CN112798699A - Method for testing gaseous pollutants by arrow-shaped solid phase microextraction - Google Patents
Method for testing gaseous pollutants by arrow-shaped solid phase microextraction Download PDFInfo
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- 238000002470 solid-phase micro-extraction Methods 0.000 title claims abstract description 96
- 238000012360 testing method Methods 0.000 title claims abstract description 43
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 40
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 138
- 230000032683 aging Effects 0.000 claims abstract description 41
- 239000012071 phase Substances 0.000 claims abstract description 30
- 238000001819 mass spectrum Methods 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000004896 high resolution mass spectrometry Methods 0.000 claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims abstract description 4
- 239000000945 filler Substances 0.000 claims description 46
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 31
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 31
- -1 polydimethylsiloxane Polymers 0.000 claims description 31
- 238000005070 sampling Methods 0.000 claims description 24
- 239000002131 composite material Substances 0.000 claims description 22
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- 238000005192 partition Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 238000007865 diluting Methods 0.000 claims description 7
- 238000013507 mapping Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 238000004458 analytical method Methods 0.000 claims description 4
- 239000012086 standard solution Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000010998 test method Methods 0.000 claims 7
- 238000004817 gas chromatography Methods 0.000 abstract description 7
- 238000009835 boiling Methods 0.000 abstract 2
- 239000007789 gas Substances 0.000 description 60
- 238000012856 packing Methods 0.000 description 11
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 5
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 5
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical class CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
- G01N1/2202—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling
- G01N1/2214—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling by sorption
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
- G01N1/2273—Atmospheric sampling
-
- 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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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Sampling And Sample Adjustment (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention relates to a gaseous pollutant testing method of arrow-shaped solid phase microextraction, firstly aging an arrow-shaped solid phase microextraction device; collecting gaseous pollutants; preparing a standard curve of the compound by using the standard substance; testing a compound standard curve by using a gas chromatography high-resolution mass spectrum; testing by gas chromatography high-resolution mass spectrometry and obtaining the content of the compound through a standard curve; generating standard gas with known concentration and simultaneously performing adsorption; and (3) performing arrow-shaped solid phase microextraction test on the adsorption standard gas by using gas chromatography high-resolution mass spectrometry, and calculating the distribution coefficient of the compound. And (3) bringing the content of the compound sampled by the arrow-shaped solid-phase micro-extraction device in the actual air environment and a calibrated distribution coefficient into a formula to obtain the gas-phase concentration of the compound. The invention can greatly reduce the workload of testing the gaseous pollutants and improve the working efficiency. The invention has good data repeatability and accuracy, and has the advantages of low boiling point and high boiling point compounds, no noise, small volume, convenient use and the like.
Description
Technical Field
The invention relates to a method for testing gaseous pollutants by arrow-shaped solid-phase microextraction, belonging to the technical field of analytical chemistry.
