A Review of Pesticide Pollution Analysis Techniques for Environmental Water Samples
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摘要:
随着农业集约化和城市化的推进,世界上大量水环境中农药残留量已超过规定的限值,水环境中农药污染问题受到社会各界的广泛关注。作为世界上最大的农药生产国和使用国,中国水环境中农药残留量远高于其他发达国家,已有研究表明在我国七个典型流域(长江、太湖、黄河、松花江、黑龙江、大运河和东江)中检测到19种农药,平均浓度范围为0.02~332.75ng/L。农药及其转化产物对生态环境和人体健康具有潜在威胁,水环境中农药残留的研究是水质评估中必不可少的组成部分,而靶向筛查难以检测未知农药及其转化产物。因此,环境中农药残留及其转化产物的非靶向筛查亟需完善。本文依据农药组分非靶向筛查的分析流程,对近五年水质样品中农药残留靶向及非靶向筛查方法进行综述,梳理了近年来国内外食品与水环境中农药残留限量的相关法律法规,对水环境中农药残留分析方法的研究进展进行概述;总结了液液萃取(LLE)、固相萃取(SPE)、固相微萃取(SPME)等样品前处理方法的特点,在这些方法中,固相萃取是农药非靶向筛查的主要前处理方法,具有良好应用前景。本文还探讨了分析仪器从色谱检测到色谱-质谱联用的发展趋势,多种高分辨率质谱的产生为农药非靶向筛查提供了多层次的分析需求;同时通过总结近年来农药筛查确证相关的指导标准、质谱数据库与多种鉴定方法,指出水环境中农药污染分析技术的发展趋势。
Abstract:BACKGROUND With the advancement of agricultural intensification and urbanization, pesticide residues in a large numbers of water environments in the world have exceeded the prescribed limit. The issue of pesticide pollution in the water environment has received extensive attention from all sectors of society. As the largest pesticide producer and user country in the world, the amount of pesticide residues in the water environment in China is much higher than other developed countries. Available studies have detected 19 pesticides in seven typical river basins in China (the Yangtze River, Taihu Lake, Yellow River, Songhua River, Heilongjiang, Grand Canal and Dongjiang), with an average concentration ranging from 0.02 to 332.75ng/L. Pesticides and their transformation products pose potential threats to the ecological environment and human health. Research on pesticide residues in the water environment is an indispensable part of water quality assessment. However, targeted screening is difficult to detect unknown pesticides and their transformation products. Therefore, the non-targeted screening of pesticide residues and their transformation products in the environment needs to be improved.
OBJECTIVES To understand the pesticide pollution analysis techniques for environmental water samples.
METHODS According to the analysis process of non-targeted screening of pesticide components, the targeted and non-targeted screening methods for pesticide residues in water quality samples in the past 5 years were reviewed, and the regulations and standards for pesticide residue limits and non-targeted screening of pesticides in water quality were summarized. The research progress of pesticide residue analysis methods in water environment in recent years was summarized.
RESULTS The characteristics of liquid-liquid extraction (LLE), solid-phase extraction (SPE), solid-phase microextraction (SPME) and other pre-treatment methods were reviewed. Among them, solid-phase extraction was the main pre-treatment method for non-targeted pesticide screening and had good applications prospects. The development trend of analytical instruments from chromatography to chromatography mass spectrometry was discussed, and the production of a variety of high-resolution mass spectrometry provided multi-level analysis requirements for non-targeted pesticide screening. Finally, the guidelines, mass spectrometry database and various identification methods related to pesticide screening confirmation in recent years were summarized, and the development trend of pesticide pollution analysis technology in the water environment was prospected.
CONCLUSIONS High resolution mass spectrometry technology poses a challenge to the sample pretreatment and purification process. The combination of multiple technologies in the water sample pretreatment process is the future development trend. Research on non-targeted pesticide screening based on high-resolution mass spectrometry is widely studied in the field of food testing although it has low priority in the environmental field. Relevant organizations at home and abroad have not yet issued relevant standards for screening and confirmation of unknown substances. Currently, the confirmation of unknown screening requires manual data analysis, which cannot be fully automated.
