CN111579668A - Method for measuring halogenated polycyclic aromatic hydrocarbon in atmospheric dust - Google Patents
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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
- 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
- G01N30/08—Preparation using an enricher
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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
- G01N2030/042—Standards
- G01N2030/045—Standards internal
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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
- G01N30/12—Preparation by evaporation
- G01N2030/126—Preparation by evaporation evaporating sample
Abstract
The invention discloses a method for measuring halogenated polycyclic aromatic hydrocarbon in atmospheric dust, which is characterized by comprising the following steps: the method comprises the following steps: 1) ultrasonic extraction; 2) concentrating by a rotary evaporator; 3) activating; 4) rinsing; 5) concentrating, collecting the concentrated substance into a cell bottle; 6) fixing the volume of the solvent; 7) sealing and labeling; 8) detecting by using a gas chromatograph-mass spectrometer; 9) recording HPAHs substance data separated according to the steps 1) to 8) displayed on the gas chromatograph-mass spectrometer. The invention solves the defects of long time consumption, large consumption of materials and complex chromatographic column manufacturing in quantitative analysis of the HPAHs content in the dust sample by adopting the prior art, establishes a simple, rapid, energy-saving and consumption-reducing pretreatment and instrument quantitative method for analyzing the HPAHs in the atmospheric dust, and is suitable for popularization and use in detection of the HPAHs content in the atmospheric dust.
Description
Technical Field
The invention relates to the field of methods for measuring halogenated polycyclic aromatic hydrocarbon in atmospheric dust, and particularly belongs to a method for measuring halogenated polycyclic aromatic hydrocarbon in atmospheric dust.
Background
Halogenated Polycyclic Aromatic Hydrocarbons (HPAHs) are a class of pollutants formed by replacing hydrogen atoms on the carbon skeleton of Polycyclic Aromatic Hydrocarbons (PAHs) with chlorine atoms or bromine atoms, and they are structurally similar to other Halogenated hydrocarbons (HAHs), such as polychlorinated dibenzo-p-dioxin (PCDD), dibenzofuran (PCDF), and biphenyls (PCBs), and the structural similarities of these substances indicate that Halogenated Polycyclic Aromatic Hydrocarbons (HPAHs) have biotoxicity and carcinogenicity similar to PAHs and dioxins, and thus are widely regarded by people. In recent years, relevant researches show that Halogenated Polycyclic Aromatic Hydrocarbons (HPAHs) mainly originate from different combustion processes of relevant substances, namely, organic substances and hydrochloric acid or other substances containing chlorine (bromine) are incompletely combusted, and the Halogenated Polycyclic Aromatic Hydrocarbons (HPAHs) can be generated. For example, during the incineration of waste, motor vehicle exhaust emissions, coal combustion, etc., large amounts of Halogenated Polycyclic Aromatic Hydrocarbons (HPAHs) are produced. From the physicochemical properties, it can be concluded that Halogenated Polycyclic Aromatic Hydrocarbons (HPAHs) have a greater n-octanol-water partition coefficient than their corresponding parent Polycyclic Aromatic Hydrocarbons (PAHs), reflecting the greater affinity of Halogenated Polycyclic Aromatic Hydrocarbons (HPAHs) for lipids than their corresponding parent Polycyclic Aromatic Hydrocarbons (PAHs). These Halogenated Polycyclic Aromatic Hydrocarbon (HPAHs) contaminants are more likely to bioaccumulate within the organism.
Although Halogenated Polycyclic Aromatic Hydrocarbons (HPAHs) are widely present in the environment, few methods have been reported for their analytical testing. Few reports on analytical test methods for Halogenated Polycyclic Aromatic Hydrocarbons (HPAHs) exist, mainly focusing on analytical test of Halogenated Polycyclic Aromatic Hydrocarbons (HPAHs) in foods. For example, Wangli and the like establish a dispersive solid phase extraction-gas chromatography-tandem mass spectrometry (GC-MS/MS) analysis method for simultaneously detecting pollution levels of 16 Polycyclic Aromatic Hydrocarbons (PAHs) and 11 Halogenated Polycyclic Aromatic Hydrocarbons (HPAHs) in vegetables, a sample is extracted by N-hexane, purified by an N-propylethylenediamine adsorbent (PSA) and an octadecyl bonded silica gel adsorbent (C18) dispersive solid phase extraction purifying agent, measured by a gas chromatography-tandem mass spectrometry method, and finally quantified by an external standard method. At the moment, under the adding concentrations of 50 mug/kg, 100 mug/kg and 200 mug/kg, the recovery rate of 16 Polycyclic Aromatic Hydrocarbons (PAHs) and 11 Halogenated Polycyclic Aromatic Hydrocarbons (HPAHs) in the vegetables is 74.7-115.1%, the relative standard deviation is 1.6-15.3%, and the detection range of the method is 0.03-7.4 mug/kg; sun Jianlin et al utilize n-hexane: soxhlet extraction of an atmospheric particulate sample by using an acetone (volume ratio of 1:1) mixed solvent, purification by using a multilayer chromatographic column, and quantitative detection in a gas chromatography mass spectrometer by using an external standard method, wherein the recovery rate of a Halogenated Polycyclic Aromatic Hydrocarbon (HPAHs) target in a blank standard addition experiment is 85-127%, and the recovery rate of the target in a matrix standard addition experiment is 107-139%. Meanwhile, in the prior art, when the halogenated polycyclic aromatic hydrocarbon in the atmospheric dust is detected, a glass fiber filter membrane is cut into fragments by using surgical scissors, a known amount of recovery rate indicator is added, and Soxhlet extraction is carried out for 24 hours by using 200mL of mixed solution of acetone and n-hexane in a volume ratio of 1: 1. Concentrating the extract to 2mL by using a rotary evaporator, separating and purifying by using a multilayer chromatographic column, wherein the fillers of the multilayer chromatographic column are 6cm of aluminum oxide, 12cm of silica gel and 3g of anhydrous sodium sulfate from bottom to top respectively, eluting the multilayer chromatographic column by using 6mL of n-hexane, discarding eluent, eluting the column by using 70mL of a mixed solution of n-hexane and dichloromethane with the volume ratio of 7: 3, collecting the eluent, concentrating by using the rotary evaporator, then carrying out constant volume to 500 mu L by using a nitrogen and nitrogen blowing instrument, putting the substance with the constant volume into a chromatographic sample feeding bottle of a gas chromatograph-mass spectrometer, and carrying out analysis and quantification by using the gas-mass spectrometer.
