CN112526050A - Method for measuring polycyclic aromatic hydrocarbon in atmospheric dry and wet sediment through GC-MS - Google Patents
Method for measuring polycyclic aromatic hydrocarbon in atmospheric dry and wet sediment through GC-MS Download PDFInfo
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- G01—MEASURING; TESTING
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- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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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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Abstract
The invention discloses a method for determining polycyclic aromatic hydrocarbon in atmospheric dry and wet sediments by GC-MS (gas chromatography-Mass spectrometer), which comprises the following steps: performing Soxhlet extraction or accelerated solvent extraction on an atmospheric sediment sample, drying, concentrating and purifying silica gel on an extract, performing full-scan detection on a sample concentrated solution by using gas chromatography-mass spectrometry (GC-MS), and then performing qualitative determination by using a mass spectrogram and retention time of a target component and a mass spectrogram and retention time in a computer library as references, wherein the concentration of each determined component depends on the mass spectrum response ratio of a quantitative ion and an internal standard substance quantitative ion; finally, an internal standard compound with known concentration is added into each sample, and the quantitative analysis is carried out by an internal standard method. The method has the advantages of short detection flow, high precision and accuracy, and can be used for large-scale detection. When the sampling amount is 1.0g, the detection limit of the method is as follows: 0.30-0.60 ng/g, and meets the analysis requirements of actual samples. Provides a feasible method for analyzing the polycyclic aromatic hydrocarbon in the atmospheric dry and wet sediment.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a method for measuring polycyclic aromatic hydrocarbon in atmospheric dry and wet sediments by GC-MS.
Background
The atmospheric dry and wet sedimentation is one of the approaches of soil pollution, and the polycyclic aromatic hydrocarbon in the atmospheric dry and wet sediment is one of the main indexes reflecting the pollution of atmospheric dust particles.
Polycyclic aromatic hydrocarbons are produced from both natural and man-made sources. Polycyclic aromatic hydrocarbons formed by biosynthesis of land, aquatic plants and microorganisms, natural fires of forests and grasslands and volcanic activity constitute the natural background value of polycyclic aromatic hydrocarbons. The background value of the soil polycyclic aromatic hydrocarbon formed by bacterial activity and plant decay is 100-1000 mug/kg. The background value of the polycyclic aromatic hydrocarbon in the underground water is 0.001-0.01 mu g/L. The background value in the freshwater lake is 0.01-0.25 mu g/L. The pollution source of the artificial polycyclic aromatic hydrocarbon is many, and the pollution source can be found in every corner of our life, and any place where organic matters are processed and discarded and are combusted or used can possibly generate the polycyclic aromatic hydrocarbon, such as any factory emitting smoke dust, such as oil refineries, coking plants, rubber plants and thermal power plants, tail gas emitted by various transportation vehicles, coal gas emitted by other heating facilities and even cooking smoke of residents, and the like.
Polycyclic aromatics have three characteristics: first, persistence. Polycyclic aromatic hydrocarbons can migrate long distances through various environmental media (atmosphere, water, organisms, etc.) and exist in the environment for a long time, thereby causing serious harm to human health and the environment. Due to the extremely low water solubility of the polycyclic aromatic hydrocarbon, the degradation and the bioavailability of the polycyclic aromatic hydrocarbon in soil are severely limited, and the polycyclic aromatic hydrocarbon has higher octanol-water partition coefficient and is easy to be distributed into environment hydrophobic organic matters, so that the polycyclic aromatic hydrocarbon is easy to be enriched and concentrated in organism lipids and has higher biological enrichment factors. Second, "three-fold effect". Polycyclic aromatic hydrocarbons have strong mutagenic, carcinogenic and teratogenic effects, referred to as "triogenic" effects. The polycyclic aromatic hydrocarbon has obvious influence on the growth of animals and plants, and the polycyclic aromatic hydrocarbon falls on plant leaves to cause the plants to discolor, shrink, curl and fall off, thereby influencing the normal growth and fruiting of the plants. The influence of polycyclic aromatic hydrocarbon on animals is serious, most of benzo [ alpha ] pyrene in human bodies can be absorbed by human bodies along with food intake, after the benzo [ alpha ] pyrene is absorbed by digestive tracts, the benzo [ alpha ] pyrene is quickly dispersed in the human bodies through blood, one part of the benzo [ alpha ] pyrene absorbed by the human bodies is combined with protein, the other part of the benzo [ alpha ] pyrene is involved in metabolic decomposition, the benzo [ alpha ] pyrene combined with the protein can be combined with electrophilic cell receptors, so that enzymes for cell growth are changed, cells lose the ability of controlling growth, and canceration is caused. Third, bioaccumulation. Polycyclic aromatic hydrocarbons are harmful to health and environment through environmental accumulation, biological accumulation, biotransformation or chemical reaction after entering the environment, and polycyclic aromatic hydrocarbons are not direct carcinogens and generate final carcinogens in vivo through the action of enzymes. Cancer is caused by irreparable damage of carcinogens to DNA or RNA.