Background
The detection of harmful gases in the air environment is the basis for the evaluation and control of the air environment. The polluting gases in the indoor and outdoor air not only have adverse effects (such as peculiar smell and discomfort) on the sensory experience of people, but also cause harm to the health of the people. Harmful gases and odor molecules in the air may originate from outdoor atmospheric pollutants, indoor building materials and human body emission processes in crowded areas. These harmful gases and odorous molecules are the main components of volatile organic compounds in the air environment. However, the current GB/T18883-2002 "indoor air quality Standard" incorporates only n-hexane to n-hexadecane compounds into the TVOC (Total volatile organic Compounds) calculation. On the one hand, this may miss the contribution of other VOCs outside the above range to air pollution, and on the other hand, one is unaware of the specific harmful gas composition and the composition of the odorous molecules, simply by the total amount of TVOC. Therefore, the screening of harmful gases and peculiar smell in the air environment is very important. Conventional mass spectrometers are equipped with a single quadrupole mass analyser which has low resolution, low sensitivity and limitations in the detection of gaseous contaminants. The gas chromatography quadrupole static electric field orbital hydrazine high-resolution mass spectrum used in the patent has ultrahigh resolution, the mass precision is less than 1.0 ppm, and the gas chromatography quadrupole static electric field orbital hydrazine high-resolution mass spectrum is widely applied to the fields of food safety, metabonomics and the like at present. Through the high-resolution mass spectrum, more abundant compound information can be obtained, and the screening of harmful gas and peculiar smell molecules in the air is realized. In addition, this patent adopts the passive form sampling mode of arrow shape solid phase microextraction. After sampling, the solid phase micro extraction sampling needle can directly enter a gas chromatography high resolution mass spectrum for testing without pretreatment. In addition, the solid-phase micro-extraction can also be used for sampling and analyzing in some closed spaces, and the inapplicability of the traditional air-extracting type active sampling method under the condition is overcome. The arrow-shaped protective head for the arrow-shaped solid-phase microextraction can ensure the feasibility of field sampling and laboratory testing in different places, and has the characteristics of accuracy and portability.
Disclosure of Invention
The invention provides a gaseous pollutant testing method of arrow-shaped solid-phase microextraction, and aims to improve a gaseous pollutant detecting method in the prior art so as to improve the detection precision, shorten the detection time and improve the detection efficiency.
The technical solution of the invention is as follows: a method for testing gaseous pollutants by arrow-shaped solid phase microextraction comprises the following steps:
(1) aging: and (3) aging the N arrow-shaped solid phase micro-extraction samplers coated with the X fillers by using an aging device, wherein the aging temperature is 100 to 300 ℃, the aging time is 2 to 60 minutes, and the aging times are 1 to 10 times.
(2) Sampling: and (2) collecting N gaseous pollutants at different spatial positions by using N aged arrow-shaped solid-phase microextraction samplers coated with X fillers in the step (1), wherein the sampling time is 2-240 minutes, and obtaining N arrow-shaped solid-phase microextraction samples.
(3) And (3) testing: and (3) testing the N arrow-shaped solid phase micro-extraction samples in the step (2) by using gas phase high resolution mass spectrometry to obtain N mass spectrograms.
(4) Diluting: the standard samples of P compounds were diluted into standard solutions of B (B > 5) concentrations, respectively, to obtain standard sequences of P compounds, respectively.
(5) Obtaining a standard curve: and (4) testing the standard sequences of the P compounds in the step (4) by using gas phase high resolution mass spectrometry, and establishing a mapping relation between the mass spectrum intensity and the content of the P compounds to obtain the standard curves of the P compounds.
(6) Mass spectrogram analysis: and (4) processing the N mass spectrograms obtained in the step (3) by using the standard curves of the P compounds obtained in the step (5) respectively to obtain the content of the P compounds in each mass spectrogram in the N mass spectrograms.
(7) Adsorption: and (3) accurately generating the standard gas with the concentration of W of P compounds by using a standard gas generating device, simultaneously adsorbing the standard gas with the concentration of P compounds with the concentration of W by using P arrow-shaped solid phase micro-extraction samplers coated with X fillers in the step (1), and then obtaining the content of P compounds adsorbed on the P arrow-shaped solid phase micro-extraction samplers coated with X fillers according to the steps (2), (3), (4), (5) and (6).
(8) Obtaining a distribution coefficient: obtaining the respective distribution coefficients of the P compounds according to the formula (1) according to the content of the P compounds adsorbed on the P arrow-shaped solid-phase micro-extraction samplers coated with the X filler obtained in the step (7);
Wherein the content of the first and second substances,Mthe content of P compounds adsorbed on the arrow-shaped solid phase microextraction coated with X filler,Kfor the partition coefficient of each of the P compounds,C a standard gas concentrations (μ g/m) of P compounds generated accurately for standard gas generating devices respectively3)，V fc Volume (m) of X coating for arrow-shaped solid phase microextraction coated with X filler3)。
(9) Obtaining gas phase concentration: and (3) obtaining the gas phase concentration of each P compound in the N mass spectrograms according to the formula (1) by using the content of the P compounds in each mass spectrogram in the N mass spectrograms obtained in the step (6) and the distribution coefficient of each P compound obtained in the step (8), and realizing the gas pollutant test of the gas phase high-resolution mass spectrograms.
