QuEChERS-气相色谱-质谱法检测鱼肉中19种氯酚类化合物

doi:10.3724/SP.J.1123.2021.12002

色谱 ›› 2022, Vol. 40 ›› Issue (5): 477-487.DOI: 10.3724/SP.J.1123.2021.12002

QuEChERS-气相色谱-质谱法检测鱼肉中19种氯酚类化合物

穆应花¹^,², 邢家溧²^,^*(), 沈坚², 应璐², 毛玲燕², 徐晓蓉², 娄永江¹^,^*(), 吴希¹

1.宁波大学食品与药品学院, 浙江宁波 315211
2.宁波市产品食品质量检验研究院(宁波市纤维所), 浙江宁波 315048

收稿日期:2021-12-03 出版日期:2022-05-08 发布日期:2022-04-28
通讯作者: 邢家溧,娄永江
基金资助:
国家市场监管总局科技计划项目(2020MK117);浙江省市场监管系统科技计划项目(20210140);浙江省基础公益研究计划项目(LGC20C200003);宁波市自然科学基金项目(202003N4196);宁波市自然科学基金项目(2019A610438);宁波市自然科学基金项目(2019A610437);宁波市泛3315创新团队项目(2018B-18-C);宁波市高新精英创新团队项目(Yong gao ke[2018]63);宁波市公益类科技计划项目(2021S194);宁波市重大科技攻关项目(2021ZDYF020179)

Determination of 19 chlorophenols in fish by QuEChERS-gas chromatography-mass spectrometry

MU Yinghua¹^,², XING Jiali²^,^*(), SHEN Jian², YING Lu², MAO Lingyan², XU Xiaorong², LOU Yongjiang¹^,^*(), WU Xi¹

1. College of Food and Pharmaceutical Sciences, Ningbo University, Ningbo 315211, China
2. Ningbo Academy of Product and Food Quality Inspection (Ningbo Fibre Inspection Institute), Ningbo 315048, China

Received:2021-12-03 Online:2022-05-08 Published:2022-04-28
Contact: XING Jiali, LOU Yongjiang
Supported by:
Science and Technology Plan Program of State Administration for Market Regulation(2020MK117);Science and Technology Program of Market Supervision System in Zhejiang(20210140);Basic Research Plan Project of Zhejiang(LGC20C200003);Natural Science Foundation of Ningbo(202003N4196);Natural Science Foundation of Ningbo(2019A610438);Natural Science Foundation of Ningbo(2019A610437);Project of Fan-3315 Innovation Team of Ningbo(2018B-18-C);Project of Ningbo High-Tech Elite Innovation Team(Yong gao ke[2018]63);Ningbo Public Welfare Science and Technology Plan Project(2021S194);Ningbo Major Science and Technology Research Project(2021ZDYF020179)

摘要/Abstract

摘要：

大量含氯农药、次氯酸消毒水以及水产品杀虫剂和杀菌剂的广泛使用,使鱼类容易受到氯酚类化合物的污染,因而建立鱼肉中氯酚类化合物的检测方法十分重要。建立了QuEChERS结合气相色谱-质谱法同时检测鱼肉中19种氯酚类化合物的分析方法。19种氯酚类化合物选用DB-5MS毛细管色谱柱(30 m×0.25 mm×0.25 μm),载气流速1 mL/min进行分离,可以得到很好的峰形。前处理采用改良的QuEChERS方法,通过对提取剂的种类和剂量、净化剂的种类和剂量,以及衍生条件中的衍生温度、衍生时间和衍生剂用量等进行优化,确定最优的前处理方法。选择10 mL乙酸乙酯作为提取剂,500 mg的C₁₈作为净化剂,加入3 g氯化钠和5 g无水硫酸镁,过0.22 μm的有机滤膜,加入50 μL的硅烷化衍生剂在45 ℃条件下衍生30 min,用EI源测定,选择离子监测模式,以外标法定量。19种氯酚类化合物在0.4~10 μg/L范围内具有良好的线性关系,相关系数R²大于0.998,方法定量限为0.04~0.16 μg/kg。空白基质不同加标水平的回收率为70.6%~115.0%,相对标准偏差为2.6%~10.5%。将建立的方法应用于实际样品的检测分析,结果显示,各种鱼肉中均有不同程度的氯酚类化合物检出,其中,黄花鱼检出的氯酚类化合物总量最大,为8.74 μg/kg;其次为鲫鱼7.59 μg/kg;米鱼的检出量最少,为1.59 μg/kg。所建立的方法简化了样品的前处理步骤,操作简单,方法灵敏度高、重复性好,可满足鱼肉中19种氯酚类化合物的高通量检测要求,能显著提高氯酚类化合物的检测效率。

