WO2020244311A1 - Method for rapid extraction and analysis of 10 polycyclic aromatic hydrocarbons in water - Google Patents
Method for rapid extraction and analysis of 10 polycyclic aromatic hydrocarbons in water Download PDFInfo
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- WO2020244311A1 WO2020244311A1 PCT/CN2020/084609 CN2020084609W WO2020244311A1 WO 2020244311 A1 WO2020244311 A1 WO 2020244311A1 CN 2020084609 W CN2020084609 W CN 2020084609W WO 2020244311 A1 WO2020244311 A1 WO 2020244311A1
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- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1826—Organic contamination in water
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
- G01N2030/8854—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds involving hydrocarbons
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- the invention relates to a method for rapidly extracting and analyzing 10 kinds of polycyclic aromatic hydrocarbons in water, using a parallel solid-phase membrane flake sample pretreatment microporous plate system to quickly extract samples, and an ultra-high performance liquid chromatography-mass spectrometry combined technology for rapid analysis and determination Method of polycyclic aromatic hydrocarbon content in water.
- PAHs Environmental pollutants, polycyclic aromatic hydrocarbons PAHs, are compounds containing two or more benzene rings. They are relatively weak in polarity and easily soluble in non-polar and medium-polar solvents.
- the extraction methods of PAHs mainly include Soxhlet extraction, ultrasonic extraction, microwave extraction, accelerated solvent extraction, and solid phase microextraction.
- the Soxhlet extraction method is cumbersome to operate, time-consuming, and solvent consumption is relatively large; the microwave extraction method is not ideal for the extraction efficiency of low-ring compounds; accelerated solvent extraction and solid phase microextraction require equipment, maintenance and use costs High; no matter which extraction method is used, a large number of samples are required and the process is complicated.
- the extraction solvent of PAHs is mainly a mixed solvent of dichloromethane, n-hexane and acetone in different proportions.
- solvents such as dichloromethane, n-hexane, acetone, etc.
- solvent conversion process involves rotary evaporation, nitrogen blowing and other steps, which easily cause the loss of the analyte, and the solvent conversion is not easy full.
- the LC/MS/MS-based parallel solid phase membrane sheet sample pretreatment microplate system extraction method provided by the present invention is convenient to operate, low in cost, small in sample volume, and suitable for simultaneous processing of large batches of samples. At the same time, it has the advantages of short test time and good reproducibility.
- the purpose of the present invention is to provide a method for rapidly extracting and analyzing 10 kinds of polycyclic aromatic hydrocarbons in water.
- the parallel solid-phase membrane sheet sample pretreatment microplate system device involved in the method is composed of membrane sheet system 1, 96-well plate 2 and
- the oscillating device 3 is composed of ultra-high performance liquid chromatography-triple quadrupole mass spectrometry technology to quantitatively determine the content of environmental pollutants polycyclic aromatic hydrocarbons.
- the detection is completed within 10 minutes, and the average pretreatment time for each sample is about 1 minute.
- the method has good reproducibility and good stability, and is a fast and effective method for extracting and determining the content of polycyclic aromatic hydrocarbons in water.
- the method for rapidly extracting and analyzing 10 kinds of polycyclic aromatic hydrocarbons in water includes the following steps:
- Sample processing add water sample to the sample container, shake the sample container, and absorb for 50 minutes at the same time, replace with a new sample container and add acetonitrile with a volume ratio of 80:20 to the sample container: water shake and desorb for 50 minutes, complete Then inject the water sample into the ultra-high performance liquid chromatography-mass spectrometry analysis to be tested;
- Ultra performance liquid chromatography conditions mobile phase: A-water, B-acetonitrile; elution gradient: 0-2 minutes, A 60%; 2-3 minutes, A 60%-20%; 3.0-8.0 minutes, A 20%; 8.0-8.1 minutes, A 20%-60%; 8.1-10.0 minutes, A60%, flow rate: 0.35mL/min; column temperature: 30°C; injection volume: 5 ⁇ L;
- Mass spectrometry conditions ion source current: +4.0v; ion source temperature: 400°C; sheath gas: 35arb; auxiliary gas: 5arb; ion transmission capillary temperature: 350°C;
- reference substance solution accurately pipet 100 ⁇ L of reference substance, dissolve it with acetonitrile and dilute to 1mL, as the reference substance solution stock solution; among them, the reference substance is 10 kinds of polycyclic aromatic hydrocarbon standard substances;
- Standard curve drawing Precisely transfer the reference solution stock solution and dilute it with diluent to different concentrations to obtain the standard solution; perform ultra-high performance liquid chromatography-mass spectrometry analysis according to chromatographic conditions; perform regression analysis on the peak area by concentration, Obtain the standard curve of its components and calculate the regression equation;
- the sample processing in the method uses a parallel solid phase membrane sheet sample pretreatment microplate system device, and the device is mainly composed of a membrane sheet System, sample container and oscillating device composition;
- sample processing add water sample to the sample container, place the sample container in the shaking device, shake by the shaking device, and at the same time be absorbed by the membrane system, replace with a new sample container and add a volume ratio of 80:20 to the sample container Acetonitrile: Water shake and desorb for 50 minutes. After completion, the water sample is injected into the ultra performance liquid chromatography-mass spectrometry for analysis.