The filler is one of acrylate, polydimethylsiloxane, composite filler of active carbon and polydimethylsiloxane or composite filler of polydimethylsiloxane and divinylbenzene.
The invention has the beneficial effects that:
1) according to the arrow-shaped solid phase microextraction gaseous pollutant testing method provided by the invention, the arrow-shaped solid phase microextraction is used for collecting gaseous pollutants, the gaseous pollutants can be collected at a plurality of positions at the same time, additional support of other equipment is not needed, low-boiling-point compounds and high-boiling-point compounds are considered, and the arrow-shaped solid phase microextraction gaseous pollutant testing method is noiseless, small in size and convenient to use.
2) The arrow-shaped solid-phase microextraction sampling method used by the invention can be suitable for but not limited to a closed small space, and overcomes the defects that vacuum is formed and the real environment to be tested is damaged due to overlarge sampling amount caused by sampling in the closed space by active sampling modes such as a sampling pipe and a Suma tank.
3) The method does not need a pretreatment step, and the arrow-shaped solid phase microextraction sampler is directly inserted into a gas chromatography sample inlet after sampling to complete analysis, thereby ensuring the recovery rate of low-boiling-point compounds and overcoming the defect of low recovery rate of certain compounds by a sampling tube in the prior art. In addition, the pretreatment time in the prior art is reduced to be less than 1% of that of the traditional method, so that the working efficiency is greatly improved, and the defect of long sampling time of polyurethane and other methods is overcome.
4) The gas phase high-resolution mass spectrum used by the invention has high resolution, high sensitivity and high stability, can reduce matrix interference when analyzing a sample, reduces false positive and false negative results in the result and ensures the accuracy of the analysis result.
5) The high resolution of the gas phase high resolution mass spectrum used by the invention has obvious advantages in the aspect of organic matter blind screening, so that harmful gas and peculiar smell molecules in the air environment can be accurately screened, and the difficulty that the indoor air quality can be judged by judging whether the total content of TVOC exceeds the standard but specific substances cannot be traced is overcome.
Detailed Description
The invention provides a method for testing gaseous pollutants by arrow-shaped solid-phase microextraction, which comprises the following steps of:
and (3) aging the N arrow-shaped solid phase micro-extraction samplers coated with the X fillers by using an aging device, wherein the aging temperature is 100 to 300 ℃, the aging time is 2 to 60 minutes, and the aging times are 1 to 10 times.
And (2) collecting N gaseous pollutants at different spatial positions by using N aged arrow-shaped solid-phase microextraction samplers coated with X fillers in the step (1), wherein the sampling time is 2-240 minutes, and obtaining N arrow-shaped solid-phase microextraction samples.
And (3) testing the N arrow-shaped solid phase micro-extraction samples in the step (2) by using gas phase high resolution mass spectrometry to obtain N mass spectrograms.
The standard samples of P compounds were diluted into standard solutions of B (B > 5) concentrations, respectively, to obtain standard sequences of P compounds, respectively.
And (4) testing the standard sequences of the P compounds in the step (4) by using gas phase high resolution mass spectrometry, and establishing a mapping relation between the mass spectrum intensity and the content of the P compounds to obtain the standard curves of the P compounds.
And (4) processing the N mass spectrograms obtained in the step (3) by using the standard curves of the P compounds obtained in the step (5) respectively to obtain the content of the P compounds in each mass spectrogram in the N mass spectrograms.