关键词: 气相色谱-质谱, QuEChERS, 氯酚类化合物, 鱼肉

Abstract:

With the increasing use of chlorine-containing pesticides, hypochlorous acid disinfection water as well as aquatic product insecticides and fungicides are widely used in the cultivation of fish. This has led to the contamination of fish by chlorophenol compounds. However, currently, there is no standard method for the simultaneous determination of 19 chlorophenol compounds in fish.

In this study, the optimum chromatography and mass spectrometry conditions were determined by investigating the instrument parameters. The 19 chlorophenol compounds were well separated using the DB-5MS capillary chromatographic column (30 m×0.25 mm×0.25 μm) with a carrier gas flow rate of 1 mL/min. Under this condition, the chromatographic peak was sharp and symmetric. An analytical method was developed for the simultaneous determination of the 19 chlorophenol compounds in fish using gas chromatography-mass spectrometry coupled with QuEChERS pretreatment. The improved QuEChERS method was used in sample preparation. The 19 chlorophenol compounds were extracted with organic solvents and purified with purifying agents. During the experiment, the effect of the kinds and volumes of the extraction solvent, as well as the types and dosages of the purifying agent, on the recoveries of the 19 chlorophenol compounds were investigated. Moreover, the temperature and time of derivatization, as well as the dosage of the derivatization agent, were optimized. All aforementioned analyses were conducted with the aim of determining the optimal pretreatment method. Finally, the optimized gas chromatography-mass spectrometry conditions were employed for the quantitative determination of 19 chlorophenol compounds in fish samples. Based on the experimental results, the best extraction method was determined to be the one where the extraction agent (10 mL ethyl acetate) was added to 3 g sodium chloride and 5 g anhydrous magnesium sulfate in the test tube, followed by ultrasonication for 15 min. The sample was centrifuged at 4500 r/min for 5 min, and 500 mg C₁₈ was selected as the purifying agent to purify the supernatant. The purified supernatant was blown with nitrogen to less than 1 mL at 45 ℃, and then redissolved with ethyl acetate to 1 mL. Subsequently, the sample solution was passed through a 0.22 μm organic filter membrane, following which 50 μL bis(trimethylsilyl)trifluoroacetamide was added for derivatization at 45 ℃ for 30 min. Lastly, the 19 chlorophenol compounds were determined by gas chromatography-mass spectrometry with an electrospray ionization source and selecting ion monitoring mode. The 19 chlorophenol compounds were then quantitatively analyzed by the external standard method. The compounds showed good linearity in the concentration range of 0.4-10 μg/L, with correlation coefficients (R²) greater than 0.998. The limits of detection and limits of quantification were 0.01-0.05 μg/kg and 0.04-0.16 μg/kg, respectively. Moreover, the average recoveries of the 19 chlorophenol compounds were in the range of 70.6%-115.0% at three spiked levels, and the relative standard deviations were in the range of 2.6%-10.5%. The established method in this study was applied to detect and analyze chlorophenol compounds in actual samples. The experimental results showed that various levels of chlorophenol compounds could be detected in different fishes. Among them, the total amount of chlorophenol compounds detected in the Corvina was 8.74 μg/kg, followed by the Crucian carp at 7.59 μg/kg, and the minimum detected amount in rice fish (1.59 μg/kg). With its simple operation, high sensitivity, and good repeatability, the established method simplifies the pre-treatment of fish samples. It can also meet the requirements for the high-throughput detection of 19 chlorophenol compounds in fish, thereby significantly improving the detection efficiency of chlorophenols. Moreover, the method provides crucial technical support and a theoretical basis for the establishment of feasible detection standards for chlorophenols in China, as well as for the control of residue levels of chlorophenol compounds in fish. The findings have important practical significance to implement management measures during fish breeding and transportation.