- the film sheet system of the present invention mainly consists of a film sheet and a fixing frame for fixing the film sheet.
- the film sheet can be 0.5-2mm thick, (1-10) ⁇ (20-80) mm stainless steel sheet (preferably 1mm thick, 5x50mm stainless steel sheet), and the stainless steel sheet is coated by chemical bonding and physical means.
- the material of the coated film can be but not limited to DVB (divinylbenzene) or C18, etc., and different coating materials can be selected according to the sample tested.
- the thickness of the coated coating can be 0.5-2mm, such as but not limited to 0.5mm, 1mm, 1.5mm, 2mm and so on.
- the oscillating device involved in the present invention can be any conventional oscillating device in the field that can realize the present invention, and there is no special limitation here.
- the sample container is directly stuck in the oscillating device and can be flexibly taken and placed in the oscillating device.
- the membrane flake system is vertically immersed in the liquid in the sample container. Adsorption and elution.
- the chromatographic column of step b ultra-high performance liquid chromatography is: Hypersil GOLD, C18 100 ⁇ 2.1mm, 1.9 ⁇ m or the like Effective column.
- the type of ion source in step c is: atmospheric pressure chemical APCI ion source.
- the diluent in step e is a water:acetonitrile solution with a volume ratio of 20:80.
- step e is diluted with a diluent to a concentration of 2ng/mL, 4ng/mL, 20ng/mL, 40ng/mL, 200ng/mL, 400ng/mL, get the standard solution.
- the sample container can be any container in the art, for example, but not limited to, a porous plate. More preferably, The sample container can be a 96-well plate.
- a method for rapidly extracting and analyzing 10 kinds of polycyclic aromatic hydrocarbons in water the parallel solid-phase membrane sheet sample pretreatment microplate system device involved in the method is composed of shaking device 1, 96-well plate 2 and membrane sheet The system consists of 3, and the specific operation is carried out according to the following steps:
- Ultra-high performance liquid chromatography conditions Column: Hypersil GOLD, C18 100 ⁇ 2.1mm, 1.9 ⁇ m; Mobile phase: A-water, B-acetonitrile; Elution gradient: 0-2 minutes, A 60%; 2- 3 minutes, A 60%-20%; 3.0-8.0 minutes, A20%; 8.0-8.1 minutes, A 20%-60%; 8.1-10.0 minutes, A60%, flow rate: 0.35mL/min; column temperature: 30°C ; Injection volume: 5 ⁇ L;
- Mass spectrometry conditions ion source current: +4.0v; ion source temperature: 400°C; sheath gas: 35arb; auxiliary gas: 5arb; ion transmission capillary temperature: 350°C; ion source type: atmospheric pressure chemical APCI ion source;
- reference substance solution accurately pipet 100 ⁇ L of reference substance, dissolve it with acetonitrile and dilute to 1mL, as the reference substance solution stock solution;
- Standard curve drawing Precisely pipette the stock solution of the reference solution, and dilute it to the concentration of 2ng/mL, 4ng/mL, 20ng/mL, 40ng/mL, 200ng with the diluent volume ratio of 20:80 water: acetonitrile solution. /mL, 400ng/mL, to obtain a standard solution; perform ultra-high performance liquid chromatography-mass spectrometry analysis according to chromatographic conditions; perform regression analysis on the peak area by concentration to obtain the standard curve of its components, and calculate the regression equation;
- f. Content determination Precisely draw the sample to be tested, perform ultra-high performance liquid chromatography-mass spectrometry analysis according to chromatographic conditions, and bring the peak area into the standard curve to calculate the content.
- the detection result naphthalene 6.0-207ng; acenaphthene 2.4-30, 7ng; acenaphthylene 1.7-48.0ng; fluorene 5.6-60.5ng; phenanthrene 11.1-64.2ng; anthracene 1.06-66.8ng; fluoranthene 5.9-52.5ng; pyrene 3.7-70.4ng; benzopyrene b-fluoranthene 1.7-16ng; Benzo a pyrene 18-118ng.
- Figure 1 is the spectrum of the standard sample of the present invention, in which the peaks of the total ion current pattern are: naphthalene (4.15min); acenaphthylene (4.30min); fluorene (4.53min); acenaphthene (4.54min); phenanthrene (4.63min) ; Anthracene (4.72min); Fluoranthene (4.94min); Pyrene (5.09min); Benzo(b)fluoranthene (6.00min); Benzo(a)pyrene(6.22min);
- Fig. 2 is a schematic diagram of a microplate system device for pre-processing parallel solid-phase membrane flake samples of the present invention.
