气相色谱法测定地下水中拟除虫菊酯有机氯百菌清等24种农药残留

郭晓辰; 饶竹; 高冉

气相色谱法测定地下水中拟除虫菊酯有机氯百菌清等24种农药残留

国家地质实验测试中心, 北京 100037

基金项目: 中国地质大调查项目（1212011120283，1212011220943）

详细信息

作者简介: 郭晓辰, 助理工程师, 从事环境污染物监测分析研究.E-mail: guoxc2012@163.com

通讯作者: 饶竹, 研究员, 从事环境有机污染物分析.E-mail: raozhu@126.com

中图分类号: P641;S482.32;O657.71

收稿日期: 2013-08-23

录用日期: 2013-09-14

刊出日期: 2014-03-25

Determination of 24 Pesticides including Pyrethroids, Organochlorines and Chlorothalonil in Underground Water by Gas Chromatography

National Research Center for Geoanalysis, Beijing 100037, China

More Information

Corresponding author: RAO Zhu, raozhu@126.com

Received Date: 23 August 2013

Accepted Date: 14 September 2013

Publish Date: 25 March 2014

摘要

摘要:
拟除虫菊酯类、有机氯、百菌清等农药均属于电负性强化合物，采用气相色谱-电子捕获检测器（GC-ECD）检测具有较高的灵敏度，但由于拟除虫菊酯类农药分子量较大，其灵敏度显著低于有机氯，使得各类化合物进行分类检测的流程长、分析效率低。本文通过优选分析色谱柱和进样口温度等条件，利用气相色谱的色谱柱程序升压功能实现了多类别24种农药残留的快速、准确测定。实验中以正己烷为溶剂进行液液萃取，Florisil固相萃取柱净化，选择有机氯专用色谱柱（RTX-CLPesticides 2）进行分析，GC-ECD仪器在0.5~6000 ng/mL浓度范围内呈线性，方法检出限为1.00~12.00 ng/L，低、中、高三个浓度水平的加标回收率分别为80.3%~116%、79.9%~117%、85.7%~102%，相应的精密度（RSD，n=7）为1.5%~6.8%、1.3%~7.6%、1.1%~6.8%。本方法选用的有机氯专用色谱柱（RTX-CLPesticides 2）对多组分、多类别目标化合物有更好的分辨率，较通用型色谱柱（DB-5MS）更具分析优势；采用的色谱柱程序升压技术解决了拟除虫菊酯类化合物在气相色谱柱中停留时间过长而导致的低灵敏度、峰拖尾等技术难题。此方法灵敏、经济，分析通量高，可有效地同时分析多种类农药残留物质。
- 地下水 /
- 拟除虫菊酯 /
- 有机氯农药 /
- 百菌清 /
- 毒死蜱 /
- 气相色谱法 /
- 液液萃取
Abstract:
High sensitivity is required to determine pyrethroids, organochlorines, chlorothalonil and chlorpyrifos by using Gas Chromatography-Micro-Electron Capture Detector (GC-μECD) due to their high electro-negativity. The sensitivity of pyrethroids, which have higher molecular weights, is much lower than organochlorines. Moreover, the efficiency of determination is very low by different analyses patterns. This problem has been solved by using a column pressure program, and 24 compounds were determined efficiently at the same time by optimizing column conditions and inlet temperature. The underground water sample was treated by liquid-liquid extraction, Florisil SPE cleanup and analyzed by RTX-CL Pesticides 2 with GC-μECD. The calibration curves for 24 compounds were linear in the range of 0.5-6000 ng/mL, and the method detection limits were in the range of 1.00-12.00 ng/L. The matrix spiked experiments were studied at three different concentration levels. The mean recoveries for low, middle and high concentration were in the range of 80.3%-116%, 79.9%-117% and 85.7%-102% with precisions of 1.5%-6.8%, 1.3%-7.6% and 1.1%-6.8%, respectively. Compared to common chromatographic column (DB-5MS), the special chromatographic column (RTX-CLPesticides 2) is more efficient for analyzing multiple targets and category compounds. The low sensitivity and peak tailing problem of pyrethroids caused by long residence time in column was solved by using a column pressure program. The method is sensitive, accurate, and economical and maintains a high flux, which is easy to determine multiple pesticide residues simultaneously.
- underground water /
- pyrethroids /
- organochlorine pesticides /
- chlorothalonil /
- chlorpyrifos /
- Gas Chromatography /
- liquid-liquid extraction

HTML全文

图 1 24种农药多残留标准品色谱图

Figure 1.