The prior art for detecting halogenated polycyclic aromatic hydrocarbons in atmospheric dust has the following defects: 1) time consuming: the Soxhlet extraction time is 24 hours each time, and the integral detection is finished by at least 144 hours continuously; 2) consumable material: the solvent required by each Soxhlet extraction is 200mL, and the solvent is 70mL when each sample is purified; 3) the complexity is as follows: when the multilayer chromatographic column is self-made, a large amount of silica gel, alumina and anhydrous sodium sulfate are needed, the whole preparation work is complex, and the stability is poor; 4) the overall repeatability of the detection process is poor, and if the multilayer chromatographic column fails to be manufactured, the overall requirements of quantitative analysis and detection cannot be met.
In a word, when the methods are actually applied to the process of detecting the halogenated polycyclic aromatic hydrocarbon in the atmospheric dust, a large amount of chemical reagents are consumed, meanwhile, the self-made chromatographic column wastes time and labor, and has poor stability and poor repeatability of detection results, so that the requirements of normal analysis and detection experiments cannot be met, and the requirements of batch repeatability experiment detection cannot be met. Therefore, there is a need to develop a novel quantitative detection method for measuring Halogenated Polycyclic Aromatic Hydrocarbons (HPAHs) in atmospheric dust, which is stable, reliable and easy to operate, and for this reason, the technical researchers of our research institute develop a method for measuring halogenated polycyclic aromatic hydrocarbons in atmospheric dust.
Disclosure of Invention
The invention aims to provide a method for measuring halogenated polycyclic aromatic hydrocarbon in atmospheric dust, which can solve the problems in the background technology, can quantitatively detect and analyze the content of HPAHs in a dust sample, and has the advantages of short detection time, less consumption of consumables, simple and quick preparation of a chromatographic column, energy conservation, good fuel consumption reduction, and suitability for popularization and application in detection of the content of HPAHs in atmospheric dust.
The technical scheme adopted by the invention is as follows:
a method for measuring halogenated polycyclic aromatic hydrocarbon in atmospheric dust is characterized in that: the method comprises the following steps:
the method comprises the following steps: ultrasonic extraction: wrapping the accurately weighed dust sample by using a glass fiber filter membrane, performing 3-time repeated ultrasonic extraction by using a mixture of dichloromethane and n-hexane, transferring an extraction liquid into a heart-shaped bottle, immersing the lower part of a solid phase extraction instrument into a bathtub containing deionized water during the ultrasonic extraction, placing the bathtub in a desktop digital ultrasonic cleaning machine, and covering an upper top cover of the desktop digital ultrasonic cleaning machine;
step two: concentrating by a rotary evaporator: collecting the extract liquid after ultrasonic extraction to a heart-shaped bottle, and concentrating the collected extract liquid by setting the heating temperature to be 60 ℃ and the vacuum degree to be more than 260Pa by using a rotary evaporator;
step three: and (3) activation: transferring the extract liquor in the heart-shaped bottle to a solid-phase extraction column for purification treatment, and activating the solid-phase extraction column by using normal hexane before the purification treatment;
step four: rinsing: rinsing the heart bottles with a mixture of dichloromethane and n-hexane, transferring the rinsing solutions to a solid phase extraction column for rinsing, and collecting rinsing solutions with the heart bottles;
step five: concentration: concentrating the leacheate through a rotary evaporator, collecting the concentrated substances in a cell bottle, transferring the leacheate collected in the heart bottle according to the step four into the cell bottle, leaching the heart bottle with a mixture of dichloromethane and n-hexane for 3 times, and transferring the leacheate into the cell bottle;
step six: solvent constant volume: slightly blowing the substances in the cell bottle under the action of nitrogen flow, and fixing the volume of the solvent to 1 mL;
step seven: sealing and labeling: sealing the cell bottle with constant volume and labeling;
step eight: detecting by using a gas chromatograph-mass spectrometer: before the substances in the cell bottles are detected and analyzed, an internal standard substance is added into the cell bottles containing the substances with the detection and analysis, the added internal standard substance is 2-fluoro-1,1-biphenyl (chemical name: 1, 1' -2 fluorobiphenyl) or p-terphenyl 14 (chemical name: deuterated terphenyl), and the concentration of the internal standard substance is 50 mug/L; the detection using the gas chromatograph-mass spectrometer requires preparation of 8 kinds of standard solutions of the HPAHs compounds, the 8 kinds of standard solutions of the HPAHs compounds are prepared by using 8 kinds of standard substances of the HPAHs compounds, such as 2-bromofluorene, 9-chlorophenanthrene, 2-chloroanthracene, 9-bromophenanthrene, 9-bromoanthracene, 9, 10-dichloroanthracene, and 7-bromobenzo [ a ] anthracene, and the 8 kinds of standard substances of the HPAHs compounds are chromatographic columns with specification types of HP-5MS,60m × 0.25 μm × 0.25 mm: 2-bromofluorene, 9-chlorophenanthrene, 2-chloroanthracene, 9-bromophenanthrene, 9-bromoanthracene, 9, 10-dichloroanthracene, 9, 10-dibromoanthracene, 7-bromobenzo [ a ] anthracene, produced by Tokyo Kasei Kogyo co., Ltd, Tokyo, japan;
step nine: and recording HPAHs substance data which is detected by adopting a gas chromatograph-mass spectrometer and is displayed on the gas chromatograph-mass spectrometer according to the steps from the first step to the eighth step.