- a laboratory water sample is used as an example. After the sample is prepared, the sample is extracted according to the preparation method provided by the present invention, and the content of polycyclic aromatic hydrocarbons is determined according to the determination method provided by the present invention:
- Ultra-performance liquid chromatography (Agilent 1290); mass spectrometer (Thermo TSQ QUANTUM ULTRA); one-tenth electronic balance (METTLER AM100); acetonitrile is a chromatographic pure reagent, polycyclic aromatic hydrocarbon reference substance (BePure);
- Mass spectrometer conditions ion source current: +4.0v; ion source temperature: 400°C; sheath gas: 35arb; auxiliary gas: 5arb; ion transmission capillary temperature: 350°C; ion source type: atmospheric pressure chemical APCI ion source;
- Sample processing Precisely aspirate 2 mL of water sample and place it in 2 wells of a 96-well plate. Place 96-well plate 2 in the parallel solid-phase membrane thin film system, shake by the shaking device 3, and absorb it by the membrane thin film system 1 for 50 minutes. Load a new 96-well plate 2. Add 1 mL of acetonitrile: water eluent with a volume ratio of 80:20 to each well, shake and desorb for 50 minutes. After completion, put the 96-well plate 2 into the autosampler for super high efficiency. Liquid chromatography-mass spectrometry analysis;
- the preparation of the reference solution the preparation of the reference solution: accurately weigh and pipet 100 ⁇ L of the reference substance, dissolve it with acetonitrile and dilute to 1mL, as the reference solution stock solution;
- sample test results naphthalene 6.0-207ng; acenaphthene 2.4-30.7ng; acenaphthylene 1.7-48.0ng; fluorene 5.6-60.5ng; phenanthrene 11.1-64.2ng; anthracene 1.06-66.8ng; fluoranthene 5.9-52.5ng; pyrene 3.7- 70.4ng; Benzopyrene b-fluoranthene 1.7-16ng; Benzoapyrene 18-118ng;
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Abstract
Description
相关申请的交叉参考Cross reference of related applications
该申请要求2019年06月06日提交的中国专利申请号为201910492469.4的专利申请的优先权，该专利申请在此被完全引入作为参考。This application claims the priority of the Chinese patent application number 201910492469.4 filed on June 6, 2019, which is fully incorporated herein by reference.
本发明涉及一种快速提取分析水中10种多环芳烃的方法，利用平行固相膜薄片样品前处理微孔板系统快速提取样品，以及一种超高效液相色谱-质谱联用技术快速分析测定水中多环芳烃含量的方法。The invention relates to a method for rapidly extracting and analyzing 10 kinds of polycyclic aromatic hydrocarbons in water, using a parallel solid-phase membrane flake sample pretreatment microporous plate system to quickly extract samples, and an ultra-high performance liquid chromatography-mass spectrometry combined technology for rapid analysis and determination Method of polycyclic aromatic hydrocarbon content in water.
环境污染物多环芳烃PAHs为含有2个及2个以上苯环的化合物,极性较弱,易溶于非极性及中等极性的溶剂。PAHs的提取方法主要有索氏提取法、超声提取法、微波提取法、加速溶剂萃取法、固相微萃取法等。索氏提取法操作繁琐，耗时较长,溶剂消耗量比较大；微波提取法对低环化合物的提取效率不是很理想；加速溶剂萃取法和固相微萃取法需要配置仪器,维护及使用成本较高；无论采用哪种提取方法，都需要大量的样品，且过程繁杂。Environmental pollutants, polycyclic aromatic hydrocarbons PAHs, are compounds containing two or more benzene rings. They are relatively weak in polarity and easily soluble in non-polar and medium-polar solvents. The extraction methods of PAHs mainly include Soxhlet extraction, ultrasonic extraction, microwave extraction, accelerated solvent extraction, and solid phase microextraction. The Soxhlet extraction method is cumbersome to operate, time-consuming, and solvent consumption is relatively large; the microwave extraction method is not ideal for the extraction efficiency of low-ring compounds; accelerated solvent extraction and solid phase microextraction require equipment, maintenance and use costs High; no matter which extraction method is used, a large number of samples are required and the process is complicated.
PAHs的提取溶剂主要为二氯甲烷、正己烷、丙酮的不同比例的混合溶剂。在液相色谱分析前需要将二氯甲烷、正己烷、丙酮等溶剂转换为乙腈、甲醇等溶剂,而溶剂转换过程涉及旋蒸、氮吹等步骤,容易引起待测物损失,溶剂转换不容易充分。The extraction solvent of PAHs is mainly a mixed solvent of dichloromethane, n-hexane and acetone in different proportions. Before liquid chromatography analysis, it is necessary to convert solvents such as dichloromethane, n-hexane, acetone, etc. into solvents such as acetonitrile and methanol, and the solvent conversion process involves rotary evaporation, nitrogen blowing and other steps, which easily cause the loss of the analyte, and the solvent conversion is not easy full.
