【引用本文】 时磊, 孙艳艳, 沈小明, 等. 全二维气相色谱-电子捕获检测器测定复杂基质土壤中24种有机氯和拟除虫菊酯类农药[J]. 岩矿测试, 2020, 39(6): 856-865. doi: 10.15898/j.cnki.11-2131/td.201906090082
SHI Lei, SUN Yan-yan, SHEN Xiao-ming, et al. Determination of 24 Organochlorine Pesticides and Pyrethroids in Complex Matrix Soils by Comprehensive Two-dimensional Gas Chromatography with Micro-electron Capture Detector[J]. Rock and Mineral Analysis, 2020, 39(6): 856-865. doi: 10.15898/j.cnki.11-2131/td.201906090082

全二维气相色谱-电子捕获检测器测定复杂基质土壤中24种有机氯和拟除虫菊酯类农药

中国地质调查局南京地质调查中心, 江苏 南京 210016

收稿日期: 2019-06-09  修回日期: 2019-09-30  接受日期: 2020-10-12

基金项目: 国家重点研发计划项目(2017YFF0206804)

作者简介: 时磊, 硕士, 工程师, 从事环境有机污染物分析研究。E-mail:njdkssl@163.com

Determination of 24 Organochlorine Pesticides and Pyrethroids in Complex Matrix Soils by Comprehensive Two-dimensional Gas Chromatography with Micro-electron Capture Detector

Nanjing Center of Geological Survey, China Geological Survey, Nanjing 210016, China

Received Date: 2019-06-09
Revised Date: 2019-09-30
Accepted Date: 2020-10-12

摘要:目前针对环境样品中有机氯和拟除虫菊酯类农药的检测方法主要有气相色谱法和气相色谱-质谱法(GC-MS),由于气相色谱法采用电子捕获检测器从而具有较高的灵敏度,在污染物的环境行为研究中得到广泛应用,GC-MS法的定性效果好,但检测灵敏度相对偏低。本文研究了2018年土壤详查江苏地区样品中有机氯农药和拟除虫菊酯的残留状况,结果显示,即使经过多次净化仍有20%的样品存在假阳性或基质干扰现象。为了提高定性准确度,同时保证检测灵敏度,实验建立了复杂基质土壤中20种有机氯农药和4种拟除虫菊酯的全二维气相色谱-电子捕获检测器检测方法,最终选择中等极性的TG-35MS为第一色谱柱,非极性的(DB-1)为第二色谱柱,将鲜样与无水硫酸钠混合均匀后,以正己烷-丙酮(1:1,V/V)为提取剂进行索氏提取,采用全二维气相色谱-电子捕获检测器进行检测,外标法定量。各物质的质量浓度均在1.0~500μg/L内与其峰面积呈线性关系,相关系数均大于0.995,检出限为0.02~0.17μg/kg。用标准加入法进行回收实验,测得回收率为80.7%~103.5%,测定值的相对标准偏差(n=6)为1.84%~10.12%。本方法将高灵敏度检测器与全二维色谱相结合,在保证检测灵敏度的同时增加了峰容量,有效去除了基质干扰。相比2018年土壤详查参考方法HJ 835—2017的检出限0.02~0.09mg/kg(全扫模式),本方法检出限显著降低,且操作简单,可为复杂基质样品中的痕量超痕量检测提供参考。

关键词: 全二维气相色谱法, 索氏提取, 有机氯农药, 拟除虫菊酯, 土壤

要点

(1)增加的峰容量有效消除了基质干扰,提高了定性、定量准确度。

(2)相比《土壤和沉积物 有机氯农药的测定 气相色谱-质谱法》(HJ 835—2017),本方法检出限降低。

(3)中等极性色谱柱与非极性色谱柱串联使用,峰容量得到显著提高。

Determination of 24 Organochlorine Pesticides and Pyrethroids in Complex Matrix Soils by Comprehensive Two-dimensional Gas Chromatography with Micro-electron Capture Detector

ABSTRACT

BACKGROUND:

Currently the analysis methods of organochlorine pesticides and pyrethroids in environment samples are gas chromatography and gas chromatography-mass spectrometry (GC-MS). Gas chromatography with electron capture detector has been widely used in the study of environmental behavior of pollutants due to its high sensitivity. GC-MS has good qualitative results, but the detection sensitivity is relatively low.

OBJECTIVES:

To establish an easy, highly efficient and precise method for determination of 20 organochlorine pesticides and 4 pyrethroids in complicated matrix soils.