Key words: gas chromatography-mass spectrometry (GC-MS), QuEChERS, chlorophenols, fish

中图分类号:

O658

穆应花, 邢家溧, 沈坚, 应璐, 毛玲燕, 徐晓蓉, 娄永江, 吴希. QuEChERS-气相色谱-质谱法检测鱼肉中19种氯酚类化合物[J]. 色谱, 2022, 40(5): 477-487.

MU Yinghua, XING Jiali, SHEN Jian, YING Lu, MAO Lingyan, XU Xiaorong, LOU Yongjiang, WU Xi. Determination of 19 chlorophenols in fish by QuEChERS-gas chromatography-mass spectrometry[J]. Chinese Journal of Chromatography, 2022, 40(5): 477-487.

图/表 11

参考文献

[1]	Tang Y H, Wei X C, Huang X K. West Leather, 2018, 40(3): 46
[1]	唐玉红, 魏小春, 黄小凯. 西部皮革, 2018, 40(3): 46
[2]	Lei B L, Jin X W, Huang S B, et al. Asian Journal of Ecotoxicology, 2009, 4(1): 40
[2]	雷炳莉, 金小伟, 黄圣彪, 等. 生态毒理学报, 2009, 4(1): 40
[3]	Xie S Y, Zhang J L, Shen H Y, et al. Chinese Journal of Analysis Laboratory, 2017, 36(11): 1351
[3]	谢晟瑜, 张佳丽, 沈昊宇, 等. 分析试验室, 2017, 36(11): 1351
[4]	Huff J. Chemosphere, 2012, 89(5): 521
[5]	Haimi J, Salminen J, Huhta V, et al. Soil Biol Biochem, 1992, 24(12): 1699
[6]	Olaniran A O, Pillay D, Pillay B. Chemosphere, 2004, 55(1): 27
[7]	Zhang X L, Guo J, Yang W L, et al. Environmental Chemistry, 2017, 36(1): 201
[7]	张秀蓝, 郭婧, 杨文龙, 等. 环境化学, 2017, 36(1): 201
[8]	GB 23200.92-2016
[9]	GB 29708-2013
[10]	SC/T 3030-2006
[11]	Fattahi N, Assadi Y, Hosseini M R M, et al. J Chromatogr A, 2007, 1157(1): 23
[12]	Zhang S J, Xu Y J, Gong X H, et al. Physical Testing and Chemical Analysis (Part B: Chemical Analysis), 2010, 46(9): 996
[12]	张世娟, 徐英江, 宫向红, 等. 理化检验(化学分册), 2010, 46(9): 996
[13]	Zhong Y, Yu C L, Peng P A. Chinese Journal of Chromatography, 2010, 28(10): 923
[13]	钟颖, 于赤灵, 彭平安. 色谱, 2010, 28(10): 923
[14]	Shi Y K, Yang M G, Yang Q H, et al. Chinese Journal of Food Hygiene, 2015, 27(1): 19
[14]	史玉坤, 杨梅桂, 杨清华, 等. 中国食品卫生杂志, 2015, 27(1): 19
[15]	Wang K D, Chen P S, Huang S D. Anal Bioanal Chem, 2014, 406(8): 2123
[16]	Wang J Q, Cao Y H, Zhu L N, et al. Analytical Instrumentation, 2020(4): 38
[16]	王嘉琦, 曹英华, 朱琳娜, 等. 分析仪器, 2020(4): 38
[17]	Zhang Z R, Zhang L Y, Wang Y J, et al. Chinese Journal of Food Hygiene, 2019, 31(3): 226
[17]	张志荣, 张来颖, 王玉江, 等. 中国食品卫生杂志, 2019, 31(3): 226
[18]	Wang T J, Lin Q B, Song H. et al. Journal of Instrumental Analysis, 2010, 29(12): 1153
[18]	王天娇, 林勤保, 宋欢, 等. 分析测试学报, 2010, 29(12): 1153
[19]	Jin M C, Chen X H, Pan B X. J Liq Chromatogr Relat Technol, 2006, 29(9): 1369
[20]	Wang C Y, Lin J F, Shen Y L. et al. Paper Science & Technology, 2015, 34(6): 68