相关文献《液相色谱-大气压光电电离源质谱法同时测定电子电气产品中16种多环芳烃残留》殷居易，谢东华，陈建国等，虽然也是用液质联用检测多环芳烃，但是相对本发明提取方法繁琐，耗时较长，而且被测样品也不相同，本发明主要针对水样中10种多环芳烃的检测方法。Related literature "Simultaneous Determination of 16 Polycyclic Aromatic Hydrocarbon Residues in Electronic and Electrical Products by Liquid Chromatography-Atmospheric Pressure Photoionization Source Mass Spectrometry" Yin Juyi, Xie Donghua, Chen Jianguo, etc., although they also use liquid chromatography mass spectrometry to detect polycyclic aromatic hydrocarbons, they are relatively extracted from the present invention The method is cumbersome, takes a long time, and the tested samples are different. The present invention is mainly aimed at the detection method of 10 kinds of polycyclic aromatic hydrocarbons in water samples.
相对而言，本发明提供的基于LC/MS/MS的平行固相膜薄片样品前处理微孔板系统提取方法操作方便、成本较低，样品量不多，适合大批量样品同时处理。同时具有测试时间短，重现性好的等优点。In contrast, the LC/MS/MS-based parallel solid phase membrane sheet sample pretreatment microplate system extraction method provided by the present invention is convenient to operate, low in cost, small in sample volume, and suitable for simultaneous processing of large batches of samples. At the same time, it has the advantages of short test time and good reproducibility.
发明内容Summary of the invention
本发明目的是，提供一种快速提取分析水中10种多环芳烃的方法，该方法 中涉及的平行固相膜薄片样品前处理微孔板系统装置是由膜薄片系统1、96孔板2和震荡装置3组成，采用超高效液相色谱-三重四极杆质谱联用技术对环境污染物多环芳烃含量进行定量测定，10分钟内完成检测，平均每个样品前处理时间1分钟左右。该方法重现性好，稳定性好，是提取测定水中多环芳烃含量的快速有效手段。The purpose of the present invention is to provide a method for rapidly extracting and analyzing 10 kinds of polycyclic aromatic hydrocarbons in water. The parallel solid-phase membrane sheet sample pretreatment microplate system device involved in the method is composed of membrane sheet system 1, 96-
本发明提供的一种快速提取分析水中10种多环芳烃的方法，包括以下步骤：The method for rapidly extracting and analyzing 10 kinds of polycyclic aromatic hydrocarbons in water provided by the present invention includes the following steps:
a、样品处理：在样品容器中加入水样品，将样品容器震荡，同时吸附50分钟，换上新的样品容器并在样品容器中加入体积比80:20的乙腈:水震荡解吸50分钟，完成后将水样品进样到超高效液相色谱-质谱分析待测；a. Sample processing: add water sample to the sample container, shake the sample container, and absorb for 50 minutes at the same time, replace with a new sample container and add acetonitrile with a volume ratio of 80:20 to the sample container: water shake and desorb for 50 minutes, complete Then inject the water sample into the ultra-high performance liquid chromatography-mass spectrometry analysis to be tested;
b、超高效液相色谱条件：流动相：A-水，B-乙腈；洗脱梯度：0-2分钟，A 60％；2-3分钟，A 60％-20％；3.0-8.0分钟，A 20％；8.0-8.1分钟，A 20％-60％；8.1-10.0分钟，A60％，流速：0.35mL/min；柱温：30℃；进样量：5μL；b. Ultra performance liquid chromatography conditions: mobile phase: A-water, B-acetonitrile; elution gradient: 0-2 minutes, A 60%; 2-3 minutes, A 60%-20%; 3.0-8.0 minutes,
c、质谱条件：离子源电流：+4.0v；离子源温度：400℃；鞘气：35arb；辅助气：5arb；离子传输毛细管温度：350℃；c. Mass spectrometry conditions: ion source current: +4.0v; ion source temperature: 400℃; sheath gas: 35arb; auxiliary gas: 5arb; ion transmission capillary temperature: 350℃;
d、对照品溶液的制备：精密移取100μL对照品，用乙腈溶解定容至1mL，作为对照品溶液储备液；其中，对照品为10种多环芳烃标准物质；d. Preparation of reference substance solution: accurately pipet 100μL of reference substance, dissolve it with acetonitrile and dilute to 1mL, as the reference substance solution stock solution; among them, the reference substance is 10 kinds of polycyclic aromatic hydrocarbon standard substances;
e、标准曲线绘制：精密移取对照品溶液储备液，并用稀释剂分别稀释成不同浓度，得到标准溶液；按色谱条件进行超高效液相色谱-质谱分析；以浓度对峰面积进行回归分析，得其组分标准曲线，计算回归方程；e. Standard curve drawing: Precisely transfer the reference solution stock solution and dilute it with diluent to different concentrations to obtain the standard solution; perform ultra-high performance liquid chromatography-mass spectrometry analysis according to chromatographic conditions; perform regression analysis on the peak area by concentration, Obtain the standard curve of its components and calculate the regression equation;
f、含量测定：精密吸取样品待测液，按色谱条件进行超高效液相色谱-质谱分析，并将峰面积带入标准曲线，计算含量，获得检测结果。f. Content determination: Precisely draw the sample to be tested, perform ultra-high performance liquid chromatography-mass spectrometry analysis according to the chromatographic conditions, and bring the peak area into the standard curve, calculate the content, and obtain the test result.