And (3) accurately generating the standard gas with the W concentration of P compounds by using a standard gas generating device, simultaneously adsorbing the standard gas with the W concentration of P compounds by using P arrow-shaped solid phase micro-extraction samplers coated with the X packing in the step (1), and then obtaining the content of the P compounds adsorbed on the P arrow-shaped solid phase micro-extraction samplers coated with the X packing according to the steps (2), (3), (4), (5) and (6).
Obtaining the content of P compounds adsorbed on the P arrow-shaped solid-phase micro-extraction samplers coated with the X filler obtained in the step (7), and obtaining the distribution coefficients of the P compounds according to a formula (1);
Wherein the content of the first and second substances,Mthe content of P compounds adsorbed on the arrow-shaped solid phase microextraction coated with X filler,Kfor the partition coefficient of each of the P compounds,C a standard gas concentrations (μ g/m) of P compounds generated accurately for standard gas generating devices respectively3)，V fc Volume (m) of X coating for arrow-shaped solid phase microextraction coated with X filler3)。
And (3) obtaining the gas phase concentration of each P compound in the N mass spectrograms according to the formula (1) by using the content of the P compounds in each mass spectrogram in the N mass spectrograms obtained in the step (6) and the distribution coefficient of each P compound obtained in the step (8), and realizing the gas pollutant test of the gas phase high-resolution mass spectrograms.
In the method for testing the gaseous pollutants, the filler is acrylate, polydimethylsiloxane, composite filler of activated carbon and polydimethylsiloxane and composite filler of polydimethylsiloxane and divinylbenzene.
Example 1
(1) Aging 10 arrow-shaped solid phase micro-extraction samplers coated with acrylate fillers by using an aging device, wherein the aging temperature is 100 ℃, the aging time is 2 minutes, and the aging times are 2 times;
(2) collecting 10 gaseous pollutants at different spatial positions by using the aged 10 arrow-shaped solid-phase microextraction samplers coated with the acrylate fillers in the step (1), wherein the sampling time is 5 minutes, and obtaining 10 arrow-shaped solid-phase microextraction samples;
(3) testing the 10 arrow-shaped solid phase micro-extraction samples in the step (2) by using gas phase high resolution mass spectrometry to obtain 10 mass spectrograms;
(4) respectively diluting the standard substance of 20 compounds into standard use solution with 10 concentrations to obtain standard sequences of 20 compounds;
(5) testing the standard sequences of the 20 compounds in the step (4) by using a gas phase high resolution mass spectrum, and establishing a mapping relation between the mass spectrum intensity and the content of the 20 compounds to obtain standard curves of the 20 compounds;
(6) processing the 10 mass spectrograms obtained in the step (3) by using the standard curves of the 20 compounds obtained in the step (5) to obtain the content of the 20 compounds in each mass spectrogram in 10 mass spectrograms;
(7) accurate generation of 0.5mg/m of 20 compounds each using standard gas generating equipment3The standard gas with concentration is used, 20 arrow-shaped solid phase micro-extraction samplers coated with the acrylate fillers in the step (1) are used for adsorbing the standard gas with concentration of 20 compounds of 0.5mg/m respectively, and then the content of the 20 compounds adsorbed on the 20 arrow-shaped solid phase micro-extraction samplers coated with the acrylate fillers is obtained according to the steps (2), (3), (4), (5) and (6);
(8) obtaining the content of 20 compounds adsorbed on the 20 arrow-shaped solid-phase micro-extraction samplers coated with the acrylate filler obtained in the step (7), and obtaining the distribution coefficients of the 20 compounds according to the formula (1);
Wherein the content of the first and second substances,Mthe content of adsorbed 20 compounds on arrow-shaped solid phase microextraction coated with acrylate filler,Kthe partition coefficient for each of the 20 compounds,C a standard gas concentrations (μ g/m) of 20 compounds generated accurately for each standard gas generator3)，V fc Volume (m) of acrylate coating for arrow-shaped solid phase microextraction coated with acrylate filler3)。
(9) And (3) obtaining the gas phase concentration of each of 20 compounds in 10 mass spectrograms according to a formula (1) by using the content of 20 compounds in each mass spectrogram in the 10 mass spectrograms obtained in the step (6) and the distribution coefficient of each of the 20 compounds obtained in the step (8), and realizing the gaseous pollutant test of arrow-shaped solid phase microextraction.