Preferably, the solid phase extractor is an SPE solid phase extractor, and the model is: supelco, manufactured by Shanghai Darlo scientific instruments, Inc.;
the desktop digital ultrasonic cleaning machine is characterized in that the model is as follows: ZC-020D produced by Shanghai Biao and instruments Co., Ltd, wherein in the ultrasonic extraction process, the ultrasonic frequency is 40KHZ, the ultrasonic power is 60W, the heating power is 100W, the temperature of an ultrasonic water body is 30 ℃, and the ultrasonic extraction time is 30 min;
in the ultrasonic extraction process, 5.00g of accurately weighed dust sample is obtained, 30mL of a dichloromethane-n-hexane mixture is used as an extraction solvent, the volume ratio of dichloromethane to n-hexane is 3:1, the extract liquid is transferred into a heart-shaped bottle, 30mL of dichloromethane-n-hexane mixture is added, ultrasonic extraction is repeated for 2 times, the ultrasonic extraction time is 20min and 10min respectively, the ultrasonic frequency is 40KHZ, the ultrasonic power is 60W, the heating power is 100W, and the temperature of an ultrasonic water body is 30 ℃;
collecting the ultrasonic extraction liquid in each step in the first step into a heart-shaped bottle, setting the heating temperature of the collected 90mL of extraction liquid at 60 ℃ by using a rotary evaporator, keeping the vacuum degree at more than 260Pa, concentrating the extraction liquid to 2 mL; the rotary evaporator is an IKA rotary evaporator produced by Germany, and has the model: RV10DS 96;
before the purification treatment, activating a solid-phase extraction column by using 10mL of n-hexane, transferring the extract in the heart bottle to the solid-phase extraction column, rinsing the heart bottle by using 20mL of a mixture of dichloromethane and n-hexane, wherein the volume ratio of dichloromethane to n-hexane is 3:7, transferring the rinsing liquid to the solid-phase extraction column for leaching, and collecting rinsing liquid by using the heart bottle; the solid phase extraction column is a small solid phase extraction column, the model is Mega BE-C18, the specification is 5g/20mL, the package is 20/pk, and the original package of Agilent company in America is imported;
1cm of anhydrous sodium sulfate is filled in the upper section of a chromatographic column of the solid-phase extraction column in the purification treatment process, the column is required to be baked for more than 4 hours at 400 ℃ in a muffle furnace before use, and the column is sealed and stored after being cooled and then used in the purification treatment process;
concentrating the leacheate by using a rotary evaporator, setting the heating temperature of the rotary evaporator at 60 ℃, keeping the vacuum degree at more than 260Pa for concentration, concentrating to 1mL, adding 10mL of n-hexane for reconcentration to 1mL, transferring the concentrated 1mL of the concentrated solution into a cell bottle, adding 1mL of n-hexane into the heart bottle for collecting the leacheate, leaching the wall of the heart bottle, transferring the liquid obtained after leaching into the cell bottle, leaching the wall of the heart bottle for collecting the leacheate by using 1mL of n-hexane each time, repeating the steps for 3 times in sequence, transferring the liquid obtained after 3 times of leaching into the cell bottle, slightly blowing the substances in the cell bottle under the action of nitrogen flow, and fixing the volume of the solvent to 1 mL;
under the slight nitrogen flow blowing effect, a nitrogen blowing instrument is used, the type of the nitrogen blowing instrument is DC-24 type, the nitrogen blowing instrument is produced by Shanghai Anpu experiment science and technology Co., Ltd, the concentration of the used nitrogen is 99.99%, the pressure is 0.1MPa, and the nitrogen flow is 0.2L/min when the nitrogen is slightly blown;
the internal standard substances 2-fluoro-1,1-biphenyl (chemical name: 1, 1' -2 fluorobiphenyl) and p-terphenyl 14 (chemical name: deuterated p-terphenyl) are purchased from certified standard substances produced by Beijing Bailingwei science and technology Limited company in 2019, 12 months and 5 days;
the 8 HPAHs compound standard substances are prepared as follows: diluting 8 HPAHs compound standard substances of 2-bromofluorene, 9-chloro phenanthrene, 2-chloroanthracene, 9-bromophenanthrene, 9-bromoanthracene, 9, 10-dichloroanthracene, 9-dibromoanthracene and 7-bromobenzo [ a ] anthracene to 10mg/L by deionized water respectively, diluting each HPAHs compound standard substance in the 8 diluted HPAHs compound standard substances by deionized water respectively to prepare a mixed standard series with 5 concentration points, ensuring that the mass concentration of each diluted compound prepared into the 5 concentration points is 5 mug/L, 10 mug/L, 20 mug/L, 50 mug/L and 100 mug/L respectively, and then adding an internal standard solution 2-fluoro-1 with the concentration of 50 mug/L into each diluted compound prepared into a single concentration point, 1-biphenyl (chemical name: 1, 1' -2 fluorobiphenyl) or p-terphenyl 14 (chemical name: deuterated p-terphenyl);
in the detection process by adopting the gas chromatograph-mass spectrometer, the used gas chromatograph-mass spectrometer is a gas chromatograph-mass spectrometer of Shimadzu, and the gas chromatograph-mass spectrometer is of the type: GC/MS-QP2010ultra, chromatographic column in gas chromatograph-mass spectrometer, specification type: HP-5MS,60 m.times.0.25 μm.times.0.25 mm, manufactured by Agilent, USA, with chromatographic conditions: sample inlet temperature: at 280 ℃, no flow splitting is carried out; sample introduction amount: 1.0 μ L, column flow: 1.0 mL/min; column temperature: keeping at 60 deg.C for 3min, heating to 200 deg.C at 5 deg.C/min, then heating to 250 deg.C at 2 deg.C/min, and finally heating to 290 deg.C/min, and keeping for 5 min; the mass spectrum conditions are as follows: ion source temperature: at 210 ℃; ionization capacity 70 eV; interface temperature: 260 ℃; quadrupole temperature: 150 ℃; scanning mode: selecting an ion mode (SIM) mode; sample introduction amount: 1.0 μ L, column flow: 1.0 mL/min; quantitative method: internal standard method.
Preferably, the glass fiber filter membrane is a glass fiber filter membrane with the diameter of 90mm and the pore diameter of 0.45 μm, and is baked for 4 hours at 400 ℃ in a muffle furnace before use, and is sealed and stored after cooling for later use.
Compared with the prior art, the invention has the following beneficial effects:
the invention solves the defects of long time consumption, large consumption of consumed materials and complex chromatographic column manufacturing in quantitative analysis of the HPAHs content in the dust sample by adopting the prior art, adopts a Soxhlet extraction-chromatographic column purification-gas chromatography mass spectrometry quantitative method, can quantitatively detect and analyze the HPAHs content in the dust sample, has short detection time, less consumed materials, simple chromatographic column manufacturing, simple and fast integration and good energy and consumption reduction, establishes a simple and fast pretreatment and instrument quantitative method for analyzing the HPAHs in the atmospheric dust with energy and consumption reduction, and is suitable for popularization and application in detection of the HPAHs content in the atmospheric dust.
Drawings
FIG. 1 is a schematic structural diagram of the detection and recovery efficiency of 8 HPAHs (H-H) compounds of 2-bromofluorene, 9-chlorophenanthrene, 2-chloroanthracene, 9-bromophenanthrene, 9-bromoanthracene, 9, 10-dichloroanthracene, 9, 10-dibromoanthracene and 7-bromobenzo [ a ] anthracene, which are practically applied to atmospheric dust;
FIG. 2 is a schematic diagram showing the actual concentration results of 8 HPAHs (hydroxy propyl fluorene) compounds, such as 2-bromofluorene, 9-chlorophenanthrene, 2-chloroanthracene, 9-bromophenanthrene, 9-bromoanthracene, 9, 10-dichloroanthracene, 9, 10-dibromoanthracene and 7-bromobenzo [ a ] anthracene, when the method is actually applied to atmospheric dust of fly ash of a circulating fluidized bed boiler exhaust stack of a Huainan coal-fired power plant.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described below with specific embodiments, and the technical solutions in the embodiments of the present invention are clearly and completely described. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention will be described in further detail with reference to examples and specific embodiments.