根据本发明所述的快速提取分析水中10种多环芳烃的方法，其中优选地，该方法中样品处理使用平行固相膜薄片样品前处理微孔板系统装置，所述装置是主要由膜薄片系统、样品容器和震荡装置组成；According to the method for rapid extraction and analysis of 10 polycyclic aromatic hydrocarbons in water according to the present invention, preferably, the sample processing in the method uses a parallel solid phase membrane sheet sample pretreatment microplate system device, and the device is mainly composed of a membrane sheet System, sample container and oscillating device composition;
样品处理时，在样品容器中加入水样品，将样品容器放置在震荡装置中，由震荡装置震荡，同时由膜薄片系统吸附，换上新的样品容器并在样品容器中加入体积比80:20的乙腈:水震荡解吸50分钟，完成后将水样品进样到超高效液相色谱-质谱分析待测。During sample processing, add water sample to the sample container, place the sample container in the shaking device, shake by the shaking device, and at the same time be absorbed by the membrane system, replace with a new sample container and add a volume ratio of 80:20 to the sample container Acetonitrile: Water shake and desorb for 50 minutes. After completion, the water sample is injected into the ultra performance liquid chromatography-mass spectrometry for analysis.
本发明的膜薄片系统主要有膜薄片及用于固定膜薄片的固定架组成。膜薄片可以采用0.5～2mm厚、(1～10)×(20～80)mm大小不锈钢薄片(优选1mm厚、5x50mm大小不锈钢薄片)，通过化学键合和物理手段在不锈钢薄片上包覆 涂层，制备成一定涂层厚度的膜状萃取薄片，所包覆薄膜的材料可以但不限于DVB(二乙烯基苯)或C18等，根据所测样品可以选不同的涂层材料。所包覆的涂层厚度可以是0.5～2mm，例如但不限于0.5mm、1mm、1.5mm、2mm等等。The film sheet system of the present invention mainly consists of a film sheet and a fixing frame for fixing the film sheet. The film sheet can be 0.5-2mm thick, (1-10)×(20-80) mm stainless steel sheet (preferably 1mm thick, 5x50mm stainless steel sheet), and the stainless steel sheet is coated by chemical bonding and physical means. Prepared into a film-like extraction sheet with a certain coating thickness, the material of the coated film can be but not limited to DVB (divinylbenzene) or C18, etc., and different coating materials can be selected according to the sample tested. The thickness of the coated coating can be 0.5-2mm, such as but not limited to 0.5mm, 1mm, 1.5mm, 2mm and so on.
本发明涉及的震荡装置可以是任意可实现本发明的本领域常规的震荡器，在此不做特殊限定。The oscillating device involved in the present invention can be any conventional oscillating device in the field that can realize the present invention, and there is no special limitation here.
本发明的平行固相膜薄片样品前处理微孔板系统，在操作时，样品容器直接卡在震荡装置中，可以灵活取放于震荡装置中，膜薄片系统垂直浸入样品容器内的液体中进行吸附洗脱。In the parallel solid-phase membrane flake sample pre-processing microplate system of the present invention, during operation, the sample container is directly stuck in the oscillating device and can be flexibly taken and placed in the oscillating device. The membrane flake system is vertically immersed in the liquid in the sample container. Adsorption and elution.
根据本发明所述的快速提取分析水中10种多环芳烃的方法，其中作为一种优选，步骤b超高效液相色谱的色谱柱为：Hypersil GOLD，C18 100×2.1mm，1.9μm或其等效柱。According to the method for rapid extraction and analysis of 10 polycyclic aromatic hydrocarbons in water according to the present invention, as a preference, the chromatographic column of step b ultra-high performance liquid chromatography is: Hypersil GOLD, C18 100×2.1mm, 1.9μm or the like Effective column.
根据本发明所述的快速提取分析水中10种多环芳烃的方法，其中作为一种优选，步骤c离子源类型为：大气压化学APCI离子源。According to the method for rapidly extracting and analyzing 10 kinds of polycyclic aromatic hydrocarbons in water according to the present invention, as a preference, the type of ion source in step c is: atmospheric pressure chemical APCI ion source.