Table 1 shows the measured partition coefficients of each of the 20 compounds.
| Serial number | Name of Compound | CAS number | Distribution coefficient K |
| 1 | Formaldehyde (I) | 50-00-0 | 1.6×105 |
| 2 | Benzene and its derivatives | 71-43-2 | 5.9×102 |
| 3 | Toluene | 108-88-3 | 2.0×103 |
| 4 | Trichloroethylene | 79-01-6 | 6.5×102 |
| 5 | Tetrachloroethylene | 127-18-4 | 3.5×103 |
| 6 | Ethylbenzene production | 100-41-4 | 4.4×103 |
| 7 | Carbon tetrachloride | 56-23-5 | 6.0×102 |
| 8 | DEHP, di (2-ethylhexyl) phthalate | 117-81-7 | 3.6×109 |
| 9 | DEP, diethyl phthalate | 84-66-2 | 3.2×104 |
| 10 | DBP, di-n-butyl phthalate | 84-74-2 | 4.3×105 |
| 11 | DiBP, diisobutyl phthalate | 84-69-5 | 2.6×105 |
| 12 | BBP, butyl benzyl phthalate | 85-68-7 | 1.0×106 |
| 13 | Naphthalene | 91-20-3 | 1.1×105 |
| 14 | Benzo [ a ]]Pyrene | 50-32-8 | 7.2×107 |
| 15 | Acenaphthene | 83-32-9 | 1.1×106 |
| 16 | Fluorene compounds | 86-73-7 | 3.8×106 |
| 17 | Anthracene | 120-12-7 | 1.2×107 |
| 18 | Fluoranthene | 206-44-0 | 4.0×108 |
| 19 | Pyrene | 129-00-0 | 1.6×108 |
| 20 | Dibenzo [ a, h ]]Anthracene | 53-70-3 | 6.0×108 |
Example 2
(1) Aging 5 arrow-shaped solid phase micro-extraction samplers coated with polydimethylsiloxane packing by using an aging device, wherein the aging temperature is 200 ℃, the aging time is 15 minutes, and the aging times are 5 times;
(2) collecting 5 gaseous pollutants at different spatial positions by using the 5 aged arrow-shaped solid-phase microextraction samplers coated with the polydimethylsiloxane packing in the step (1), wherein the sampling time is 30 minutes, and obtaining 5 arrow-shaped solid-phase microextraction samples;
(3) testing the 5 arrow-shaped solid phase micro-extraction samples in the step (2) by using a gas phase high resolution mass spectrum to obtain 5 mass spectrograms;
(4) respectively diluting the standard substance of 12 compounds into standard use solution with 8 concentrations to obtain standard sequences of 12 compounds;
(5) testing the standard sequences of the 12 compounds in the step (4) by using a gas phase high resolution mass spectrum, and establishing a mapping relation between the mass spectrum intensity and the content of the 12 compounds to obtain standard curves of the 12 compounds;
(6) processing the 5 mass spectrograms obtained in the step (3) by using the standard curves of the 12 compounds obtained in the step (5) to obtain the content of the 12 compounds in each mass spectrogram of the 5 mass spectrograms;
(7) accurate generation of 0.02mg/m of 12 compounds each using a standard gas generating apparatus3Respectively adsorbing 12 standard gases with the concentration of 0.02mg/m by using 5 arrow-shaped solid phase micro-extraction samplers coated with polydimethylsiloxane packing in the step (1), and then obtaining the content of 12 compounds adsorbed on the 5 arrow-shaped solid phase micro-extraction samplers coated with polydimethylsiloxane packing according to the steps (2), (3), (4), (5) and (6);
(8) obtaining the content of 12 compounds adsorbed on 12 arrow-shaped solid-phase micro-extraction samplers coated with polydimethylsiloxane packing obtained in the step (7), and obtaining the distribution coefficients of the 12 compounds according to the formula (1);
Wherein the content of the first and second substances,Mthe content of 12 compounds adsorbed on arrow-shaped solid phase microextraction coated with polydimethylsiloxane packing,Kthe partition coefficient for each of the 12 compounds,C a standard gas concentrations (μ g/m) of 12 compounds generated accurately for each standard gas generator3)，V fc Volume (m) of polydimethylsiloxane coating for arrow-shaped solid phase microextraction coated with polydimethylsiloxane Filler3)。