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Key words:
- high resolution mass spectrometry /
- non-targeted screening /
- pesticide /
- database
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表 1 基于高分辨率质谱(HRMS)不同分析方法的应用
Table 1. Application of different analysis methods based on high-resolution mass spectrometry (HRMS)
方法应用 发表时间 筛查策略 样品基质 检测物质 样品前处理方法 检测仪器 数据分析软件 数据库 参考文献 非靶向筛查涪陵地区有机污染物 2020 非靶向筛查 表层水、土壤及沉积物 农药、药物及个人护理产品、塑料添加剂 固相萃取(HLB柱) 超高效液相色谱- 四极杆/静电场轨道阱高分辨质谱 Compound Discoverer 3.0 mzCloud数据库 [14] 检测青菜中214种农药残留 2020 靶向筛查 青菜样品 农药 QuEChERS方法 超高效液相色谱- 四极杆飞行时间质谱 - - [29] 婴儿配方食品中兽药和农药的多残留筛选 2020 靶向筛查 婴儿配方奶粉 兽药、农药 分散固相萃取(CleanertLipoNo管) 超高效液相色谱- 四极杆/静电场轨道阱高分辨质谱联用 TraceFinder 4.0、MZvault 2.0 - [30] 非靶向筛查谷物中农药残留 2020 非靶向筛查 谷物 农药 QuEChERS方法 超高效液相色谱串联三重四极杆质谱、液相色谱-四极杆飞行时间质谱 - - [31] 定量检测加工水果中的250种农药 2020 靶向筛查 加工水果 农药 QuEChERS方法 超高效液相色谱- 串联质谱 - - [3] 可疑和非靶向筛查表征普吉特海湾近海海洋环境中新兴污染物 2020 可疑和非靶向筛查 水 除草剂、药物、增塑剂、阻燃剂等 固相萃取(HLB柱) 液相色谱-四极杆飞行时间质谱 MassHunterProfinder (B.08.00)、Profiler Professional (B.13.00,MPP)、MassHunter定性分析(B.08.00)、XCMS Online NORMAN数据库、内部数据库、mzCloud数据库、EU MassBank数据库 [1] 中国淀山湖潜在污染物的非目标和目标分析 2020 靶向和非靶向筛查 水 农药、药物、表面活性剂、塑料添加剂 固相萃取(Oasis WAX,MCX、HLB) 超高效液相色谱- 四极杆/轨道阱质谱 Composite Discoverer 3.0 mzCloud数据库 [2] 水中2316种新兴污染物的综合定量分析方法 2020 靶向筛查 水 农药、药物、工业化学品等 固相萃取(Oasis HLB、Isolute ENV+、Strata-X-AW、Strata-X-CV) 超高效液相色谱- 四极杆飞行时间质谱 - - [6] 食品样品中农药多残留综合筛选和鉴定 2020 靶向和非靶向筛查 食品 农药 QuEChERS方法 气相色谱-串联质谱、超高效液相色谱-四极杆/静电场轨道阱高分辨质谱 Compound Discoverer 在线数据库(ChemSpider、Massbank和mzCloud等) [32] 可疑和非目标筛查评估德涅斯特河流域的化学污染状况 2020 可疑和非靶向筛查 水 农药、药物、兴奋剂等 固相萃取(HLB圆盘) 超高效液相色谱- 四极杆飞行时间质谱 TASQ Client 2.1、DataAnalysis 5.1 内部数据库 [12] 可疑筛查分析废水处理过程中的微量污染物 2019 可疑筛查 水 阻燃剂、农药、抗氧化剂、多环芳烃 固相萃取(Elut-Bond C18滤筒) 气相色谱-四极杆飞行时间质谱 Agilent Unknown Analysis software (B.08.00) NIST 14、大型个人化合物数据库(PCDL) [33] 茶叶中农药的非靶向筛选和靶向测定 2019 靶向和非靶向筛查 茶叶 农药 分散固相萃取 液相色谱-四极杆/静电场轨道阱高分辨质谱仪 - 内部数据库 [24] 可疑筛查表征受污染的地下水和径流中的新兴污染物 2019 可疑筛查 水 杀真菌剂、除草剂、抗生素等 固相膜萃取(SDB-RPS、SDB-XC) 液相色谱-四极杆飞行时间质谱联用 Data AnalysisⓇ4.4、TASQⓇ 1.4 Pesticide Screener 2.1、ToxScreener 2.1 [13] 海洋环境中的新兴有机污染物的靶向和非靶向筛查 2019 靶向和非靶向筛查 水 药物个人护理产品农药 固相萃取 超高效液相色谱-四极杆/静电场轨道阱高分辨质谱 Compound Discoverer 2.1、SIMCA 2.2 ChemSpider数据库 [11] 目标和可疑筛查表征瑞士地下水样中的农药及农药转化产物 2019 靶向和可疑筛查 水 农药及农药转化产物 