根据本发明所述的快速提取分析水中10种多环芳烃的方法，其中作为一种优选，步骤e所述稀释剂为体积比20:80的水:乙腈溶液。According to the method for rapidly extracting and analyzing 10 kinds of polycyclic aromatic hydrocarbons in water according to the present invention, as a preference, the diluent in step e is a water:acetonitrile solution with a volume ratio of 20:80.
根据本发明所述的快速提取分析水中10种多环芳烃的方法，其中作为一种优选，步骤e用稀释剂分别稀释成浓度为2ng/mL，4ng/mL，20ng/mL，40ng/mL，200ng/mL，400ng/mL，得到标准溶液。According to the method for rapidly extracting and analyzing 10 polycyclic aromatic hydrocarbons in water according to the present invention, as a preferred method, step e is diluted with a diluent to a concentration of 2ng/mL, 4ng/mL, 20ng/mL, 40ng/mL, 200ng/mL, 400ng/mL, get the standard solution.
根据本发明所述的快速提取分析水中10种多环芳烃的方法，其中作为一种优选，所述样品容器可以本领域的任意容器，例如但不限于可以是多孔板，进一步优选的，所述样品容器可以为96孔板。According to the method for rapidly extracting and analyzing 10 kinds of polycyclic aromatic hydrocarbons in water according to the present invention, as a preference, the sample container can be any container in the art, for example, but not limited to, a porous plate. More preferably, The sample container can be a 96-well plate.
根据本发明所述的快速提取分析水中10种多环芳烃的方法，作为一种优选方式，本发明的技术方案可以如下所述：According to the method for rapid extraction and analysis of 10 polycyclic aromatic hydrocarbons in water according to the present invention, as a preferred way, the technical scheme of the present invention can be as follows:
本发明所述的一种快速提取分析水中10种多环芳烃的方法，该方法中涉及的平行固相膜薄片样品前处理微孔板系统装置是由震荡装置1、96孔板2和膜薄片系统3组成，具体操作按下列步骤进行：According to the present invention, a method for rapidly extracting and analyzing 10 kinds of polycyclic aromatic hydrocarbons in water, the parallel solid-phase membrane sheet sample pretreatment microplate system device involved in the method is composed of shaking device 1, 96-
a、样品处理：在96孔板2中加入水样品，将96孔板2放置在震荡装置3中，由震荡装置3震荡，同时由膜薄片系统1吸附50分钟，换上新的96孔板2每个孔中加入体积比80:20的乙腈:水震荡解吸50分钟，完成后将96孔板2放入自动进样器中进样到超高效液相色谱-质谱分析待测；a. Sample processing: Add water sample to the 96-
b、超高效液相色谱条件：色谱柱：Hypersil GOLD，C18 100×2.1mm，1.9μm； 流动相：A-水，B-乙腈；洗脱梯度：0-2分钟，A 60％；2-3分钟，A 60％-20％；3.0-8.0分钟，A20％；8.0-8.1分钟，A 20％-60％；8.1-10.0分钟，A60％，流速：0.35mL/min；柱温：30℃；进样量：5μL；b. Ultra-high performance liquid chromatography conditions: Column: Hypersil GOLD, C18 100×2.1mm, 1.9μm; Mobile phase: A-water, B-acetonitrile; Elution gradient: 0-2 minutes, A 60%; 2- 3 minutes, A 60%-20%; 3.0-8.0 minutes, A20%; 8.0-8.1 minutes, A 20%-60%; 8.1-10.0 minutes, A60%, flow rate: 0.35mL/min; column temperature: 30°C ; Injection volume: 5μL;
c、质谱条件：离子源电流：+4.0v；离子源温度：400℃；鞘气：35arb；辅助气：5arb；离子传输毛细管温度：350℃；离子源类型：大气压化学APCI离子源；c. Mass spectrometry conditions: ion source current: +4.0v; ion source temperature: 400°C; sheath gas: 35arb; auxiliary gas: 5arb; ion transmission capillary temperature: 350°C; ion source type: atmospheric pressure chemical APCI ion source;
d、对照品溶液的制备：精密移取100μL对照品，用乙腈溶解定容至1mL，作为对照品溶液储备液；d. Preparation of reference substance solution: accurately pipet 100μL of reference substance, dissolve it with acetonitrile and dilute to 1mL, as the reference substance solution stock solution;
e、标准曲线绘制：精密移取对照品溶液储备液，并用稀释剂体积比20:80的水:乙腈溶液分别稀释成浓度为2ng/mL，4ng/mL，20ng/mL，40ng/mL，200ng/mL，400ng/mL，得到标准溶液；按色谱条件进行超高效液相色谱-质谱分析；以浓度对峰面积进行回归分析，得其组分标准曲线，计算回归方程；e. Standard curve drawing: Precisely pipette the stock solution of the reference solution, and dilute it to the concentration of 2ng/mL, 4ng/mL, 20ng/mL, 40ng/mL, 200ng with the diluent volume ratio of 20:80 water: acetonitrile solution. /mL, 400ng/mL, to obtain a standard solution; perform ultra-high performance liquid chromatography-mass spectrometry analysis according to chromatographic conditions; perform regression analysis on the peak area by concentration to obtain the standard curve of its components, and calculate the regression equation;
f、含量测定：精密吸取样品待测液，按色谱条件进行超高效液相色谱-质谱分析，并将峰面积带入标准曲线，计算含量，检测结果：萘6.0-207ng；苊2.4-30，7ng；苊烯1.7-48.0ng；芴5.6-60.5ng；菲11.1-64.2ng；蒽1.06-66.8ng；荧蒽5.9-52.5ng；芘3.7-70.4ng；苯并芘b荧蒽1.7-16ng；苯并a芘18-118ng。f. Content determination: Precisely draw the sample to be tested, perform ultra-high performance liquid chromatography-mass spectrometry analysis according to chromatographic conditions, and bring the peak area into the standard curve to calculate the content. The detection result: naphthalene 6.0-207ng; acenaphthene 2.4-30, 7ng; acenaphthylene 1.7-48.0ng; fluorene 5.6-60.5ng; phenanthrene 11.1-64.2ng; anthracene 1.06-66.8ng; fluoranthene 5.9-52.5ng; pyrene 3.7-70.4ng; benzopyrene b-fluoranthene 1.7-16ng; Benzo a pyrene 18-118ng.
图1为本发明标样的谱图，其中总离子流图谱峰依次为：萘(4.15min)；苊烯(4.30min)；芴(4.53min)；苊(4.54min)；菲(4.63min)；蒽(4.72min)；荧蒽(4.94min)；芘(5.09min)；苯并(b)荧蒽(6.00min)；苯并(a)芘(6.22min)；Figure 1 is the spectrum of the standard sample of the present invention, in which the peaks of the total ion current pattern are: naphthalene (4.15min); acenaphthylene (4.30min); fluorene (4.53min); acenaphthene (4.54min); phenanthrene (4.63min) ; Anthracene (4.72min); Fluoranthene (4.94min); Pyrene (5.09min); Benzo(b)fluoranthene (6.00min); Benzo(a)pyrene(6.22min);
图2为本发明平行固相膜薄片样品前处理微孔板系统装置示意图。Fig. 2 is a schematic diagram of a microplate system device for pre-processing parallel solid-phase membrane flake samples of the present invention.
实施例Example
本发明用实验室水样为例，样品制备后按本发明提供的制备方法提取样品，按照本发明提供的测定方法进行多环芳烃的含量测定：In the present invention, a laboratory water sample is used as an example. After the sample is prepared, the sample is extracted according to the preparation method provided by the present invention, and the content of polycyclic aromatic hydrocarbons is determined according to the determination method provided by the present invention:
仪器与试剂：Instruments and reagents:
超高效液相色谱仪(Agilent 1290)；质谱仪(Thermo TSQ QUANTUM ULTRA)；万分之一电子天平(METTLER AM100)；乙腈为色谱纯试剂，多环芳烃对照品(BePure)；Ultra-performance liquid chromatography (Agilent 1290); mass spectrometer (Thermo TSQ QUANTUM ULTRA); one-tenth electronic balance (METTLER AM100); acetonitrile is a chromatographic pure reagent, polycyclic aromatic hydrocarbon reference substance (BePure);
仪器条件：Instrument conditions:
超高效液相色谱仪条件：Ultra performance liquid chromatograph conditions:
色谱柱：Hypersil GOLD，C18 100×2.1mm，1.9μm；流动相：A-超纯水，B-乙腈；洗脱梯度：Chromatographic column: Hypersil GOLD, C18 100×2.1mm, 1.9μm; Mobile phase: A-ultra pure water, B-acetonitrile; Elution gradient:
流速：0.35mL/min；柱温：30℃；进样量：5μL；Flow rate: 0.35mL/min; Column temperature: 30℃; Injection volume: 5μL;
质谱仪条件：离子源电流：+4.0v；离子源温度：400℃；鞘气：35arb；辅助气：5arb；离子传输毛细管温度：350℃；离子源类型：大气压化学APCI离子源；Mass spectrometer conditions: ion source current: +4.0v; ion source temperature: 400℃; sheath gas: 35arb; auxiliary gas: 5arb; ion transmission capillary temperature: 350℃; ion source type: atmospheric pressure chemical APCI ion source;
样品处理：精密吸取2mL水样，置于96孔板2孔中，将96孔板2放置在平行固相膜薄片系统中，由震荡装置3震荡，同时由膜薄片系统1吸附50分钟，换上新的96孔板2每个孔中加入1mL体积比80:20的乙腈:水洗脱液，震荡解吸50分钟，完成后将96孔板2放入自动进样器中进样到超高效液相色谱-质谱分析；Sample processing: Precisely aspirate 2 mL of water sample and place it in 2 wells of a 96-well plate. Place 96-
对照品溶液的制备：对照品溶液的制备：精密称移取100μL对照品，用乙腈溶解定容至1mL，作为对照品溶液储备液；The preparation of the reference solution: the preparation of the reference solution: accurately weigh and pipet 100μL of the reference substance, dissolve it with acetonitrile and dilute to 1mL, as the reference solution stock solution;
标准曲线绘制：精密移取对照品溶液储备液，并用稀释剂体积比20:80的水: 乙腈溶液分别稀释成浓度为2ng/mL，4ng/mL，20ng/mL，40ng/mL，200ng/mL，400ng/mL，得到标准溶液；按色谱条件进行超高效液相色谱-质谱分析；以浓度对峰面积进行回归分析，得其组分标准曲线，计算回归方程；萘Y＝2178.29+67.6777*X，R 2＝0.9975，n＝6；苊Y＝4028.56+100.466*X，R 2＝0.9993，n＝6；苊烯Y＝6233.36+616.158*X，R 2＝0.9989，n＝7；芴Y＝3119.73+163.784*X，R 2＝0.9993，n＝6；菲Y＝6227.49+286.401*X，R 2＝0.9982，n＝8；蒽Y＝6399.69+593.228*X，R 2＝0.9988，n＝7；荧蒽Y＝13232.8+501.493*X，R 2＝0.9987，n＝7；芘Y＝10948.7+861.248*X，R 2＝0.9991，n＝7；苯并芘b荧蒽Y＝151.247+2556.68*X，R 2＝0.9992，n＝6；苯并a芘Y＝-23181+2382.35*X，R 2＝0.9987，n＝6； Standard curve drawing: Precisely pipette the stock solution of the reference solution and dilute it with 20:80 diluent volume ratio of water: acetonitrile solution to the concentration of 2ng/mL, 4ng/mL, 20ng/mL, 40ng/mL, 200ng/mL , 400ng/mL, to obtain a standard solution; perform ultra-high performance liquid chromatography-mass spectrometry analysis according to chromatographic conditions; perform regression analysis on the peak area by concentration to obtain its component standard curve, and calculate the regression equation; naphthalene Y=2178.29+67.6777*X , R 2 =0.9975, n=6; Acenaphthene Y=4028.56+100.466*X, R 2 =0.9993, n=6; Acenaphthene Y=6233.36+616.158*X, R 2 =0.9989, n=7; fluorene Y= 3119.73+163.784*X, R 2 =0.9993, n=6; phenanthrene Y=6227.49+286.401*X, R 2 =0.9982, n=8; anthracene Y=6399.69+593.228*X, R 2 =0.9988, n=7 Fluoranthene Y=13232.8+501.493*X, R 2 =0.987, n=7; Pyrene Y=19948.7+861.248*X, R 2 ＝0.9991, n=7; Benzopyrene bfluoranthene Y=151.247+2556.68* X, R 2 =0.9992, n=6; Benzo apyrene Y=-23181+2382.35*X, R 2 =0.9987, n=6;
含量测定：精密吸取样品待测液，按色谱条件进行超高效液相色谱-质谱分析，并将峰面积带入标准曲线，计算含量；Content determination: Precisely draw the sample to be tested, perform ultra-high performance liquid chromatography-mass spectrometry analysis according to chromatographic conditions, and bring the peak area into the standard curve to calculate the content;
样品检测结果，萘6.0-207ng；苊2.4-30.7ng；苊烯1.7-48.0ng；芴5.6-60.5ng；菲11.1-64.2ng；蒽1.06-66.8ng；荧蒽5.9-52.5ng；芘3.7-70.4ng；苯并芘b荧蒽1.7-16ng；苯并a芘18-118ng；The sample test results, naphthalene 6.0-207ng; acenaphthene 2.4-30.7ng; acenaphthylene 1.7-48.0ng; fluorene 5.6-60.5ng; phenanthrene 11.1-64.2ng; anthracene 1.06-66.8ng; fluoranthene 5.9-52.5ng; pyrene 3.7- 70.4ng; Benzopyrene b-fluoranthene 1.7-16ng; Benzoapyrene 18-118ng;
重复性试验：取样品共7份，按所述步骤，RSD结果为：萘4.19％；苊4.01％；苊烯3.98％；芴1.55％；菲6.19％；蒽4.6％；荧蒽4.82％；芘5.33％；苯并芘b荧蒽2.82％；苯并a芘1.87％。Repeatability test: A total of 7 samples were taken. According to the steps described, the RSD results were: naphthalene 4.19%; acenaphthylene 4.01%; acenaphthylene 3.98%; fluorene 1.55%; phenanthrene 6.19%; anthracene 4.6%; fluoranthene 4.82%; pyrene 5.33%; Benzopyrene b-fluoranthene 2.82%; Benzoapyrene 1.87%.
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