(9) And (3) obtaining the gas phase concentration of each of the 12 compounds in the 5 mass spectrograms according to the formula (1) by using the content of the 12 compounds in each mass spectrogram in the 5 mass spectrograms obtained in the step (6) and the distribution coefficient of each of the 12 compounds obtained in the step (8), and realizing the gaseous pollutant test of arrow-shaped solid phase microextraction.
Example 3
(1) Aging 15 arrow-shaped solid-phase micro-extraction samplers coated with activated carbon and polydimethylsiloxane composite fillers by using an aging device, wherein the aging temperature is 300 ℃, the aging time is 30 minutes, and the aging times are 10 times;
(2) collecting 15 gaseous pollutants at different spatial positions by using 15 arrow-shaped solid-phase micro-extraction samplers coated with activated carbon and polydimethylsiloxane composite fillers after aging in the step (1), wherein the sampling time is 150 minutes, and obtaining 15 arrow-shaped solid-phase micro-extraction samples;
(3) testing the 15 arrow-shaped solid phase micro-extraction samples in the step (2) by using a gas phase high resolution mass spectrum to obtain 15 mass spectrograms;
(4) respectively diluting the standard substance of 33 compounds into standard use solution with 14 concentrations to obtain standard sequences of the 33 compounds;
(5) testing the standard sequences of the 33 compounds in the step (4) by using a gas phase high resolution mass spectrum, and establishing a mapping relation between the mass spectrum intensity and the content of the 33 compounds to obtain standard curves of the 33 compounds;
(6) processing the 15 mass spectrograms obtained in the step (3) by using the standard curves of the 33 compounds obtained in the step (5) to obtain the content of the 33 compounds in each mass spectrogram in the 15 mass spectrograms;
(7) accurate generation of 1.2mg/m of 33 compounds using a standard gas generating apparatus3Respectively adsorbing 33 standard gases with the concentration of 1.2mg/m of compounds by using 5 arrow-shaped solid-phase microextraction samplers coated with the composite filler of the activated carbon and the polydimethylsiloxane in the step (1), and then obtaining the content of the 33 compounds adsorbed on 15 arrow-shaped solid-phase microextraction samplers coated with the composite filler of the activated carbon and the polydimethylsiloxane according to the steps (2), (3), (4), (5) and (6);
(8) obtaining the content of 33 compounds adsorbed on 33 arrow-shaped solid-phase micro-extraction samplers coated with activated carbon and polydimethylsiloxane composite fillers obtained in the step (7), and obtaining the distribution coefficients of the 33 compounds according to a formula (1);
Wherein the content of the first and second substances,Mthe content of 33 compounds adsorbed on arrow-shaped solid-phase microextraction coated with activated carbon and polydimethylsiloxane composite filler,Kthe partition coefficient for each of the 33 compounds,C a standard gas concentrations (μ g/m) of 33 compounds generated accurately for each standard gas generating device3)，V fc Volume (m) of arrow-shaped solid-phase microextraction activated carbon and polydimethylsiloxane composite coating coated with activated carbon and polydimethylsiloxane composite filler3)。
(9) And (3) obtaining the gas phase concentration of each 33 compounds in the 15 mass spectrograms according to the formula (1) by using the content of the 33 compounds in each mass spectrogram in the 15 mass spectrograms obtained in the step (6) and the distribution coefficient of each 33 compounds obtained in the step (8), and realizing the gaseous pollutant test of arrow-shaped solid phase microextraction.