A method for measuring halogenated polycyclic aromatic hydrocarbon in atmospheric dust is characterized in that: the method comprises the following steps:
the method comprises the following steps: ultrasonic extraction: wrapping the accurately weighed dust sample by using a glass fiber filter membrane, performing 3-time repeated ultrasonic extraction by using a mixture of dichloromethane and n-hexane, transferring an extraction liquid into a heart-shaped bottle, immersing the lower part of a solid phase extraction instrument into a bathtub containing deionized water during the ultrasonic extraction, placing the bathtub in a desktop digital ultrasonic cleaning machine, and covering an upper top cover of the desktop digital ultrasonic cleaning machine;
step two: concentrating by a rotary evaporator: collecting the extract liquid after ultrasonic extraction to a heart-shaped bottle, and concentrating the collected extract liquid by setting the heating temperature to be 60 ℃ and the vacuum degree to be more than 260Pa by using a rotary evaporator;
step three: and (3) activation: transferring the extract liquor in the heart-shaped bottle to a solid-phase extraction column for purification treatment, and activating the solid-phase extraction column by using normal hexane before the purification treatment;
step four: rinsing: rinsing the heart bottles with a mixture of dichloromethane and n-hexane, transferring the rinsing solutions to a solid phase extraction column for rinsing, and collecting rinsing solutions with the heart bottles;
step five: concentration: concentrating the leacheate through a rotary evaporator, collecting the concentrated substances in a cell bottle, transferring the leacheate collected in the heart bottle according to the step four into the cell bottle, leaching the heart bottle with a mixture of dichloromethane and n-hexane for 3 times, and transferring the leacheate into the cell bottle;
step six: solvent constant volume: slightly blowing the substances in the cell bottle under the action of nitrogen flow, and fixing the volume of the solvent to 1 mL;
step seven: sealing and labeling: sealing the cell bottle with constant volume and labeling;
step eight: detecting by using a gas chromatograph-mass spectrometer: before the substances in the cell bottles are detected and analyzed, an internal standard substance is added into the cell bottles containing the substances with the detection and analysis, the added internal standard substance is 2-fluoro-1,1-biphenyl (chemical name: 1, 1' -2 fluorobiphenyl) or p-terphenyl 14 (chemical name: deuterated terphenyl), and the concentration of the internal standard substance is 50 mug/L; the detection using the gas chromatograph-mass spectrometer requires preparation of 8 kinds of standard solutions of the HPAHs compounds, the 8 kinds of standard solutions of the HPAHs compounds are prepared by using 8 kinds of standard substances of the HPAHs compounds, such as 2-bromofluorene, 9-chlorophenanthrene, 2-chloroanthracene, 9-bromophenanthrene, 9-bromoanthracene, 9, 10-dichloroanthracene, and 7-bromobenzo [ a ] anthracene, and the 8 kinds of standard substances of the HPAHs compounds are chromatographic columns with specification types of HP-5MS,60m × 0.25 μm × 0.25 mm: 2-bromofluorene, 9-chlorophenanthrene, 2-chloroanthracene, 9-bromophenanthrene, 9-bromoanthracene, 9, 10-dichloroanthracene, 9, 10-dibromoanthracene, 7-bromobenzo [ a ] anthracene, produced by Tokyo Kasei Kogyo co., Ltd, Tokyo, japan;
step nine: and recording HPAHs substance data which is detected by adopting a gas chromatograph-mass spectrometer and is displayed on the gas chromatograph-mass spectrometer according to the steps from the first step to the eighth step.
Preferably, the solid phase extractor is an SPE solid phase extractor, and the model is: supelco, manufactured by Shanghai Darlo scientific instruments, Inc.;
the desktop digital ultrasonic cleaning machine is characterized in that the model is as follows: ZC-020D produced by Shanghai Biao and instruments Co., Ltd, wherein in the ultrasonic extraction process, the ultrasonic frequency is 40KHZ, the ultrasonic power is 60W, the heating power is 100W, the temperature of an ultrasonic water body is 30 ℃, and the ultrasonic extraction time is 30 min;
in the ultrasonic extraction process, 5.00g of accurately weighed dust sample is obtained, 30mL of a dichloromethane-n-hexane mixture is used as an extraction solvent, the volume ratio of dichloromethane to n-hexane is 3:1, the extract liquid is transferred into a heart-shaped bottle, 30mL of dichloromethane-n-hexane mixture is added, ultrasonic extraction is repeated for 2 times, the ultrasonic extraction time is 20min and 10min respectively, the ultrasonic frequency is 40KHZ, the ultrasonic power is 60W, the heating power is 100W, and the temperature of an ultrasonic water body is 30 ℃;
collecting the ultrasonic extraction liquid in each step in the first step into a heart-shaped bottle, setting the heating temperature of the collected 90mL of extraction liquid at 60 ℃ by using a rotary evaporator, keeping the vacuum degree at more than 260Pa, concentrating the extraction liquid to 2 mL; the rotary evaporator is an IKA rotary evaporator produced by Germany, and has the model: RV10DS 96;
before the purification treatment, activating a solid-phase extraction column by using 10mL of n-hexane, transferring the extract in the heart bottle to the solid-phase extraction column, rinsing the heart bottle by using 20mL of a mixture of dichloromethane and n-hexane, wherein the volume ratio of dichloromethane to n-hexane is 3:7, transferring the rinsing liquid to the solid-phase extraction column for leaching, and collecting rinsing liquid by using the heart bottle; the solid phase extraction column is a small solid phase extraction column, the model is Mega BE-C18, the specification is 5g/20mL, the package is 20/pk, and the original package of Agilent company in America is imported;
1cm of anhydrous sodium sulfate is filled in the upper section of a chromatographic column of the solid-phase extraction column in the purification treatment process, the column is required to be baked for more than 4 hours at 400 ℃ in a muffle furnace before use, and the column is sealed and stored after being cooled and then used in the purification treatment process;