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图 2 RTX-CLPesticides 2色谱柱与DB-5MS色谱柱的色谱图对比

Figure 2.

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图 3 柱压力对分析灵敏度影响

Figure 3.

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图 4 变压控制与恒压控制对比色谱图

Figure 4.

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图 5 进样口温度对分析灵敏度的影响

Figure 5.

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图 6 萃取溶剂对目标物加标回收率的影响

Figure 6.

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表 1 线性回归方程、相关系数、适用范围及方法检出限

Table 1. The linear regression equation, correlation coefficient, applicable concentration range and the detection limit

化合物	线性方程	相关系数 (R²)	检测范围 (ng/mL)	方法检出限 (ng/L)
六氯苯	y=262.92x+761.03	0.9999	0.50~500	1.00
α-六六六	y=373.08x+265.06	1.0000	0.50~500	1.00
γ-六六六	y=359.8x+227.04	1.0000	0.50~500	1.00
β-六六六	y=160.74x+443.96	0.9998	0.50~500	1.00
δ-六六六	y=313.15x-184.06	1.0000	0.50~500	1.00
七氯	y=291.06x+135.53	1.0000	0.50~500	1.00
百菌清	y=279.48x-2437.8	0.9996	1.00~1000	2.00
艾氏剂	y=289.8x+730.5	0.9998	0.50~500	1.00
毒死蜱	y=121.13x+581.76	0.9999	1.00~1000	2.00
三氯杀螨醇	y=34.886x+570.02	0.9999	3.00~3000	6.00
p, p’-DDE	y=271.48x+684.7	0.9998	0.50~500	1.50
狄氏剂	y=307.6x+416.01	0.9999	0.50~500	1.00
o, p’-DDT	y=178.14x-41.2	1.0000	0.50~500	1.50
p, p’-DDD	y=232.48x+324.2	1.0000	0.50~500	1.50
p, p’-DDT	y=218.48x-644.63	0.9997	0.50~500	1.50
联苯菊酯	y=55.832x+544.26	0.9999	1.60~1600	3.20
甲氰菊酯	y=63.579x-145.68	0.9999	1.60~1600	3.20
灭蚁灵	y=168.73x+829.94	0.9999	0.80~800	1.60
三氟氯氰菊酯	y=160.55x-1060.5	0.9996	1.20~1200	2.40
氯氰菊酯	y=106.77x-3342.1	0.9998	6.00~6000	12.0
氯菊酯	y=27.019x+714.92	0.9997	3.20~3200	6.40
高效氰戊菊酯	y=129.21x-2414.1	0.9991	2.00~2000	4.00
氟胺氰菊酯	y=126.73x-11235	0.9971	5.00~5000	10.0
溴氰菊酯	y=88.937x-688.5	0.9999	3.20~3200	6.40

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表 2 基质加标回收率及精密度

Table 2. The spike recoveries and the precision of the method for low, middle and high concentration