Example 4
(1) Aging 30 arrow-shaped solid phase micro-extraction samplers coated with polydimethylsiloxane and divinylbenzene composite fillers by using an aging device, wherein the aging temperature is 300 ℃, the aging time is 220 minutes, and the aging times are 6 times;
(2) collecting 30 gaseous pollutants at different spatial positions by using 30 arrow-shaped solid phase microextraction samplers coated with polydimethylsiloxane and divinylbenzene composite fillers after aging in the step (1), wherein the sampling time is 240 minutes, and obtaining 30 arrow-shaped solid phase microextraction samples;
(3) testing the 30 arrow-shaped solid phase micro-extraction samples in the step (2) by using gas phase high resolution mass spectrometry to obtain 30 mass spectrograms;
(4) respectively diluting the standard substance of 54 compounds into standard use solution with 15 concentrations to obtain standard sequences of 54 compounds;
(5) testing the standard sequences of the 54 compounds in the step (4) by using a gas phase high resolution mass spectrum, and establishing a mapping relation between the mass spectrum intensity and the content of the 54 compounds to obtain standard curves of the 54 compounds;
(6) processing the 30 mass spectrograms obtained in the step (3) by using the standard curves of the 154 compounds obtained in the step (5) to obtain the content of 54 compounds in each mass spectrogram in the 30 mass spectrograms;
(7) accurate generation of 6.0mg/m of 54 compounds each using a standard gas generating apparatus3Respectively adsorbing 54 standard gases with the concentration of 6.0mg/m by using 30 arrow-shaped solid-phase microextraction samplers coated with the polydimethylsiloxane-divinylbenzene composite packing in the step (1), and then obtaining the content of the 54 compounds adsorbed on the 30 arrow-shaped solid-phase microextraction samplers coated with the polydimethylsiloxane-divinylbenzene composite packing according to the steps (2), (3), (4), (5) and (6);
(8) the content of 54 compounds adsorbed on 30 arrow-shaped solid phase microextraction samplers coated with polydimethylsiloxane and divinylbenzene composite packing obtained in the step (7) is obtained, and distribution coefficients of the 54 compounds are obtained according to a formula (1);
Wherein the content of the first and second substances,Mthe content of 54 compounds adsorbed on arrow-shaped solid phase microextraction coated with composite filler of polydimethylsiloxane and divinylbenzene,Kfor each of the 54 compounds the partition coefficient,C a standard gas concentrations (μ g/m) of 54 compounds generated accurately for each standard gas generating device3)，V fc Volume (m) of composite coating of polydimethylsiloxane and divinylbenzene coated with arrow-shaped solid phase microextraction of polydimethylsiloxane and divinylbenzene composite3)。
(9) And (3) obtaining the gas phase concentrations of the 54 compounds in the 30 mass spectrograms according to the formula (1) by using the content of the 54 compounds in each mass spectrogram in the 30 mass spectrograms obtained in the step (6) and the distribution coefficients of the 54 compounds obtained in the step (8), and realizing the gaseous pollutant test of the arrow-shaped solid phase microextraction.
Claims (10)
1. A method for testing gaseous pollutants by arrow-shaped solid phase microextraction is characterized by comprising the following steps: (1) aging; (2) sampling; (3) testing; (4) diluting; (5) obtaining a standard curve; (6) analyzing a mass spectrogram; (7) adsorption; (8) obtaining a distribution coefficient; (9) the gas phase concentration is obtained.