[20]	王成云, 林君峰, 沈雅蕾, 等. 造纸科学与技术, 2015, 34(6): 68
[21]	Mo X K, Huang Z L, Liu L Q. Leather Science and Engineering, 2017, 27(1): 58
[21]	莫贤科, 黄泽琳, 刘丽琴. 皮革科学与工程, 2017, 27(1): 58
[22]	Fu C Y, Duan W F, Shi J W, et al. Journal of Food Safety & Quality, 2016, 7(7): 2852
[22]	符昌雨, 段文锋, 施敬文, 等. 食品安全质量检测学报, 2016, 7(7): 2852
[23]	Zhong H Y, Liu H, Chai L Y, et al. Journal of Analytical Science, 2016, 32(3): 371
[23]	钟惠英, 柳海, 柴丽月, 等. 分析科学学报, 2016, 32(3): 371
[24]	Swagata M, Rajlakshmi P, Sudip B, et al. J AOAC Int, 2020, 103(1):62
[25]	Bresin B, Piol M, Fabbro D, et al. J Chromatogr A, 2015, 1376: 167
[26]	Padilla-Sanchez J A, Plaza-Bolanos P, Romero-Gonzalez R, et al. J Chromatogr A, 2010, 1217(36): 5724
[27]	Wang L Z, Fang E H, Wang C J, et al. Chinese Journal of Chromatography, 2018, 36(6): 518
[27]	王连珠, 方恩华, 王彩娟, 等. 色谱, 2018, 36(6): 518
[28]	Huang J F. Modern Food, 2020(21): 170
[28]	黄建芳. 现代食品, 2020(21): 170
[29]	Wang M T, Mou J, Jin Y, et al. Chinese Dyeing & Finishing, 2007(5): 31
[29]	王明泰, 牟峻, 靳颖, 等. 印染, 2007(5): 31
[30]	GB/T 18414.2-2006
[31]	ISO 17070-2015
[32]	Huang W, Li H Q, Liu J F, et al. Journal of Food Safety & Quality, 2018, 9(2): 422
[32]	黄武, 李红权, 刘建芳, 等. 食品安全质量检测学报, 2018, 9(2): 422
[33]	Xian Y P, Guo X D, Hou X C, et al. J Chromatogr A, 2017, 1526: 31
[34]	Wang J Z, Liu J, Luo X, et al. Tobacco Science & Technology, 2017, 50(6): 53
[34]	王加忠, 刘剑, 罗熹, 等. 烟草科技, 2017, 50(6): 53
[35]	Yao L, Zhao J L, Liu Y S, et al. Anal Bioanal Chem, 2016, 408(28): 8177
[36]	Qin F, Deng Q D, Li Y, et al. Journal of Instrumental Analysis, 2018, 37(8): 879
[36]	秦富, 邓全道, 李湧, 等. 分析测试学报, 2018, 37(8): 879
[37]	Xu W J, Wang Z G, Ding K Y, et al. Journal of Instrumental Analysis, 2017, 36(1): 54
[37]	许文娟, 王振刚, 丁葵英, 等. 分析测试学报, 2017, 36(1): 54
[38]	Zhang C, Zhou C Y, Jiang F, et al. Journal of Instrumental Analysis, 2018, 37(8): 887
[38]	张聪, 周常义, 江锋, 等. 分析测试学报, 2018, 37(8): 887
[39]	Wang J, Ling Y, Deng Y M, et al. Chinese Journal of Chromatography, 2020, 38(6): 655
[39]	王佳, 凌云, 邓亚美, 等. 色谱, 2020, 38(6): 655
[40]	Huang J, Chen Y W, Ma M, et al. Journal of Hubei University (Natural Science), 2015, 37(4): 391
[40]	黄姣, 陈有为, 马明, 等. 湖北大学学报(自然科学版), 2015, 37(4): 391
[41]	Chen Q K, Yan Y Z, Liu Z R, et al. West Leather, 2020, 42(5): 37
[41]	陈秋凯, 颜远瞻, 刘志荣, 等. 西部皮革, 2020, 42(5): 37
[42]	Leng J, Xia Q, Tang J. Environmental Monitoring and Forewarning, 2016, 8(2): 20
[42]	冷俊, 夏青, 汤洁. 环境监控与预警, 2016, 8(2): 20

Chlorophenol	Retention time/min	Quantitation ion (m/z)	Identification ions (m/z)
2-Chlorophenol (2-CP)	8.04	185	185, 187, 200
3-Chlorophenol (3-CP)	8.29	185	185, 187, 200
4-Chlorophenol (4-CP)	8.16	185	185, 187, 200
2,5-Dichlorophenol (2,5-DCP)	10.50	219	93, 219, 234
2,6-Dichlorophenol (2,6-DCP)	10.54	219	93, 219, 234
3,5-Dichlorophenol (3,5-DCP)	10.55	219	93, 219, 234
2,4-Dichlorophenol (2,4-DCP)	10.80	219	93, 219, 234
2,3-Dichlorophenol (2,3-DCP)	11.21	219	93, 219, 234
3,4-Dichlorophenol (3,4-DCP)	11.39	219	93, 219, 234
2,4,6-Trichlorophenol (2,4,6-TrCP)	12.75	253	253, 255, 268
2,3,5-Trichlorophenol (2,3,5-TrCP)	13.05	253	253, 255, 268
2,4,5-Trichlorophenol (2,4,5-TrCP)	13.16	253	253, 255, 268
2,3,6-Trichlorophenol (2,3,6-TrCP)	13.34	253	253, 255, 268
3,4,5-Trichlorophenol (3,4,5-TrCP)	13.80	253	253, 255, 268
2,3,4-Trichlorophenol (2,3,4-TrCP)	14.18	253	253, 255, 268
2,3,5,6-Tetrachlorophenol (2,3,5,6-TeCP)	16.10	289	287, 289, 304
2,3,4,6-Tetrachlorophenol (2,3,4,6-TeCP)	16.32	289	287, 289, 304
2,3,4,5-Tetrachlorophenol (2,3,4,5-TeCP)	16.83	289	287, 289, 304
Pentachlorophenol (PCP)	20.62	323	321, 323, 325, 338

Chlorophenol	Retention time/min	Quantitation ion (m/z)	Identification ions (m/z)
2-Chlorophenol (2-CP)	8.04	185	185, 187, 200
3-Chlorophenol (3-CP)	8.29	185	185, 187, 200
4-Chlorophenol (4-CP)	8.16	185	185, 187, 200
2,5-Dichlorophenol (2,5-DCP)	10.50	219	93, 219, 234
2,6-Dichlorophenol (2,6-DCP)	10.54	219	93, 219, 234
3,5-Dichlorophenol (3,5-DCP)	10.55	219	93, 219, 234
2,4-Dichlorophenol (2,4-DCP)	10.80	219	93, 219, 234
2,3-Dichlorophenol (2,3-DCP)	11.21	219	93, 219, 234
3,4-Dichlorophenol (3,4-DCP)	11.39	219	93, 219, 234
2,4,6-Trichlorophenol (2,4,6-TrCP)	12.75	253	253, 255, 268
2,3,5-Trichlorophenol (2,3,5-TrCP)	13.05	253	253, 255, 268
2,4,5-Trichlorophenol (2,4,5-TrCP)	13.16	253	253, 255, 268
2,3,6-Trichlorophenol (2,3,6-TrCP)	13.34	253	253, 255, 268
3,4,5-Trichlorophenol (3,4,5-TrCP)	13.80	253	253, 255, 268
2,3,4-Trichlorophenol (2,3,4-TrCP)	14.18	253	253, 255, 268
2,3,5,6-Tetrachlorophenol (2,3,5,6-TeCP)	16.10	289	287, 289, 304
2,3,4,6-Tetrachlorophenol (2,3,4,6-TeCP)	16.32	289	287, 289, 304
2,3,4,5-Tetrachlorophenol (2,3,4,5-TeCP)	16.83	289	287, 289, 304
Pentachlorophenol (PCP)	20.62	323	321, 323, 325, 338

Chlorophenol	Average recoveries/%
Chlorophenol	AL-N	PSA	C₁₈	GCB
2-CP	98.7	81.6	92.5	85.7
3-CP	106.0	101.0	102.0	102.0
4-CP	87.2	79.8	82.8	77.3
2,5-DCP	76.4	82.5	89.4	68.2
2,6-DCP+3,5-DCP	76.4	76.9	99.8	68.2
2,4-DCP	98.7	101.0	108.0	109.7
2,3-DCP	66.2	93.4	86.7	69.3
3,4-DCP	101.3	83.4	89.0	92.4
2,4,6-TrCP	56.8	64.3	83.5	58.7
2,3,5-TrCP	53.7	81.4	89.4	88.3
2,4,5-TrCP	64.3	82.7	82.0	51.3
2,3,6-TrCP	96.3	72.1	90.2	101.0
3,4,5-TrCP	95.3	101.0	103.5	89.2
2,3,4-TrCP	94.2	68.9	99.3	90.2
2,3,5,6-TeCP	101.9	103.0	106.7	94.4
2,3,4,6-TeCP	91.4	71.1	86.0	88.4
2,3,4,5-TeCP	112.0	87.4	107.9	110.0
PCP	58.0	60.5	69.8	57.8

Chlorophenol	Average recoveries/%
Chlorophenol	AL-N	PSA	C₁₈	GCB
2-CP	98.7	81.6	92.5	85.7
3-CP	106.0	101.0	102.0	102.0
4-CP	87.2	79.8	82.8	77.3
2,5-DCP	76.4	82.5	89.4	68.2
2,6-DCP+3,5-DCP	76.4	76.9	99.8	68.2
2,4-DCP	98.7	101.0	108.0	109.7
2,3-DCP	66.2	93.4	86.7	69.3
3,4-DCP	101.3	83.4	89.0	92.4
2,4,6-TrCP	56.8	64.3	83.5	58.7
2,3,5-TrCP	53.7	81.4	89.4	88.3
2,4,5-TrCP	64.3	82.7	82.0	51.3
2,3,6-TrCP	96.3	72.1	90.2	101.0
3,4,5-TrCP	95.3	101.0	103.5	89.2
2,3,4-TrCP	94.2	68.9	99.3	90.2
2,3,5,6-TeCP	101.9	103.0	106.7	94.4
2,3,4,6-TeCP	91.4	71.1	86.0	88.4
2,3,4,5-TeCP	112.0	87.4	107.9	110.0
PCP	58.0	60.5	69.8	57.8

Chlorophenol	Average recoveries/%
Chlorophenol	30 μL	40 μL	50 μL	60 μL	70 μL
2-CP	80.7	87.1	86.5	87.0	85.0
3-CP	92.2	100.7	101.0	99.5	97.8
4-CP	72.4	82.6	81.5	82.0	80.0
2,6-DCP+3,5-DCP	84.5	91.4	90.3	89.0	86.5
2,5-DCP	89.7	101.0	102.0	101.0	98.6
2,4-DCP	99.1	102.0	103.0	101.0	98.4
2,3-DCP	89.3	98.6	115.0	112.0	109.0
3,4-DCP	83.7	96.4	112.0	109.0	105.0
2,6-DCP	76.0	93.2	98.4	98.5	97.2
2,4,6-TrCP	79.0	87.1	95.4	96.0	93.0
2,3,5-TrCP	86.5	98.4	101.0	99.6	98.7
2,4,5-TrCP	76.0	88.4	97.8	98.0	87.6
2,3,6-TrCP	85.2	98.6	106.0	104.0	101.0
3,4,5-TrCP	83.7	89.8	96.7	97.0	92.4
2,3,4-TrCP	89.5	96.8	108.0	107.0	105.0
2,3,5,6-TeCP	84.3	96.8	99.6	97.7	96.2
2,3,4,6-TeCP	99.8	100.4	106.0	104.0	101.0
2,3,4,5-TeCP	78.8	87.4	93.6	94.0	92.1
PCP	62.3	65.4	68.9	68.7	67.6

QuEChERS-气相色谱-质谱法检测鱼肉中19种氯酚类化合物

Determination of 19 chlorophenols in fish by QuEChERS-gas chromatography-mass spectrometry

RichHTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 11

参考文献

相关文章 15

编辑推荐

Metrics

Chlorophenol	Linear range/(μg/L)	Linear equation	R²	LOD/(μg/kg)	LOQ/(μg/kg)
2-CP	0.4-10	y=7.758×10⁴x+1.023×10⁴	0.9990	0.02	0.07
3-CP	0.4-10	y=1.549×10⁵x+2.241×10⁴	0.9990	0.05	0.15
4-CP	0.4-10	y=1.427×10⁵x-9.968×10³	0.9995	0.03	0.10
2,5-DCP	0.4-10	y=5.411×10⁴x-6.486×10²	0.9997	0.01	0.04
2,6-DCP+3,5-DCP	0.4-10	y=1.719×10⁵x+3.156×10⁴	0.9983	0.01	0.04
2,4-DCP	0.4-10	y=5.162×10⁴x-2.254×10³	0.9997	0.02	0.06
2,3-DCP	0.4-10	y=5.653×10⁴x-4.791×10³	0.9993	0.02	0.08
3,4-DCP	0.4-10	y=7.47×10⁴x-3.027×10²	0.9997	0.01	0.04
2,4,6-TrCP	0.4-10	y=3.203×10⁴x-2.479×10³	0.9996	0.04	0.14
2,3,5-TrCP	0.4-10	y=4.044×10⁴x-4.319×10³	0.9990	0.03	0.12
2,4,5-TrCP	0.4-10	y=3.232×10⁴x+1.416×10³	0.9992	0.04	0.14
2,3,6-TrCP	0.4-10	y=3.974×10⁴x-3.531×10³	0.9993	0.03	0.10
3,4,5-TrCP	0.4-10	y=4.474×10⁴x-1.513×10³	0.9998	0.01	0.04
2,3,4-TrCP	0.4-10	y=3.388×10⁴x-4.986×10²	0.9996	0.05	0.16
2,3,5,6-TeCP	0.4-10	y=2.850×10⁴x-1.921×10³	0.9993	0.04	0.12
2,3,4,6-TeCP	0.4-10	y=2.732×10⁴x-2.681×10³	0.9991	0.02	0.07
2,3,4,5-TeCP	0.4-10	y=2.845×10⁴x-2.113×10³	0.9992	0.04	0.15
PCP	0.4-10	y=1.361×10⁴x-7.501×10²	0.9991	0.05	0.16

Chlorophenol	Low level (0.16 μg/kg)		Medium level (0.32 μg/kg)		High level (1.6 μg/kg)
Chlorophenol	Recovery/%	RSD/%	Recovery/%	RSD/%	Recovery/%	RSD/%
2-CP	76.5	8.7	78.7	6.8	75.0	7.5
3-CP	94.0	8.9	96.5	7.6	86.4	6.8
4-CP	82.0	7.6	86.4	6.2	82.7	4.3
2,5-DCP	93.0	6.8	97.0	5.7	107.0	7.6
2,6-DCP+3,5-DCP	98.5	6.5	102.0	7.4	114.0	8.2
2,4-DCP	109.0	9.4	103.0	10.5	97.0	7.3
2,3-DCP	76.0	10.5	79.4	7.1	82.0	6.2
3,4-DCP	102.0	5.5	96.0	4.2	98.5	4.7
2,4,6-TrCP	79.0	7.5	82.0	3.5	83.0	5.6
2,3,5-TrCP	96.5	3.5	98.0	6.2	95.0	5.2
2,4,5-TrCP	97.2	3.6	94.6	4.5	103.8	4.3
2,3,6-TrCP	80.4	2.6	88.7	2.8	94.2	7.4
3,4,5-TrCP	93.6	6.2	95.7	3.6	102.0	3.4
2,3,4-TrCP	96.5	8.3	84.2	3.2	88.7	4.6
2,3,5,6-TeCP	79.6	5.4	76.5	4.3	86.0	6.6
2,3,4,6-TeCP	89.6	4.2	87.5	5.4	95.1	6.1
2,3,4,5-TeCP	102.0	7.1	103.0	7.3	115.0	2.9
PCP	74.9	9.5	70.6	3.7	73.5	5.7

Chlorophenol	Matrix effects/%
Chlorophenol	Hairtail	Corvina	Cyprinoid
2-CP	16.8	-5.7	7.4
3-CP	-7.5	-6.3	11.7
4-CP	-11.9	-13.2	-7.5
2,5-DCP	73.0	17.6	16.9
2,6-DCP+3,5-DCP	34.8	-21.2	1.8
2,4-DCP	13.8	-16.4	19.8
2,3-DCP	26.4	-70.0	34.5
3,4-DCP	21.2	17.3	33.2
2,4,6-TrCP	9.2	-21.7	17.4
2,3,5-TrCP	-1.0	-24.1	1.1
2,4,5-TrCP	9.7	-12.5	19.3
2,3,6-TrCP	14.0	-28.0	38.0
3,4,5-TrCP	-5.2	-13.0	5.5
2,3,4-TrCP	14.3	-20.0	26.4
2,3,5,6-TeCP	15.7	-80.0	-3.4
2,3,4,6-TeCP	-20.9	-73.0	-13.8
2,3,4,5-TeCP	11.0	-40.7	20.0
PCP	-27.3	-37.6	-28.4

[1]	赵芮, 黄晴雯, 余智颖, 韩铮, 范楷, 赵志辉, 聂冬霞. QuEChERS-超高效液相色谱-串联质谱法同时测定水果中36种真菌毒素[J]. 色谱, 2023, 41(9): 760-770.
[2]	李洁, 鞠香, 王艳丽, 田其燕, 梁秀清, 李海霞, 刘艳明. QuEChERS-在线凝胶渗透色谱-气相色谱-串联质谱法高通量筛查动物源性食品中的多农药残留[J]. 色谱, 2023, 41(7): 610-621.
[3]	童学智, 陈东洋, 冯家力, 范翔, 张昊, 杨胜园. QuEChERS-超高效液相色谱-串联质谱法快速测定水产品中5种卤代苯醌[J]. 色谱, 2023, 41(6): 490-496.
[4]	王亚婷, 杨阳, 孙秀兰, 纪剑. 基于气相色谱-质谱法的广泛靶向代谢组学方法开发[J]. 色谱, 2023, 41(6): 520-526.
[5]	吴瑛瑕, 牟燕, 刘佩珊, 张易天, 曾颖炫, 周枝凤. 气相色谱-质谱法测定大鼠肝脏中的39种脂肪酸[J]. 色谱, 2023, 41(5): 443-449.
[6]	陈佳, 刘玉龙, 徐斌, 刘勤, 谢剑炜. 顶空固相微萃取-气相色谱-质谱法快速筛查油性基质中化学武器公约相关化合物[J]. 色谱, 2023, 41(4): 348-358.
[7]	刘柏林, 赵紫微, 詹子悦, 戴雁羽, 丁刚, 谢继安, 许相川, 孔洪涛. 改进QuEChERS法结合超高效液相色谱-串联质谱法同时测定冷冻食品中7种季铵盐化合物[J]. 色谱, 2023, 41(3): 233-240.
[8]	吴丽娟, 杨丽莉, 胡恩宇, 王美飞, 杨超, 尹明明. 气相色谱-质谱法测定土壤中14种苯胺类和联苯胺类化合物[J]. 色谱, 2023, 41(12): 1127-1134.
[9]	宁霄, 金绍明, 李志远, 杨崇俊, 貌达, 曹进. 功能性老年乳粉中300种非法添加药物及其类似物的液相色谱-高分辨质谱分析[J]. 色谱, 2023, 41(11): 960-975.
[10]	章璐幸, 周征, 曹琳, 钱江. 基于自建数据库的超高效液相色谱-四极杆-飞行时间质谱法测定谷物中7种真菌毒素[J]. 色谱, 2023, 41(11): 1002-1009.
[11]	李康聪, 杨吉双, 李秀琴, 高燕, 张庆合. QuEChERS-气相色谱-四极杆飞行时间质谱筛查大米中有机磷阻燃剂残留[J]. 色谱, 2023, 41(11): 1021-1029.
[12]	冯军军, 姜海云, 王静, 景正义, 张帆, 谭天宇, 贺锋, 江利华, 李海芹, 常世敏, 李腾飞. QuEChERS-高效液相色谱-串联质谱法同时测定豆芽中40种植物生长调节剂、杀菌剂、杀虫剂和抗生素类药物残留[J]. 色谱, 2022, 40(9): 843-853.
[13]	胡国绅, 王红, 余可垚, 沈伟健, 侯燕, 季美泉, 朱一鸣, 田雯, 李锡东. 气相色谱-负化学源质谱法测定船舶压载水中4种三卤甲烷[J]. 色谱, 2022, 40(6): 584-589.
[14]	张权, 毕珊, 吴玉田, 李磊, 周贻兵, 刘利亚, 刘文政, 陈庆园, 周雪, 郭华. Sin-QuEChERS Nano净化柱结合气相色谱-串联质谱法快速筛查石斛中84种农药残留[J]. 色谱, 2022, 40(6): 565-575.
[15]	冯月超, 王建凤, 侯帆, 丁奇, 楚弘宇, 刘艳. QuEChERS结合超高效液相色谱-串联质谱法同时测定畜禽肉中44种食源性兴奋剂和6种孕激素[J]. 色谱, 2022, 40(5): 409-422.