化合物	低浓度加标浓度(ng/L)	回收率平均值 (%)	RSD (%)	中间浓度加标浓度(ng/L)	回收率平均值 (%)	RSD (%)	高浓度加标浓度(ng/L)	回收率平均值 (%)	RSD (%)
六氯苯	5.00	88.0	2.7	75.0	84.6	2.6	400	91.5	1.9
α-六六六	5.00	93.9	2.0	75.0	92.9	2.4	400	93.4	2.0
γ-六六六	5.00	97.5	1.9	75.0	92.6	2.0	400	92.8	2.3
β-六六六	5.00	100	2.1	75.0	91.1	3.0	400	92.7	2.3
δ-六六六	5.00	108	3.1	75.0	94.9	2.3	400	93.6	2.1
七氯	5.00	100	2.1	75.0	96.8	2.2	400	96.0	2.2
百菌清	10.0	98.8	4.6	150	100	1.8	800	94.1	3.3
艾氏剂	5.00	80.6	2.6	75.0	82.4	4.5	400	89.0	1.7
毒死蜱	10.0	102	2.3	150	100	1.8	800	97.3	3.0
三氯杀螨醇	30.0	105	2.2	450	91.3	2.1	2400	90.1	1.1
p, p′-DDE	5.00	99.8	1.9	75.0	92.8	1.8	400	93.9	1.9
狄氏剂	5.00	96.3	2.2	75.0	94.3	1.7	400	94.7	3.8
o, p′-DDT	5.00	105	2.6	75.0	99.7	1.8	400	96.8	2.2
p, p′-DDD	5.00	97.4	1.5	75.0	96.5	1.9	400	96.3	3.7
p, p′-DDT	5.00	116	2.5	75.0	103	1.8	400	97.7	2.3
联苯菊酯	16.0	97.7	2.6	240	94.8	1.4	1280	95.0	2.6
甲氰菊酯	16.0	96.4	3.5	240	99.0	1.5	1280	95.7	6.8
灭蚁灵	8.00	102	2.6	120	92.0	1.6	640	93.7	1.8
三氟氯氰菊酯	12.0	99.2	2.6	180	102	2.2	960	96.1	1.7
氯氰菊酯	60.0	91.5	4.5	900	103	7.6	4800	96.1	1.3
氯菊酯	32.0	102	5.1	480	93.5	1.5	2560	94.8	1.9
高效氰戊菊酯	20.0	94.0	5.4	300	103	4.4	1600	95.5	2.2
氟胺氰菊酯	50.0	103	6.8	750	117	4.8	4000	102	2.2
溴氰菊酯	32.0	97.7	4.9	480	107	3.9	2560	97.5	2.7
2, 4, 5, 6-四氯间二甲苯	-	80.3	3.2	-	79.9	5.5	-	85.7	2.5
二丁基氯菌酸酯	-	95.6	1.9	-	96.3	1.3	-	94.0	3.9

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参考文献(23)

[1]	http://www.cnki.com.cn/Article/CJFDTOTAL-IAOB200402020.htm
[2]	http://www.cnki.com.cn/Article/CJFDTOTAL-ZGGX201533046.htm
[3]	http://www.cnki.com.cn/Article/CJFDTOTAL-TEST201103021.htm
[4]	http://www.cnki.com.cn/Article/CJFDTOTAL-HXXB201204020.htm
[5]	http://www.cnki.com.cn/Article/CJFDTOTAL-SPZZ201107007.htm
[6]	doi: 10.1007/s10337-011-1921-x
[7]	doi: 10.1007/s10337-012-2329-y
[8]	http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS201005006.htm
[9]	http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS201105016.htm
[10]	http://www.cnki.com.cn/Article/CJFDTOTAL-HGBJ201710022.htm
[11]	http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS201005008.htm
[12]	doi: 10.1007/s10311-012-0392-0
[13]	doi: 10.1007/s10337-012-2272-y
[14]	http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS200802005.htm
[15]	http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS200801004.htm
[16]	http://www.cnki.com.cn/Article/CJFDTOTAL-FXSY201002004.htm
[17]	http://www.cnki.com.cn/Article/CJFDTOTAL-TEST201102008.htm
[18]	doi: 10.1365/s10337-009-1136-6
[19]	doi: 10.1007/s10337-011-1971-0
[20]	doi: 10.3969/j.issn.1000-0720.2010.01.031
[21]	doi: 10.1007/s10337-013-2408-8
[22]	http://www.cnki.com.cn/Article/CJFDTOTAL-YKCS201302025.htm
[23]	http://www.cnki.com.cn/Article/CJFDTOTAL-SYHG200305017.htm

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气相色谱法测定地下水中拟除虫菊酯有机氯百菌清等24种农药残留

国家地质实验测试中心, 北京 100037

作者简介: 郭晓辰, 助理工程师, 从事环境污染物监测分析研究.E-mail: guoxc2012@163.com

通讯作者: 饶竹, 研究员, 从事环境有机污染物分析.E-mail: raozhu@126.com

Determination of 24 Pesticides including Pyrethroids, Organochlorines and Chlorothalonil in Underground Water by Gas Chromatography

National Research Center for Geoanalysis, Beijing 100037, China

Corresponding author: RAO Zhu, raozhu@126.com

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