2. The arrow-shaped solid phase microextraction test method for gaseous pollutants according to claim 1, wherein said step (1) of aging: aging the N arrow-shaped solid-phase micro-extraction samplers coated with the X fillers by using an aging device, wherein the aging temperature is 100-300 ℃, the aging time is 2-60 minutes, and the aging times are 1-10 times; the filler is one of acrylate, polydimethylsiloxane, composite filler of active carbon and polydimethylsiloxane or composite filler of polydimethylsiloxane and divinylbenzene.
3. The arrow-shaped solid phase microextraction test method for gaseous pollutants according to claim 1, wherein said step (2) of sampling: and (2) collecting N gaseous pollutants at different spatial positions by using N aged arrow-shaped solid-phase microextraction samplers coated with X fillers in the step (1), wherein the sampling time is 2-240 minutes, and obtaining N arrow-shaped solid-phase microextraction samples.
4. The method for testing gaseous pollutants by arrow-shaped solid phase microextraction according to claim 1, wherein said step (3) tests: and (3) testing the N arrow-shaped solid phase micro-extraction samples in the step (2) by using gas phase high resolution mass spectrometry to obtain N mass spectrograms.
5. The arrow-shaped solid phase microextraction test method for gaseous pollutants according to claim 1, wherein said step (4) of diluting: the standard samples of P compounds were diluted into standard solutions of B (B > 5) concentrations, respectively, to obtain standard sequences of P compounds, respectively.
6. The arrow-shaped solid phase microextraction test method for gaseous pollutants according to claim 1, wherein said step (5) obtains a standard curve: and (4) testing the standard sequences of the P compounds in the step (4) by using gas phase high resolution mass spectrometry, and establishing a mapping relation between the mass spectrum intensity and the content of the P compounds to obtain the standard curves of the P compounds.
7. The arrow-shaped solid phase microextraction test method for gaseous pollutants according to claim 1, wherein said step (6) of mass spectrogram analysis: and (4) processing the N mass spectrograms obtained in the step (3) by using the standard curves of the P compounds obtained in the step (5) respectively to obtain the content of the P compounds in each mass spectrogram in the N mass spectrograms.
8. The arrow-shaped solid phase microextraction test method for gaseous pollutants according to claim 1, wherein said step (7) of adsorbing: and (3) accurately generating the standard gas with the concentration of W of P compounds by using a standard gas generating device, simultaneously adsorbing the standard gas with the concentration of P compounds with the concentration of W by using P arrow-shaped solid phase micro-extraction samplers coated with X fillers in the step (1), and then obtaining the content of P compounds adsorbed on the P arrow-shaped solid phase micro-extraction samplers coated with X fillers according to the steps (2), (3), (4), (5) and (6).
9. The method for testing gaseous pollutants by arrow-shaped solid phase microextraction according to claim 1, wherein said step (8) obtains a partition coefficient: obtaining the respective distribution coefficients of the P compounds according to the formula (1) according to the content of the P compounds adsorbed on the P arrow-shaped solid-phase micro-extraction samplers coated with the X filler obtained in the step (7);
Wherein the content of the first and second substances,Mthe content of P compounds adsorbed on the arrow-shaped solid phase microextraction coated with X filler,Kfor the partition coefficient of each of the P compounds,C a standard gas concentrations (μ g/m) of P compounds generated accurately for standard gas generating devices respectively3)，V fc Volume (m) of X coating for arrow-shaped solid phase microextraction coated with X filler3)。
10. The arrow-shaped solid phase microextraction test method for gaseous pollutants according to claim 1, wherein said step (9) obtains a gas phase concentration: and (3) obtaining the gas phase concentration of each P compound in the N mass spectrograms according to the formula (1) by using the content of the P compounds in each mass spectrogram in the N mass spectrograms obtained in the step (6) and the distribution coefficient of each P compound obtained in the step (8), and realizing the gas pollutant test of the gas phase high-resolution mass spectrograms.
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