METHODS:

The residues of organochlorine pesticides and pyrethroids in samples from Jiangsu Province in 2018 were studied. In order to improve the qualitative accuracy and ensure the detection sensitivity, a comprehensive two-dimensional gas chromatography-electron capture detector detection method for determination of 20 organochlorine pesticides and 4 pyrethroids in complex-matrix soils was established. TG-35MS column (30m×0.25mm×0.25μm) was chosen as the column for the first dimension, and a DB-1 column (0.8m×0.18mm×0.18μm) was chosen as the column for the second dimension. The fresh sample was mixed with anhydrous sodium sulfate and extracted with hexane-acetone (1:1, V/V), subsequently purified by activated sheet copper. The analysis was conducted by GC×GC-μECD, qualified by retention time and quantified by external standard.

RESULTS:

The proposed method showed good linearity with correlation coefficients (r) higher than 0.995 in the concentration range of 1.0-500μg/L, with the detection limits of 0.02-0.17μg/kg. The recovery of standard addition method ranged from 80.7% to 103.5%, and the relative standard deviations (n=6) were 1.84%-10.12%.

CONCLUSIONS:

The proposed method combined high sensitivity detector with comprehensive two-dimension gas chromatography overcomes the matrix interference in complex sample, which shows a good detection sensitivity and peak capacity. The detection limit of the method is far lower than that of HJ 835-2017 standard (0.02-0.09). This method can provide reference for the analysis of multiple organochlorine pesticides and pyrethroids in complex-matrix soil.

KEY WORDS: comprehensive two dimensional gas chromatography, Soxhlet's extraction, organochlorine pesticides, pyrethroids, soils

HIGHLIGHTS

(1) The method can effectively remove matrix interference and improve the accuracy of qualitative and quantitative measurement.

(2) Compared with ‘Soil and Sediment—Determination of Organochlorine Pesticides—Gas Chromatography/Mass Spectrometry’(HJ 835—2017), the detection limit of this method is lower.

(3) The peak capacity is improved significantly by using medium-polar column and non-polar column.

本文参考文献

[1]

Mohammad A, Masarrat J Y, Sohail S, et al. Serum organochlorine pesticides residues and risk of cancer:A case-control study[J].Saudi Journal of Biological Sciences, 2018, 25(7): 1284-1290. doi: 10.1016/j.sjbs.2017.10.023

[2]

Harriet K M, Sampson M A, Linda M N P, et al. Determination of organochlorine pesticide residue in sediment and water from the Densu River Basin, Ghana[J].Chemosphere, 2012, 86(3): 286-292. doi: 10.1016/j.chemosphere.2011.10.031

[3]

赵玲, 滕应, 骆永明, 等. 我国有机氯农药场地污染现状与修复技术研究进展[J]. 土壤, 2018, 50(3): 435-445.

Zhao L, Teng Y, Luo Y M, et al. Status of organochlorine pesticide contaminated sites in China and advances in site remediation[J]. Soils, 2018, 50(3): 435-445.

[4]

朱帅, 沈亚婷, 贾静, 等. 环境介质中典型新型有机污染物分析技术研究进展[J]. 岩矿测试, 2018, 37(5): 586-606.

Zhu S, Shen Y T, Jia J, et al. Review on the analytical methods of typical emerging organic pollutants in the environment[J]. Rock and Mineral Analysis, 2018, 37(5): 586-606.

[5]

时磊, 孙艳艳, 吕爱娟, 等. 长三角部分地区土壤中22种有机氯农药的分布特征[J]. 岩矿测试, 2016, 35(1): 75-81.

Shi L, Sun Y Y, Lü A J, et al. Distribution characteristics of 22 organochlorine pesticides in soils from some areas of the Yangtze River Delta[J]. Rock and Mineral Analysis, 2016, 35(1): 75-81.