真空辅助蒸发浓缩 超高效液相色谱-四极杆/静电场轨道阱高分辨质谱 MetFrag ChemSpider数据库 [8] 宽范围筛选地表水及地下水中农药 2019 非靶向筛查 水 农药及农药转化产物 固相萃取(HLB柱) 液相色谱-四极杆飞行时间质谱 MassLynx v4.1 自制数据库 [34] 宽范围筛选和定量分析综合调查巴西地表水中的农药 2019 靶向和非靶向筛查 水 农药及农药转化产物 固相萃取 气相色谱-四极杆飞行时间质谱、液相色谱-四极杆飞行时间质谱 商业软件 气相、液相色谱专用数据库 [35] 目标分析和可疑分析评估农业食品工业废水中农药水平 2019 靶向和可疑筛查 水 农药及农药转化产物 固相萃取(HLB柱) 液相色谱-四极杆线性离子阱串联质谱、液相色谱-四极杆飞行时间质谱 MasterViewTM1.1、PeakViewTM、AnalystTMTF 1.5、PathPred、EAWAG-BBD MassBank数据库 [36] 可疑、非目标和目标筛查评估地中海流域中新兴污染物 2019 靶向、可疑和非靶向筛查 水 农药、药物、个人护理产品及其他毒素 固相萃取(HLB柱) 液相色谱-四极杆飞行时间质谱 Waters UNIFI软件 ChemSpider数据库 [10] 非靶向快速筛查茶饮料中未知农药残留 2019 非靶向筛查 茶饮料 农药 分散液液微萃取 超高效液相色谱-四极杆飞行时间质谱 PeakView2.0、ChemDraw Ultra 14.0 - [37] 利用果蔬中485种农药的精确质量数据库和光谱库直接进行定性鉴定的新方法 2018 非靶向筛查 水果 农药 固相萃取 液相色谱-四极杆飞行时间质谱 Agilent MassHunter PCDL Manager (B.04.00)、Qualitative MassHunter 自制数据库 [17] 圣华金河三角洲的目标化合物和可疑化合物筛查 2017 靶向和可疑筛查 水 药物、阻燃剂、转化产物等 固相萃取(HLB、Strata XAW,Strata XCW、Isolute ENV+) 液相色谱-飞行时间质谱、气相色谱-飞行时间质谱 Agilent MassHunter定性分析B.07、Eawag途径预测系统(EAWAG-PPS25)、安捷伦分子结构关联器(MSC,B.07) Agilent LC/MS农药PCDL、Agilent GC/Q- TOF-农药PCDL [38] 快速筛查和识别地表和饮用水中的化学危害 2017 靶向、可疑和非靶向筛查 水 农药、药品、个人护理产品 直接进样/ 固相萃取(HLB柱) 液相色谱-四极杆飞行时间串联质谱 PeakView、MultiQuant ChemSpider数据库 [39] 综合分析水样中符合LC-MS要求且具有广泛理化性质的有机化学品 2017 靶向筛查 水 农药 固相萃取 液相色谱-飞行时间质谱 - - [40] 非靶向快速筛查进口粮谷中未知的农药残留 2017 非靶向筛查 粮谷 农药 快速提取农药 超高效液相色谱-四极杆飞行时间质谱 Agilent MassHunter定性软件、PCDL (Personal Compound Database & Library) 自制数据库 [41] 废水样品的非目标分析 2016 非靶向筛查 水 农药、药物等 固相萃取(Oasis MAX和Oasis MCX柱) 超高效液相色谱-离子淌度-四极杆串联飞行时间质谱仪、二维液相色谱-离子淌度-四极杆串联飞行时间质谱仪 Agilent IMMS Browser B.07.01 software CCS数据库 [7] 华北地区北京和天津地下水中1300种有机污染物的筛选 2016 靶向筛查 水 农药、多环芳烃、香料等 固相萃膜取(玻璃膜纤维盘、苯乙烯二乙烯基苯圆盘、活性炭圆盘) 液相色谱-飞行时间质谱 - - [42] 非目标筛查方法检测合法和非法药物以及个人护理产品 2016 非靶向筛查 水 药物、农药、多酚等 固相萃取 超高效液相色谱- 四极杆飞行时间二级质谱 Analyst、Peak View 1.0、XICmanager、MultiQuant 2.0 - [43] 水果、蔬菜中208种农药残留筛查确证能力的对比 2015 靶向和非靶向筛查 蔬菜、水果 农药 QuEChERS方法 气相色谱-三重四极杆质谱仪、气相色谱-四极杆飞行时间质谱仪 - NIST数据库 [26] 表 2 质谱数据确认化学残留物的验收标准
Table 2. Acceptance criteria for confirmation of identification of chemical residues using exact mass data
MS模式 MS数据验收标准 MS/MS数据验收标准 MS和MS/MS数据验收标准 信噪比 S/N≥3 S/N≥3 S/N≥3 保留时间 ≤0.2min,或2.5%以内(不超过0.5min),或在建立的误差范围内(不超过0.5min) 具有结构意义的离子数 2 2 2 质量精度 ≤5ppm ≤10ppm MS≤5ppm; MS/MS≤10ppm -
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