concentrating the leacheate by using a rotary evaporator, setting the heating temperature of the rotary evaporator at 60 ℃, keeping the vacuum degree at more than 260Pa for concentration, concentrating to 1mL, adding 10mL of n-hexane for reconcentration to 1mL, transferring the concentrated 1mL of the concentrated solution into a cell bottle, adding 1mL of n-hexane into the heart bottle for collecting the leacheate, leaching the wall of the heart bottle, transferring the liquid obtained after leaching into the cell bottle, leaching the wall of the heart bottle for collecting the leacheate by using 1mL of n-hexane each time, repeating the steps for 3 times in sequence, transferring the liquid obtained after 3 times of leaching into the cell bottle, slightly blowing the substances in the cell bottle under the action of nitrogen flow, and fixing the volume of the solvent to 1 mL;
under the slight nitrogen flow blowing effect, a nitrogen blowing instrument is used, the type of the nitrogen blowing instrument is DC-24 type, the nitrogen blowing instrument is produced by Shanghai Anpu experiment science and technology Co., Ltd, the concentration of the used nitrogen is 99.99%, the pressure is 0.1MPa, and the nitrogen flow is 0.2L/min when the nitrogen is slightly blown;
the internal standard substances 2-fluoro-1,1-biphenyl (chemical name: 1, 1' -2 fluorobiphenyl) and p-terphenyl 14 (chemical name: deuterated p-terphenyl) are purchased from certified standard substances produced by Beijing Bailingwei science and technology Limited company in 2019, 12 months and 5 days;
the 8 HPAHs compound standard substances are prepared as follows: diluting 8 HPAHs compound standard substances of 2-bromofluorene, 9-chloro phenanthrene, 2-chloroanthracene, 9-bromophenanthrene, 9-bromoanthracene, 9, 10-dichloroanthracene, 9-dibromoanthracene and 7-bromobenzo [ a ] anthracene to 10mg/L by deionized water respectively, diluting each HPAHs compound standard substance in the 8 diluted HPAHs compound standard substances by deionized water respectively to prepare a mixed standard series with 5 concentration points, ensuring that the mass concentration of each diluted compound prepared into the 5 concentration points is 5 mug/L, 10 mug/L, 20 mug/L, 50 mug/L and 100 mug/L respectively, and then adding an internal standard solution 2-fluoro-1 with the concentration of 50 mug/L into each diluted compound prepared into a single concentration point, 1-biphenyl (chemical name: 1, 1' -2 fluorobiphenyl) or p-terphenyl 14 (chemical name: deuterated p-terphenyl);
in the detection process by adopting the gas chromatograph-mass spectrometer, the used gas chromatograph-mass spectrometer is a gas chromatograph-mass spectrometer of Shimadzu, and the gas chromatograph-mass spectrometer is of the type: GC/MS-QP2010ultra, chromatographic column in gas chromatograph-mass spectrometer, specification type: HP-5MS,60 m.times.0.25 μm.times.0.25 mm, manufactured by Agilent, USA, with chromatographic conditions: sample inlet temperature: at 280 ℃, no flow splitting is carried out; sample introduction amount: 1.0 μ L, column flow: 1.0 mL/min; column temperature: keeping at 60 deg.C for 3min, heating to 200 deg.C at 5 deg.C/min, then heating to 250 deg.C at 2 deg.C/min, and finally heating to 290 deg.C/min, and keeping for 5 min; the mass spectrum conditions are as follows: ion source temperature: at 210 ℃; ionization capacity 70 eV; interface temperature: 260 ℃; quadrupole temperature: 150 ℃; scanning mode: selecting an ion mode (SIM) mode; sample introduction amount: 1.0 μ L, column flow: 1.0 mL/min; quantitative method: internal standard method.
Preferably, the glass fiber filter membrane is a glass fiber filter membrane with the diameter of 90mm and the pore diameter of 0.45 μm, and is baked for 4 hours at 400 ℃ in a muffle furnace before use, and is sealed and stored after cooling for later use.
According to the steps from one to nine, the method is practically applied to atmospheric dust, and the 2-bromofluorene, 9-chlorophenanthrene, 2-chloroanthracene, 9-bromophenanthrene, 9-bromoanthracene, 9, 10-dichloroanthracene, 9, 10-dibromoanthracene, 7-bromobenzo [ a ] is]When 8 kinds of HPAHs compounds of anthracene are quantitatively detected and analyzed, after the chromatographic separation of a gas chromatograph-mass spectrometer, 2-bromofluorene, 9-chlorophenanthrene, 2-chloroanthracene, 9-bromophenanthrene, 9-bromoanthracene, 9, 10-dichloroanthracene, 9, 10-dibromoanthracene and 7-bromobenzo [ a ] a]All 8 target compounds of HPAHs from anthracene were efficiently separated, with specific separation times as follows (Table 1)) In the separation process of the 8 HPAHs target compounds, the corresponding quantitative ions respectively correspond to: 165. 176, 256, 246, 176, and 306, standard curve equation of gas chromatography quantitative ion equation, calculated R2All above 0.999. (retention time unit: minutes; quantitative ion unit: Da Dalton, conventional written m/z.)
Table 1:
meanwhile, in the ultrasonic extraction process, the selection of the used extraction solvent has great influence on the recovery rate of 8 HPAHs target substance compounds in atmospheric dust, such as 2-bromofluorene, 9-chlorophenanthrene, 2-chloroanthracene, 9-bromophenanthrene, 9-bromoanthracene, 9, 10-dichloroanthracene, 9, 10-dibromoanthracene and 7-bromobenzo [ a ] anthracene. In the actual test process, four extraction solvents, namely n-hexane, a mixed solvent of n-hexane and dichloromethane (volume ratio of 1: 3), dichloromethane and acetone, are used for extracting 8 HPAHs target compounds in an atmospheric dust sample, all treatments are set for 3 times, and the results are shown as the following (table 2) in terms of the recovery average value +/-standard error:
table 2:
the results show that when n-hexane is used as an extraction solvent, the recovery efficiency is the lowest, the recovery efficiency of all 8 HPAHs target compounds is lower than 80%, and the recovery efficiency of 7-bromobenzo [ a ] anthracene is only (55.3 +/-8.7)%; it can be seen that n-hexane was not able to completely extract 8 HPAHs target compounds from the atmospheric dust sample due to: the 8 HPAHs target compounds are relatively weak in polarity and difficult to completely dissolve in n-hexane, and the solvation degree of the target compounds is gradually reduced particularly as the molecular weight is increased.
The n-hexane-dichloromethane mixed solvent (1: 3), dichloromethane and acetone are used as extraction solvents, the effect can reach a better level, the recovery efficiency of all 8 HPAHs target substance compounds is over 85 percent, and compared with the n-hexane-dichloromethane mixed solvent and acetone, the recovery efficiency of dichloromethane used as the extraction solvent is slightly lower. The reason is that: dichloromethane is easy to volatilize, and during the extraction process, dichloromethane is more volatilized, so that the extraction efficiency is reduced. Considering that dichloromethane is a toxic and harmful solvent and is easy to volatilize, and acetone is an easy-to-prepare toxic solvent, finally, the n-hexane-dichloromethane mixed solvent (1: 3) is selected as a final extraction solvent.
In order to optimize the experimental conditions of the purification treatment process and on the premise of ensuring the best recovery efficiency, the leaching solvent can be saved, and 3 groups of leaching schemes with different volumes are arranged:
the first embodiment is as follows: a standard solution containing 50ppb in 1mL of n-hexane was transferred to a Mega BE-C18 column under the following elution conditions: adding 5mL of n-hexane to drip wash the chromatographic column, and discarding; then adding 5mL of n-hexane for leaching, and collecting a liquid component 1; adding 15mL of n-hexane for leaching, and collecting the component 2; then 5mL of n-hexane was added for leaching, and the fraction 3 was collected. Concentrating and measuring by using a computer.
Example two: a standard solution containing 50ppb in 1mL of n-hexane was transferred to a Mega BE-C18 column under the following elution conditions: adding 5mL of dichloromethane to drip wash the chromatographic column, and discarding; then adding 5mL of dichloromethane for leaching, and collecting a liquid component 1; adding 5mL of dichloromethane for leaching, and collecting the component 2; 5mL of dichloromethane was added for rinsing, and fraction 3 was collected. Concentrating and measuring by using a computer.
Example three: a standard solution containing 50ppb in 1mL of n-hexane was transferred to a Mega BE-C18 column under the following elution conditions: adding 5mL of a mixed solvent (7: 3) of n-hexane and dichloromethane to drip wash the chromatographic column, and discarding; then adding 5mL of n-hexane-dichloromethane mixed solvent (7: 3) for leaching, and collecting a liquid component 1; then 10mL of n-hexane-dichloromethane mixed solvent (7: 3) is added for leaching, and the component 2 is collected; then 5mL of n-hexane-dichloromethane mixed solvent (7: 3) is added for leaching, and the component 3 is collected. Concentrating and measuring by using a computer.
In the first, second and third examples, the standard solution containing 50ppb in 1mL of n-hexane was either internal standard solution 2-fluoro-1,1-biphenyl (chemical name: 1, 1' -2 fluorobiphenyl) or p-terphenyl 14 (chemical name: deuterated p-terphenyl).
The analysis results (FIG. 1) are shown below: in the first example, n-hexane is used as a leaching solvent, the recovery efficiency is low and is below 80%, wherein the relative proportion of 8 HPAHs target compounds recovered by the component 2 in the first example is the highest, but the relative proportion is below 80%. It can be seen from this that n-hexane does not leach well the 8 target compounds of HPAHs in a solid phase extraction column.
In the second embodiment, dichloromethane is used as the leaching solvent, so that better recovery efficiency can be obtained, mainly comprising the component 1 and the component 2 in the second embodiment, and the component 3 in the second embodiment accounts for less than 10%.
In the third example, a mixed solvent of n-hexane and dichloromethane (7: 3) is used as a leaching solvent, so that better recovery efficiency can be obtained, the 8 target compounds of HPAHs are all higher than 90%, mainly comprising the component 1 and the component 2 in the second example, and the component 3 in the third example accounts for less than 10%. From this it can be known that: and the n-hexane-dichloromethane mixed solvent (7: 3) is used as a leaching solvent, and when the volume of the leaching solvent is 20ml, 8 HPAHs target compounds in the atmospheric dust sample can be well leached. Considering that dichloromethane is a toxic and harmful solvent, a mixed solvent of n-hexane-dichloromethane (7: 3) is finally selected as a rinsing solvent.
In order to verify that the solvent is not polluted by new 8 HPAHs target compounds in the preparation process, the experimental pretreatment and other processes, the following quartz sand blank labeling detection is carried out: the method comprises the following specific steps:
taking quartz sand with the particle size of 150 mu m as a blank test sample and a blank marking verification sample respectively, adding 50ppb of standard solution into the blank test sample to prepare the blank marking verification sample, wherein the standard solution is any one of internal standard solution 2-fluoro-1,1-biphenyl (chemical name: 1, 1' -2 fluorobiphenyl) or p-terphenyl 14 (chemical name: deuterated p-terphenyl). The specific detection steps are carried out according to the steps from the first step to the ninth step, and the ultrasonic extraction, the purification treatment, the pre-purification treatment, the used instrument parameters, the GC-MS chromatographic separation and the standard curve in the matching process are completely the same as those in the invention. The sample testing was verified by labeling 3 blank test samples and 3 blanks, with the results shown below (table 3):
table 3:
| 8 HPAHs target objects | Blank test sample | Blank marking verification sample |
| 2-bromofluorene | ND | 86.7±12.3 |
| 9-chloro-phenanthrene | ND | 87.9±10.6 |
| 2-chloroanthracene | ND | 92±6.9 |
| 9-bromophenanthrene | ND | 85.3±16.3 |
| 9-Bromoanthracene | ND | 101.9±12.5 |
| 9, 10-Dichloroanthracene | ND | 105.3±16.8 |
| 9, 10-dibromoanthracene | ND | 91.6±13.1 |
| 7-bromo-benzo [ a ]]Anthracene | ND | 80.5±10.3 |
The results show that: no 8 HPAHs target substances are detected in 3 blank test samples, and the fact that new 8 HPAHs target substance compounds are not polluted by the atmospheric dust sample in the preparation process, the pretreatment process of the experiment and other processes can be known.
The detection results of the blank labeling verification samples show that the recovery efficiencies of 2-bromofluorene, 9-chlorophenanthrene, 2-chloroanthracene, 9-bromophenanthrene, 9-bromoanthracene, 9, 10-dichloroanthracene, 9, 10-dibromoanthracene and 7-bromobenzo [ a ] anthracene in the 3 times blank labeling verification samples are (86.7 +/-12.3)%, (87.9 +/-10.6)%, (92 +/-6.9)%, (85.3 +/-16.3), (101.9 +/-12.5)%, (105.3 +/-16.8)%, (91.6 +/-13.1)% and (80.5 +/-10.3)%, respectively.
In summary, the following steps: the method has good recovery efficiency of 8 HPAHs target substance compounds of 2-bromofluorene, 9-chloro phenanthrene, 2-chloroanthracene, 9-bromo phenanthrene, 9-bromoanthracene, 9, 10-dichloroanthracene, 9, 10-dibromoanthracene and 7-bromobenzo [ a ] anthracene in the atmospheric dust, can well process and detect the 8 HPAHs target substance compounds in the atmospheric dust, and can perform rapid extraction, simple and rapid purification process treatment and quantitative detection and analysis on the target substance compounds.
In order to verify the repeatability popularization analysis application of the invention, the following tests are carried out:
the method comprises the following steps of collecting fly ash of an exhaust funnel of a circulating fluidized bed boiler of a Huainan coal-fired power plant as an actual atmospheric dust sample by utilizing a special low-concentration smoke gun device (JH-6066, produced by Qingdao Jingcheng instruments and meters, Inc.: meanwhile, the circulating fluidized bed boiler is provided with a limestone injection system for controlling SO 2; a urea injection system for controlling NOx; bag house dust collectors (FFs) for removing PMs from flue gases.
According to the steps one to nine of the invention, the ultrasonic extraction, the purification process treatment, the process before the purification treatment, the used instrument parameters, the GC-MS chromatographic separation and the standard curve in the matching process are all completely the same as those in the invention, and the parallel detection is repeated for 3 times, and the result is as follows:
the measured concentrations of 8 HPAHs target compounds of 2-bromofluorene, 9-chloro phenanthrene, 2-chloroanthracene, 9-bromo phenanthrene, 9-bromoanthracene, 9, 10-dichloroanthracene, 9, 10-dibromoanthracene and 7-bromobenzo [ a ] anthracene in an actual atmospheric dust sample are respectively 2-bromofluorene: 7.27 +/-0.46 ug/kg, 9-chlorophenanthrene 3.18 +/-0.048 ug/kg, 2-chloroanthracene: 2.65 ± 0.41ug/kg, 9-bromophenanthrene: 19.3 ± 1.4ug/kg, 9-bromoanthracene: 28.2 ± 2.45ug/kg, 9, 10-dichloroanthracene: 0.17 ± 0.018ug/kg, 9, 10-dibromoanthracene: 1.16. + -. 0.10ug/kg, 7-bromobenzo [ a ] anthracene: 2.71 + -0.39 ug/kg with relative standard deviations of 6.3%, 1.5%, 15.3%, 7.3%, 8.7%, 10.5%, 8.6% and 14.2%, respectively (as shown in fig. 2). From this it can be known that: the method is used for detecting and analyzing 8 HPAHs target substance compounds of 2-bromofluorene, 9-chlorophenanthrene, 2-chloroanthracene, 9-bromophenanthrene, 9-bromoanthracene, 9, 10-dichloroanthracene, 9, 10-dibromoanthracene and 7-bromobenzo [ a ] anthracene in an actual atmospheric dust sample, and has strong repeatability.
The method solves the problems that the existing methods are actually applied to the process of detecting the halogenated polycyclic aromatic hydrocarbon in the atmospheric dust, a large amount of chemical reagents are consumed, the self-made chromatographic column is time-consuming and labor-consuming, the stability is poor, the repeatability of the detection result is poor, the requirements of normal analysis and detection experiments can not be met, and the requirement of batch repeatability experiment detection can not be met. The method can be used for quantitatively detecting the content of the HPAHs in the dust sample, is short in detection time, small in consumption of consumables, simple in manufacturing of the chromatographic column, simple and rapid in whole, good in energy-saving and consumption-reducing performance, and high in recovery efficiency of 8 HPAHs target compounds such as 2-bromofluorene, 9-chlorophenanthrene, 2-chloroanthracene, 9-bromophenanthrene, 9-bromoanthracene, 9, 10-dichloroanthracene, 9, 10-dibromoanthracene and 7-bromobenzo [ a ] anthracene in the atmospheric dust, establishes a simple, rapid, energy-saving and consumption-reducing pretreatment and instrument quantitative method for analyzing the HPAHs in the atmospheric dust, and is suitable for popularization and use in detection of the content of the HPAHs in the atmospheric dust.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications are all within the scope of the present invention.
Claims (3)
1. A method for measuring halogenated polycyclic aromatic hydrocarbon in atmospheric dust is characterized in that: the method comprises the following steps:
the method comprises the following steps: ultrasonic extraction: wrapping the accurately weighed dust sample by using a glass fiber filter membrane, performing 3-time repeated ultrasonic extraction by using a mixture of dichloromethane and n-hexane, transferring an extraction liquid into a heart-shaped bottle, immersing the lower part of a solid phase extraction instrument into a bathtub containing deionized water during the ultrasonic extraction, placing the bathtub in a desktop digital ultrasonic cleaning machine, and covering an upper top cover of the desktop digital ultrasonic cleaning machine;
step two: concentrating by a rotary evaporator: collecting the extract liquid after ultrasonic extraction to a heart-shaped bottle, and concentrating the collected extract liquid by setting the heating temperature to be 60 ℃ and the vacuum degree to be more than 260Pa by using a rotary evaporator;
step three: and (3) activation: transferring the extract liquor in the heart-shaped bottle to a solid-phase extraction column for purification treatment, and activating the solid-phase extraction column by using normal hexane before the purification treatment;
step four: rinsing: rinsing the heart bottles with a mixture of dichloromethane and n-hexane, transferring the rinsing solutions to a solid phase extraction column for rinsing, and collecting rinsing solutions with the heart bottles;
step five: concentration: concentrating the leacheate through a rotary evaporator, collecting the concentrated substances in a cell bottle, transferring the leacheate collected in the heart bottle according to the step four into the cell bottle, leaching the heart bottle with a mixture of dichloromethane and n-hexane for 3 times, and transferring the leacheate into the cell bottle;
step six: solvent constant volume: slightly blowing the substances in the cell bottle under the action of nitrogen flow, and fixing the volume of the solvent to 1 mL;
step seven: sealing and labeling: sealing the cell bottle with constant volume and labeling;
step eight: detecting by using a gas chromatograph-mass spectrometer: before the substances in the cell bottles are detected and analyzed, an internal standard substance is added into the cell bottles containing the substances with the detection and analysis, the added internal standard substance is 2-fluoro-1,1-biphenyl or p-terphenyl 14, and the concentration of the internal standard substance is 50 mug/L; the detection using the gas chromatograph-mass spectrometer requires preparation of 8 kinds of standard solutions of the HPAHs compounds, the 8 kinds of standard solutions of the HPAHs compounds are prepared by using 8 kinds of standard substances of the HPAHs compounds, such as 2-bromofluorene, 9-chlorophenanthrene, 2-chloroanthracene, 9-bromophenanthrene, 9-bromoanthracene, 9, 10-dichloroanthracene, and 7-bromobenzo [ a ] anthracene, and the 8 kinds of standard substances of the HPAHs compounds are chromatographic columns with specification types of HP-5MS,60m × 0.25 μm × 0.25 mm: 2-bromofluorene, 9-chlorophenanthrene, 2-chloroanthracene, 9-bromophenanthrene, 9-bromoanthracene, 9, 10-dichloroanthracene, 9, 10-dibromoanthracene, 7-bromobenzo [ a ] anthracene, produced by Tokyo Kasei Kogyo co., Ltd, Tokyo, japan;
step nine: and recording HPAHs substance data which is detected by adopting a gas chromatograph-mass spectrometer and is displayed on the gas chromatograph-mass spectrometer according to the steps from the first step to the eighth step.
2. The method for determining halogenated polycyclic aromatic hydrocarbon in atmospheric dust according to claim 1, wherein the solid phase extractor is an SPE solid phase extractor, and the type is as follows: supelco, manufactured by Shanghai Darlo scientific instruments, Inc.;
the desktop digital ultrasonic cleaning machine is characterized in that the model is as follows: ZC-020D produced by Shanghai Biao and instruments Co., Ltd, wherein in the ultrasonic extraction process, the ultrasonic frequency is 40KHZ, the ultrasonic power is 60W, the heating power is 100W, the temperature of an ultrasonic water body is 30 ℃, and the ultrasonic extraction time is 30 min;
in the ultrasonic extraction process, 5.00g of accurately weighed dust sample is obtained, 30mL of a dichloromethane-n-hexane mixture is used as an extraction solvent, the volume ratio of dichloromethane to n-hexane is 3:1, the extract liquid is transferred into a heart-shaped bottle, 30mL of dichloromethane-n-hexane mixture is added, ultrasonic extraction is repeated for 2 times, the ultrasonic extraction time is 20min and 10min respectively, the ultrasonic frequency is 40KHZ, the ultrasonic power is 60W, the heating power is 100W, and the temperature of an ultrasonic water body is 30 ℃;
collecting the ultrasonic extraction liquid in each step in the first step into a heart-shaped bottle, setting the heating temperature of the collected 90mL of extraction liquid at 60 ℃ by using a rotary evaporator, keeping the vacuum degree at more than 260Pa, concentrating the extraction liquid to 2 mL; the rotary evaporator is an IKA rotary evaporator produced by Germany, and has the model: RV10DS 96;
before the purification treatment, activating a solid-phase extraction column by using 10mL of n-hexane, transferring the extract in the heart bottle to the solid-phase extraction column, rinsing the heart bottle by using 20mL of a mixture of dichloromethane and n-hexane, wherein the volume ratio of dichloromethane to n-hexane is 3:7, transferring the rinsing liquid to the solid-phase extraction column for leaching, and collecting rinsing liquid by using the heart bottle; the solid phase extraction column is a small solid phase extraction column, the model is Mega BE-C18, the specification is 5g/20mL, the package is 20/pk, and the original package of Agilent company in America is imported;
1cm of anhydrous sodium sulfate is filled in the upper section of a chromatographic column of the solid-phase extraction column in the purification treatment process, the column is required to be baked for more than 4 hours at 400 ℃ in a muffle furnace before use, and the column is sealed and stored after being cooled and then used in the purification treatment process;
concentrating the leacheate by using a rotary evaporator, setting the heating temperature of the rotary evaporator at 60 ℃, keeping the vacuum degree at more than 260Pa for concentration, concentrating to 1mL, adding 10mL of n-hexane for reconcentration to 1mL, transferring the concentrated 1mL of the concentrated solution into a cell bottle, adding 1mL of n-hexane into the heart bottle for collecting the leacheate, leaching the wall of the heart bottle, transferring the liquid obtained after leaching into the cell bottle, leaching the wall of the heart bottle for collecting the leacheate by using 1mL of n-hexane each time, repeating the steps for 3 times in sequence, transferring the liquid obtained after 3 times of leaching into the cell bottle, slightly blowing the substances in the cell bottle under the action of nitrogen flow, and fixing the volume of the solvent to 1 mL;
under the slight nitrogen flow blowing effect, a nitrogen blowing instrument is used, the type of the nitrogen blowing instrument is DC-24 type, the nitrogen blowing instrument is produced by Shanghai Anpu experiment science and technology Co., Ltd, the concentration of the used nitrogen is 99.99%, the pressure is 0.1MPa, and the nitrogen flow is 0.2L/min when the nitrogen is slightly blown;
the internal standard substances 2-fluoro-1,1-biphenyl and p-terphenyl 14 are purchased from certified standard substances and produced by Beijing Bailingwei science and technology Limited company in 2019, 12 months and 5 days;
the 8 HPAHs compound standard substances are prepared as follows: diluting 8 HPAHs compound standard substances of 2-bromofluorene, 9-chloro phenanthrene, 2-chloroanthracene, 9-bromophenanthrene, 9-bromoanthracene, 9, 10-dichloroanthracene, 9-dibromoanthracene and 7-bromobenzo [ a ] anthracene to 10mg/L by deionized water respectively, diluting each HPAHs compound standard substance in the 8 diluted HPAHs compound standard substances by deionized water respectively to prepare a mixed standard series with 5 concentration points, ensuring that the mass concentration of each diluted compound prepared into the 5 concentration points is 5 mug/L, 10 mug/L, 20 mug/L, 50 mug/L and 100 mug/L respectively, and then adding an internal standard solution 2-fluoro-1 with the concentration of 50 mug/L into each diluted compound prepared into a single concentration point, 1-biphenyl or p-terphenyl 14;
in the detection process by adopting the gas chromatograph-mass spectrometer, the used gas chromatograph-mass spectrometer is a gas chromatograph-mass spectrometer of Shimadzu, and the gas chromatograph-mass spectrometer is of the type: GC/MS-QP2010ultra, chromatographic column in gas chromatograph-mass spectrometer, specification type: HP-5MS,60 m.times.0.25 μm.times.0.25 mm, manufactured by Agilent, USA, with chromatographic conditions: sample inlet temperature: at 280 ℃, no flow splitting is carried out; sample introduction amount: 1.0 μ L, column flow: 1.0 mL/min; column temperature: keeping at 60 deg.C for 3min, heating to 200 deg.C at 5 deg.C/min, then heating to 250 deg.C at 2 deg.C/min, and finally heating to 290 deg.C/min, and keeping for 5 min; the mass spectrum conditions are as follows: ion source temperature: at 210 ℃; ionization capacity 70 eV; interface temperature: 260 ℃; quadrupole temperature: 150 ℃; scanning mode: selecting an ion mode (SIM) mode; sample introduction amount: 1.0 μ L, column flow: 1.0 mL/min; quantitative method: internal standard method.
3. The method for measuring halogenated polycyclic aromatic hydrocarbon in atmospheric dust according to any one of claims 1 to 2, wherein the glass fiber filter membrane is a glass fiber filter membrane with the diameter of 90mm and the pore diameter of 0.45 μm, and the glass fiber filter membrane is baked in a muffle furnace at 400 ℃ for 4 hours before use, and is sealed and stored after cooling for later use.
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