼. 分析化学, 2016, 44(5):707-715
21. [21]
  Orozco-Guareño E, Santiago-Gutiérrez F, Morán-Quiroz J L, Moran-Quiroz, J L, Hernandez-Olmos S L, Soto V, de la Cruz W, Manriquez R, Gomez-Salazar S. J. Colloid Interface Sci., 2010, 349(2):583-593
22. [22]
  Wang R Z, Huang D L, Liu Y G,Peng Z W, Zeng G M, Lai C, Xu P, Huang C, Zhang C, Gong X M. RSC Adv., 2016, 6(108):106201-106210
23. [23]
  Ke Y Y, Zhu F, Zeng F, Luan T G, Su C Y, Ou Yang G F. J. Chromatogr. A, 2013, 1300(14):187-192
24. [24]
  Pintado-Herrera M G, González-Mazo E, Lara-Martín P A. Chemosphere, 2014, 95(1):478-485

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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

磁性氮掺杂石墨烯固相萃取环境水样中的4种有机氯污染物

English

Magnetic Solid Phase Extraction with Fe₃O₄-Grafted Nitrogen- Doped Graphene for Determination of Four Organochlorine Contaminants in Environmental Water Samples

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

磁性氮掺杂石墨烯固相萃取环境水样中的4种有机氯污染物

English

Magnetic Solid Phase Extraction with Fe3O4-Grafted Nitrogen- Doped Graphene for Determination of Four Organochlorine Contaminants in Environmental Water Samples

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Magnetic Solid Phase Extraction with Fe₃O₄-Grafted Nitrogen- Doped Graphene for Determination of Four Organochlorine Contaminants in Environmental Water Samples

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs