CN113866314B - Method for measuring content of nonafluorobutyl ethyl ether in soil and sediment - Google Patents
Method for measuring content of nonafluorobutyl ethyl ether in soil and sediment Download PDFInfo
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- CN113866314B CN113866314B CN202111174741.8A CN202111174741A CN113866314B CN 113866314 B CN113866314 B CN 113866314B CN 202111174741 A CN202111174741 A CN 202111174741A CN 113866314 B CN113866314 B CN 113866314B
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- 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
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- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
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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
Abstract
The invention relates to a method for determining the content of nonafluorobutyl ethyl ether in soil and sediments, which comprises the steps of firstly, collecting samples, collecting soil and sediment samples by using an injection type sampler, injecting the soil and sediment samples into a brown glass bottle, sealing and storing, and collecting parallel samples; the samples are refrigerated and stored in the transportation process after being collected; then, purging and trapping equipment is used, and nitrogen is used for purging the nonafluorobutyl ethyl ether in the sample by utilizing the volatility of the target object, so that the nonafluorobutyl ethyl ether is enriched by the adsorption trap; and analyzing the concentration of the nonafluorobutyl ethyl ether in the sample by adopting a gas chromatography-mass spectrometer. The method disclosed by the invention is quick and simple, and can realize accurate determination of the content of the nonafluorobutyl ethyl ether in soil and sediments.
Description
Technical Field
The invention relates to the technical field of detection and analysis, in particular to a method for determining the content of nonafluorobutyl ethyl ether in soil and sediments.
Background
Nonafluorobutyl ethyl ether, also known as perfluorobutyl ether; ethyl nonafluorobutyl ether; ethyl nonafluorobutyl ether; english name: ethyl Nonafluorobutyl Ether, CAS No. 163702-06-5, molecular formula C6H5F9O, molecular weight 264.08, boiling point 49.5 deg.C (760mmHg), density: 1.441g/cm3, vapor pressure: 311mmHg (25 ℃), is flammable, has a molecular structure shown in figure 1, is a green cleaning agent which is increasingly widely applied in recent years, and is industrially used as a chlorofluorocarbon substitute, a heat transfer agent, a lubricant and a solvent. The medicine is used for organ storage, retinal detachment treatment and the like.
The nonafluorobutyl ethyl ether has the characteristics of low boiling point, easy volatilization and flammability, and has inhalation allergy, volatile VOC is defined by the national environmental protection department of China as all possible volatile hydrocarbons except formaldehyde, and the national mandatory execution environmental protection standard HJ38-2017 is the residual value after methane is deducted from the total hydrocarbon measurement result; the total hydrocarbon refers to the sum of gaseous organic matters which generate response on a gas chromatography hydrogen flame ionization detector under specified conditions, and the ethyl nonafluorobutyl ether and the ethyl perfluorobutyl ether respond on the gas chromatography, and belong to volatile VOC (volatile organic Compounds). The method for quickly measuring the content of the nonafluorobutyl ethyl ether in the environmental soil and the sediment has important significance.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provide a method for rapidly determining the content of nonafluorobutyl ethyl ether in soil and sediments.
The technical scheme for solving the technical problems is as follows:
a method for determining the content of nonafluorobutylethyl ether in soil and sediments comprises the following steps:
s1, collecting samples: collecting soil and sediment samples by using an injection type sampler, injecting the soil and sediment samples into a brown glass bottle, sealing and storing the samples, and collecting two parallel samples;
s2, sample preservation: the samples are refrigerated and stored in the transportation process after being collected;
s3, introducing and enriching samples: purging and trapping equipment is used, and nitrogen is used for purging the nonafluorobutyl ethyl ether in the sample by utilizing the volatility of the target object, so that the nonafluorobutyl ethyl ether is enriched by an adsorption trap;
s4, analysis of the sample: analyzing the concentration of the nonafluorobutyl ethyl ether in the sample by adopting a gas chromatography-mass spectrometer, wherein the working conditions of the gas chromatography-mass spectrometer are as follows:
chromatography capillary column: DM-62430 m × 0.25mm × 1.4 μm;
sample inlet temperature: split-flow sample injection is carried out at 220 ℃, and the split-flow ratio is 5: 1;
column flow rate: 1.0ml/min, constant current;
column temperature: keeping at 35 deg.C for 2 min; heating to 120 deg.C at 5 deg.C/min, heating to 220 deg.C at 10 deg.C/min, and maintaining for 2 min;
mass spectrometry electron bombardment source: EI, ion source temperature: 230 ℃, ionization energy: 70eV, interface temperature: 280 ℃;
quadrupole temperature: 150 ℃, mass scan range: 35amu-270 amu;
solvent delay time: 3.0 min;
scanning mode: full scanning; a tuning mode: BFB tuning;
selection of characteristic ions: and (3) quantifying ions: 69, qualitative ion: 263. 131, 197;
comparing the retention time of the sample peak and the standard peak, and comparing the characteristic ion pairs and the ion pair abundance ratio in the sample peak mass spectrogram with the standard mass spectrogram to determine whether the nonafluorobutyl ethyl ether is detected in the sample; according to a calibration curve of a relative response factor, an internal standard method is adopted for quantification, the content of the nonafluorobutyl ethyl ether in the sample is determined, and the lowest quantitative concentration is 7.2 mu g/Kg;
further, in the step S1, when a sample is collected, 5g of the sample is injected into a brown glass bottle, the brown glass bottle has a cover with a teflon surface sealing gasket, 10mL of reagent water is added into the brown glass bottle in advance, the sampling amount of the sample is calculated by weighing the weight before and after sampling, the mass of the sample is confirmed by two times of weighing, and the sample is prevented from being disturbed and exposed in the air in the weighing process;
further, in the step S2, the sample needs to be refrigerated, stored and transported, specifically, the sample is refrigerated by adopting an incubator and cold row mode, and is immediately placed into a refrigerator after being transported back to a laboratory, and is stored at a temperature below 4 ℃, and the analysis is completed within 14 d;
further, in step S3, the operation conditions for purging and trapping are, soil mode:
a trap: 1/3Tenax, 1/3 silica gel, 1/3 active carbon mixed adsorbent;
purging flow rate: 40mL/min, purge time: 11min, purge temperature: 30 ℃;
desorption temperature: at 190 ℃, desorption time: 2 min;
baking temperature: baking time at 200 ℃: 8 min;
transmission line temperature: 200 ℃;
the beneficial effects of the invention are: the method is quick and simple, and can realize accurate determination of the content of the nonafluorobutyl ethyl ether in soil and sediments.
Drawings
FIG. 1 is a schematic structural diagram of a nonafluorobutylethyl ether compound;
FIG. 2 is a chromatogram of purge trap gas chromatography mass spectrometry for the determination of nonafluorobutylethyl ether in soils and sediments;
FIG. 3 is a standard mass spectrum of nonafluorobutylethyl ether.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
A method for determining the content of nonafluorobutylethyl ether in soil and sediments comprises the following steps:
s1, collecting samples: collecting soil and sediment samples by using an injection type sampler, injecting the soil and sediment samples into a brown glass bottle, sealing and storing the samples, and collecting two parallel samples;
s2, sample preservation: after the sample is collected, the sample is refrigerated and stored in the transportation process;
s3, introducing and enriching samples: purging the nonafluorobutyl ethyl ether in the sample by using purging and trapping equipment and using the volatility of the target object, and enriching the nonafluorobutyl ethyl ether by an adsorption trap;
s4, analysis of the sample: analyzing the concentration of the nonafluorobutyl ethyl ether in the sample by adopting a gas chromatography-mass spectrometer;
as a preferred embodiment of the technical solution of the present invention, in step S1, when collecting a sample, 5g of the sample is injected into a brown glass bottle, the brown glass bottle has a cap with a teflon face seal gasket, 10mL of reagent water is added into the brown glass bottle in advance, the sampling amount of the sample is calculated by weighing the weight before and after sampling, the sample mass is confirmed by two weighing methods, and the sample is prevented from being disturbed and exposed in the air during the weighing process;
as a preferred embodiment of the technical solution of the present invention, in step S2, the sample is to be refrigerated, stored and transported, specifically, refrigerated by using a heat preservation box and a cold row mode, transported back to the laboratory and immediately placed in a refrigerator, stored at a temperature below 4 ℃, and analyzed within 14 d;
in a preferred embodiment of the present invention, in step S3, the working conditions for purging and trapping are, in soil mode:
a trap: 1/3Tenax, 1/3 silica gel, 1/3 active carbon mixed adsorbent;
purge flow rate: 40mL/min, purge time: 11min, purge temperature: 30 ℃;
desorption temperature: at 190 ℃, desorption time: 2 min;
baking temperature: baking time at 200 ℃: 8 min;
transmission line temperature: 200 ℃;
as a preferred embodiment of the technical solution of the present invention, in step S4, the operating conditions of the gas chromatograph-mass spectrometer are as follows:
chromatography capillary column: DM-62430 m × 0.25mm × 1.4 μm;
sample inlet temperature: split-flow sample injection is carried out at 220 ℃, and the split-flow ratio is 5: 1;
column flow rate: 1.0ml/min, constant current;
column temperature: maintaining at 35 deg.C for 2 min; heating to 120 deg.C at 5 deg.C/min, heating to 220 deg.C at 10 deg.C/min, and maintaining for 2 min;
mass spectrometry electron bombardment source: EI, ion source temperature: 230 ℃, ionization energy: 70eV, interface temperature: 280 ℃;
quadrupole temperature: 150 ℃, mass scan range: 35amu-270 amu;
solvent delay time: 3.0 min;
scanning mode: full scanning; the tuning mode is as follows: BFB tuning;
selection of characteristic ions: and (3) quantifying ions: 69, qualitative ion: 263. 131, 197;
in step S4, comparing the retention time of the sample peak and the standard peak, and comparing the characteristic ion pair and the abundance ratio of the ion pair in the sample peak mass spectrogram with the standard mass spectrogram to determine whether the sample has nonafluorobutyl ethyl ether detected; according to the calibration curve of the relative response factor, the content of the nonafluorobutyl ethyl ether in the sample is determined by an internal standard method, and the lowest quantitative concentration is 7.2 mu g/Kg.
Wherein the standard gas chromatogram is shown in FIG. 2, and the standard mass spectrum of nonafluorobutylethyl ether is shown in FIG. 3; 1 of FIG. 2 represents nonafluorobutylethyl ether; 2. represents fluorobenzene (internal standard); 3. 5, 7, representing VOC (internal standard); 4. represents toluene-D8 (alternative), 6 represents 4-bromofluorobenzene (alternative);
the invention also provides a method for adding substitutes (toluene-D8 and 4-bromofluorobenzene) into a sample to characterize the recovery effect of measuring the content of the nonafluorobutyl ethyl ether in the soil and the sediments by using a gas chromatography mass spectrometer under the condition of purging and trapping, the measuring method is quick and simple, the accurate measurement of the content of the nonafluorobutyl ethyl ether in the soil, the sediments and other solid samples directly introduced into equipment for analysis can be realized, and the detection limit is 1.8 mu g/Kg.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (4)
1. A method for measuring the content of nonafluorobutylethyl ether in soil and sediments is characterized by comprising the following steps:
s1, collecting samples: collecting soil and sediment samples by using an injection type sampler, injecting the soil and sediment samples into a brown glass bottle, sealing and storing the samples, and collecting two parallel samples;
s2, sample preservation: the samples are refrigerated and stored in the transportation process after being collected;
s3, introducing and enriching samples: purging the nonafluorobutyl ethyl ether in the sample by using purging and trapping equipment and using the volatility of the target object, and enriching the nonafluorobutyl ethyl ether by an adsorption trap;
s4, analysis of the sample: analyzing the concentration of the nonafluorobutyl ethyl ether in the sample by adopting a gas chromatography-mass spectrometer, wherein the working conditions of the gas chromatography-mass spectrometer are as follows:
chromatographic capillary column: DM-62430 m is multiplied by 0.25mm by 1.4 mu m;
sample inlet temperature: split-flow sample injection is carried out at 220 ℃, and the split-flow ratio is 5: 1;
column flow rate: 1.0ml/min, constant current;
column temperature: keeping at 35 deg.C for 2 min; heating to 120 deg.C at 5 deg.C/min, heating to 220 deg.C at 10 deg.C/min, and maintaining for 2 min;
mass spectrometry electron bombardment source: EI, ion source temperature: 230 ℃, ionization energy: 70eV, interface temperature: 280 ℃;
quadrupole temperature: 150 ℃, mass scan range: 35amu-270 amu;
solvent delay time: 3.0 min;
scanning mode: full scanning; the tuning mode is as follows: BFB tuning;
selection of characteristic ions: and (3) quantifying ions: 69, qualitative ion: 263. 131, 197;
comparing the retention time of the sample peak and the standard peak, and comparing the characteristic ion pairs and the ion pair abundance ratio in the sample peak mass spectrogram with the standard mass spectrogram to determine whether the nonafluorobutyl ethyl ether is detected in the sample; according to the calibration curve of the relative response factor, the content of the nonafluorobutyl ethyl ether in the sample is determined by an internal standard method, and the lowest quantitative concentration is 7.2 mu g/Kg.
2. The method for determining the content of nonafluorobutylethyl ether in soil and sediments as claimed in claim 1, wherein: in the step S1, when a sample is collected, 5g of the sample is injected into a brown glass bottle, the brown glass bottle has a cover with a teflon face seal gasket, 10mL of reagent water is added into the brown glass bottle in advance, the sampling amount of the sample is calculated by weighing the weight before and after sampling, the sample mass is confirmed by two weighing methods, and the sample is prevented from being disturbed and exposed in the air during the weighing process.
3. The method of claim 1 for determining the amount of nonafluorobutylethyl ether in soils and sediments, wherein: in the step S2, the sample is to be refrigerated, stored and transported, specifically, the sample is refrigerated by adopting a mode of heating and cold discharging of an incubator, is immediately placed into a refrigerator after being transported back to a laboratory, is stored at a temperature below 4 ℃, and is analyzed within 14 days.
4. The method for determining the content of nonafluorobutylethyl ether in soil and sediments as claimed in claim 1, wherein in step S3, the working conditions of purging and trapping are that the soil mode is:
a trap: 1/3Tenax, 1/3 silica gel, 1/3 active carbon mixed adsorbent;
purging flow rate: 40mL/min, purge time: 11min, purge temperature: 30 ℃;
desorption temperature: at 190 ℃, desorption time: 2 min;
baking temperature: baking time at 200 ℃: 8 min;
transmission line temperature: at 200 ℃.
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| CN112379025B (en) * | 2020-12-11 | 2023-02-24 | 广州广电计量检测股份有限公司 | Gas chromatography-mass spectrometry detection method of hydrofluoroether solvent |
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