[6]

雷云, 吴珊月, 刘文菁, 等. SPME-GC-ECD法测定含硫蔬菜中的有机氯农药[J]. 化学研究与应用, 2018, 30(9): 1560-1565. doi: 10.3969/j.issn.1004-1656.2018.09.027

Lei Y, Wu S Y, Liu W J, et al. Determination of organochlorine pesticides in sulfur-containing vegetables with SPME-GC-ECD[J].Chemical Research and Application, 2018, 30(9): 1560-1565. doi: 10.3969/j.issn.1004-1656.2018.09.027

[7]

于英鹏, 刘敏. 太湖流域水源地有机氯农药分布特征与生态风险评价[J]. 环境污染与防治, 2017, 39(8): 829-834. doi: 10.15985/j.cnki.1001-3865.2017.08.004

Yu Y P, Liu M. Distribution characteristics and ecological risk assessment of organochlorine pesticides in water sources of Taihu Lake Basin[J].Environmental Pollution & Control, 2017, 39(8): 829-834. doi: 10.15985/j.cnki.1001-3865.2017.08.004

[8]

鲁垠涛, 薛宏慧, 张士超, 等. 长江流域岸边土中OCPs的残留特征、来源及风险评价[J]. 中国环境科学, 2019, 39(9): 3897-3904. doi: 10.3969/j.issn.1000-6923.2019.09.036

Lu Y T, Xue H H, Zhang S C, et al. Residue characteristics, sources and risk assessment of organochlorine pesticides in riparian soils of the Yangtze River Basin[J].China Environmental Science, 2019, 39(9): 3897-3904. doi: 10.3969/j.issn.1000-6923.2019.09.036

[9]

Tsygankov V Y, Boyarova M D. Sample preparation method for the determination of organochlorine pesticides in aquatic organisms by gas chromatography[J].Achievements in the Life Sciences, 2015, 9(1): 65-68. doi: 10.1016/j.als.2015.05.010

[10]

李晓晶, 于鸿, 黄聪, 等. QuEChERS-气相色谱法测定蔬菜中有机磷和拟除虫菊酯类农药残留量[J]. 理化检验(化学分册), 2011, 47(11): 1316-1319.

Li X J, Yu H, Huang C, et al. GC determination of residual amounts of organophosphorus and pyrethroid pesticides in vegetables with QuEChERS[J]. Physical Testing and Chemical Analysis (Part B:Chemical Analysis), 2011, 47(11): 1316-1319.

[11]

万益群, 陈宗保. 土壤中多种有机氯及拟除虫菊酯类农药的GC-ECD测定[J]. 分析试验室, 2006, 25(9): 60-63. doi: 10.3969/j.issn.1000-0720.2006.09.016

Wan Y Q, Chen Z B. Study on determination of organochlorine and pyrethroid pesticide residues in soil by gas chromatography[J].Chinese Journal of Analysis Laboratory, 2006, 25(9): 60-63. doi: 10.3969/j.issn.1000-0720.2006.09.016

[12]

成昊, 张丽君, 张磊, 等. 基质固相分散萃取-分散液相微萃取-气相色谱质谱法测定土壤中拟除虫菊酯类农药[J]. 分析化学, 2015, 43(1): 137-140.

Cheng H, Zhang L J, Zhang L, et al. Determination of three pyrethroids in soil by matrix solid phase dispersion extraction-dispersed liquid phase microextraction-gas chromatography mass spectrometry[J]. Chinese Journal of Analytical Chemistry, 2015, 43(1): 137-140.

[13]

李俊, 肖雅雯, 王震, 等. 加速溶剂萃取-气相色谱/质谱法同时测定土壤中拟除虫菊酯类等18种农药残留[J]. 岩矿测试, 2011, 30(5): 590-595. doi: 10.3969/j.issn.0254-5357.2011.05.014

Li J, Xiao Y W, Wang Z, et al. Simultaneous determination of pesticide residues including pyrethroids in soils by gas chromatography-mass spectrometry with accelerated solvent extraction[J]. Rock and Mineral Analysis, 2011, 30(5): 590-595. doi: 10.3969/j.issn.0254-5357.2011.05.014

[14]

黄旭, 张兵, 邓泽元, 等. 超声波提取-气相色谱法同时检测白菜中拟除虫菊酯残留[J]. 中国食品学报, 2018, 18(2): 238-243.

Huang X, Zhang B, Deng Z Y, et al. Simultaneous determination of pyrethroid residue in cabbage using ultrasonic extraction GC-ECD[J]. Journal of Chinese Institute of Food Science and Technology, 2018, 18(2): 238-243.

[15]

黄微, 李娜, 徐瑞晗, 等. 加速溶剂萃取-固相萃取净化-气相色谱-串联质谱法检测茶叶中9种拟除虫菊酯类农药残留[J]. 色谱, 2018, 36(12): 1303-1310.

Huang W, Li N, Xu R H, et al. Determination of nine pyrethroid pesticide residues in tea by gas chromatography-tandem mass spectrometry combined with accelerated solvent extraction and solid phase extraction[J]. Chinese Journal of Chromatography, 2018, 36(12): 1303-1310.

[16]

焦慧泽, 陆世清, 侯迪, 等. 加速溶剂萃取-超高效液相色谱-串联质谱法测定茶叶中拟除虫菊酯类农药残留[J]. 色谱, 2019, 37(6): 605-611.

Jiao H Z, Lu S Q, Hou D, et al. Determination of pyrethroid pesticides in tea by accelerated solvent extraction and ultra-performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2019, 37(6): 605-611.

[17]

张聪, 周常义, 江锋, 等. 超高效液相色谱-串联质谱法测定动物性食品中10种拟除虫菊酯类农药残留[J]. 分析测试学报, 2018, 37(8): 887-893. doi: 10.3969/j.issn.1004-4957.2018.08.003

Zhang C, Zhou C Y, Jiang F, et al. Determination of 10 pyrethroid pesticide residues in animal foods by ultra performance liquid chromatography-tandem mass spectrometry[J].Journal of Instrumental Analysis, 2018, 37(8): 887-893. doi: 10.3969/j.issn.1004-4957.2018.08.003

[18]

符靖雯, 林玉婵, 黄梅花, 等. QuEChERS萃取结合GC-ECD测定甜玉米中多种有机氯及拟除虫菊酯类农药残留[J]. 理化检验(化学分册), 2017, 53(9): 1036-1041.

Fu J W, Lin Y C, Huang M H, et al. Determination of organochlorine and pyrethroid pesticide residues in sweet corn by GC-ECD with QuEChERS extraction method[J]. Physical Testing and Chemical Analysis (Part B:Chemical Analysis), 2017, 53(9): 1036-1041.

[19]

沈丹玉, 袁新跃, 刘毅华, 等. 分散固相净化与气相色谱测定竹笋中21种农药残留[J]. 食品科学, 2017, 38(16): 268-273. doi: 10.7506/spkx1002-6630-201716043

Shen D Y, Yuan X Y, Liu Y H, et al. Determination of 21 pesticide residues in bamboo shoots by dispersive solid phase extraction cleanup and gas chromatography[J].Food Science, 2017, 38(16): 268-273. doi: 10.7506/spkx1002-6630-201716043

[20]

刘丽, 张琦, 王海雁, 等. 串联双柱固相萃取-气相色谱-串联质谱法检测茶叶中拟除虫菊酯[J]. 色谱, 2017, 35(8): 860-866.

Liu L, Zhang Q, Wang H Y, et al. Determination of pyrethroid pesticides in tea by series two-solid phase extraction-columns cleanup and gas chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2017, 35(8): 860-866.

[21]

史晓梅, 章睛, 杨永坛, 等. 凝胶渗透色谱净化结合气相色谱-三重四极杆质谱法测定植物油中多农药残留量[J]. 中国粮油学报, 2017, 32(10): 156-162. doi: 10.3969/j.issn.1003-0174.2017.10.027

Shi X M, Zhang Q, Yang Y T, et al. Determination of multi-pesticides residues in vegetable oil by gel permeation chromatography purifying method combined with gas chromatography tandem mass spectrometry[J].Journal of the Chinese Cereals and Oils Association, 2017, 32(10): 156-162. doi: 10.3969/j.issn.1003-0174.2017.10.027

[22]

邢燕, 曹楷华, 刘玉栋, 等. 超声波辅助提取GC/MS法测定蔬菜中18种农药[J]. 食品研究与开发, 2016, 37(15): 171-175. doi: 10.3969/j.issn.1005-6521.2016.15.039

Xing Y, Cao K H, Liu Y D, et al. Ultrasonic assisted extraction-gas chromatography-mass spectrometry method for the determination of 18 kinds of pesticides in vegetables[J].Food Research and Development, 2016, 37(15): 171-175. doi: 10.3969/j.issn.1005-6521.2016.15.039

[23]

彭晓俊, 梁优珍, 梁伟华, 等. QuEChERS结合气相色谱-质谱法测定农产品中杀螨剂和拟除虫菊酯农药残留[J]. 分析科学学报, 2017, 33(6): 863-868.

Peng X J, Liang Y Z, Liang W H, et al. Determination of acaricide and pyrethroid pesticides residues in farm produce by QuEChERS and gas chromatography-mass spectrometry[J]. Journal of Analytical Science, 2017, 33(6): 863-868.

[24]

Higgins K E A, Jenkins C L, Davis T J, et al. Advances in the application of comprehensive two-dimensional gas chromatography in metabolomics[J].Trends in Analytical Chemistry, 2018, 109: 275-286. doi: 10.1016/j.trac.2018.10.015

[25]

Jáčová J, Gardlo A, Dimandja J M D, et al. Impact of sample dimensionality on orthogonality metrics in comprehensive two-dimensional separations[J].Analytica Chimica Acta, 2019, 1064: 138-149. doi: 10.1016/j.aca.2019.03.018

[26]

战楠, 朱帅, 郭峰, 等. 顶空-固相微萃取-全二维气相色谱-飞行时间质谱测定水中短链氯化石蜡[J]. 分析化学, 2018, 46(12): 2004-2010. doi: 10.11895/j.issn.0253-3820.181309

Zhan N, Zhu S, Guo F, et al. Determination of short-chain chlorinated paraffins in water by headspace solid phase micro-extraction and comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry[J].Chinese Journal of Analytical Chemistry, 2018, 46(12): 2004-2010. doi: 10.11895/j.issn.0253-3820.181309

[27]

张兵, 郑明辉, 刘国瑞, 等. 全二维气相色谱-电子捕获检测器法分析土壤中毒杀芬同类物的残留[J]. 分析化学, 2012, 40(8): 1213-1218.

Zhang B, Zheng M H, Liu G R, et al. Comprehensive two-dimensional gas chromatography with micro-electron capture detector for analysis of toxaphene congeners in soil[J]. Chinese Journal of Analytical Chemistry, 2012, 40(8): 1213-1218.

[28]

时秋娜, 刘占芳, 朱军, 等. 全二维气相色谱-质谱法检测动植物油[J]. 中国油脂, 2017, 42(6): 138-142. doi: 10.3969/j.issn.1003-7969.2017.06.030

Shi Q N, Liu Z F, Zhu J, et al. Detection of fatty acids in animal fats and vegetable oils by comprehensive two-dimensional gas chromatography coupled with mass spectrometry[J].China Oils and Fats, 2017, 42(6): 138-142. doi: 10.3969/j.issn.1003-7969.2017.06.030

[29]

Silva R C, Silva R S F, Castro E V R, et al. Extended diamondoid assessment in crude oil using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry[J]. Fuel, 2013, 112(5): 125-133.

[30]

郭晓辰, 饶竹, 高冉, 等. 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[J]. 岩矿测试, 2014, 33(3): 406-412. doi: 10.3969/j.issn.0254-5357.2014.03.020

Guo X C, Rao Z, Gao R, et al. Determination of 24 pesticides including pyrethroids, organochlorines and chlorothalonil in underground water by gas chromatography[J]. Rock and Mineral Analysis, 2014, 33(3): 406-412. doi: 10.3969/j.issn.0254-5357.2014.03.020

[31]

魏峰, 沈小明, 陈海英, 等. 土壤和沉积物中22种有机氯农药和8种多氯联苯的气相色谱分析[J]. 岩矿测试, 2013, 32(6): 952-958. doi: 10.3969/j.issn.0254-5357.2013.06.018

Wei F, Shen X M, Chen H Y, et al. Method for the analysis of 22 organochlorine pesticides and 8 polychlorinated biphenyls in soils and sediments using gas chromatography[J]. Rock and Mineral Analysis, 2013, 32(6): 952-958. doi: 10.3969/j.issn.0254-5357.2013.06.018

[32]

马玲, 秦婷, 周晨忱, 等. 超声波提取-硫酸净化-气相色谱/质谱法同时测定土壤样品中23种有机氯农药[J]. 分析试验室, 2019, 38(3): 346-350.

Ma L, Qin T, Zhou C C, et al. Simultaneous determination of twenty-three organochlorine pesticides in soil by ultrasonic extraction-sulfuric acid purification-gas chromatograph/mass spectrometry[J]. Chinese Journal of Analysis Laboratory, 2019, 38(3): 346-350.

[33]

Senar O, Ali T, Mehmet E A, et al. Application of miniaturised ultrasonic extraction to the analysis of organochlorine pesticides in soil[J].Analytica Chimica Acta, 2009, 640: 52-57. doi: 10.1016/j.aca.2009.03.030

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全二维气相色谱-电子捕获检测器测定复杂基质土壤中24种有机氯和拟除虫菊酯类农药

时磊, 孙艳艳, 沈小明, 吕爱娟, 蔡小虎, 刘娇, 沈加林