At present, a plurality of methods for measuring polycyclic aromatic hydrocarbons in the atmosphere are available in foreign countries, ISO 12884: 2000 "gas chromatography-Mass Spectrometry of polycyclic aromatic hydrocarbons in gas phase and particulate matter collected by ambient air adsorbent-Filter Membrane", USEPA Standard: determination of toxic organic compounds in air the polycyclic aromatic hydrocarbons in ambient air were determined by methods of assembling TO-13A gas chromatography-mass spectrometry on-line method for determining polycyclic aromatic hydrocarbons in ambient air and 8270E gas chromatography/mass spectrometry for testing semi-volatile organic compounds (revised 6.6.2018), separation by capillary column and gas chromatography-mass spectrometry (GC-MS) in PA/625/R-96/010B, second edition of the method for determining toxic organic compounds in air. There are some related detection methods in China, for example, the determination methods of polycyclic aromatic hydrocarbons are available in the gas chromatography-mass spectrometry for determining semi-volatile organic compounds of HJ 834 and 2017 soil and sediments, the gas chromatography-mass spectrometry for determining polycyclic aromatic hydrocarbons of HJ805-2016 soil and sediments, the gas chromatography-mass spectrometry for determining polycyclic aromatic hydrocarbons in HJ646-2013 ambient air, waste gas and particles, and the related contents such as external chromatographic conditions of pretreatment can be referred to. However, no report is found about the method for detecting polycyclic aromatic hydrocarbons in the dry and wet sediments in the atmosphere.
Disclosure of Invention
At present, no report is found for the development of a method for detecting polycyclic aromatic hydrocarbons in atmospheric dry and wet sediments. In order to meet the detection requirement, the method firstly proposes to establish a GC-MS detection method for 16 kinds of polycyclic aromatic hydrocarbons in the atmospheric dry and wet sediments by referring to a gas chromatography-mass spectrometry for determining polycyclic aromatic hydrocarbons in HJ805-2016 soil and sediments, a gas chromatography-mass spectrometry for determining polycyclic aromatic hydrocarbons in HJ646-2013 ambient air, waste gas and particles.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for determining polycyclic aromatic hydrocarbons in atmospheric dry and wet sediments by GC-MS comprises the following steps: performing Soxhlet extraction or accelerated solvent extraction on an atmospheric sediment sample, drying, concentrating and purifying silica gel on an extract, performing full-scan detection on a sample concentrated solution by using gas chromatography-mass spectrometry (GC-MS), and then performing qualitative determination by using a mass spectrogram and retention time of a target component and a mass spectrogram and retention time in a computer library as references, wherein the concentration of each determined component depends on the mass spectrum response ratio of a quantitative ion and an internal standard substance quantitative ion; finally, an internal standard compound with known concentration is added into each sample, and the quantitative analysis is carried out by an internal standard method.
The extraction method comprises the following steps: mixing a proper amount of atmospheric sediment sample and 10.0g of anhydrous sodium sulfate, adding a proper amount of substitute, and placing the mixture into an extraction sleeve; using 100mL of n-hexane: extracting with acetone (v: v ═ 1: 1) for 12 h; after the extract was cooled, it was transferred to a 500mL separatory funnel, and an appropriate amount of 2% sodium sulfate solution was added to wash off the acetone. Dehydrating, concentrating to about 1mL by rotary evaporation, and purifying.
The purification method comprises the following steps:
a. activation of solid phase extraction column
Filling 0.5cm of anhydrous sodium sulfate at the upper end of the solid phase extraction column, leaching the small column with 15mL of dichloromethane and 10mL of n-hexane in sequence, and closing the piston when the anhydrous sodium sulfate is about to be exposed; the anhydrous sodium sulfate can not be exposed in the air during the operation of the step, and the small column needs to be conditioned again if the situation occurs;
b. sample transfer and decontamination
Transferring the concentrated sample to a solid phase extraction column without damage, finishing the transfer of all compounds by using another 1mL of n-hexane, keeping for 5min after the transfer is finished, opening a piston, discarding the part of effluent liquid, and closing the piston when anhydrous sodium sulfate is about to be exposed;
c. elution of the sample
Eluting the solid phase extraction column with 20mL of eluent (1.6) for several times, and filling the eluent with 10mL of nitrogen blowing tubes for several times;
d. concentrating to constant volume
Blowing nitrogen at 40 deg.C to concentrate 3.1.3.3 effluent to slightly less than 500.00 μ L, metering volume to 500.00 μ L with micro syringe, adding internal standard 10.0 μ L, shaking, and measuring on machine.
The chromatographic conditions are as follows:
sample inlet temperature: 280 ℃; the sample is injected without shunting, and the sample injection amount is 2 mu L; the pressure of a sample inlet is 9.95psi, the purging flow is 11.0mL/min, and the purging time is 2 min; the flow rate of the chromatographic column is 1.1mL/min, and the flow rate is 39 cm/sec; temperature rising procedure: keeping at 70 deg.C for 4min, heating to 300 deg.C at a rate of 10 deg.C/min, keeping for 2min, heating to 340 deg.C at a rate of 5 deg.C/min, and keeping until all components flow out; interface temperature: 285 deg.C.
The mass spectrum conditions are as follows:
the tuning mode is as follows: DFTTP; the scanning mode is as follows: full scanning, wherein the scanning range is 50-450 amu; ion source temperature: 230 ℃; the temperature of the quadrupole rods is 150 ℃; ionization energy: 70 ev.
Drawing of standard curve
a. Preparation of the calibration series: sucking a proper amount of standard stock solution and internal standard stock solution, fixing the volume to 10mL by using normal hexane, preparing calibration points with the concentration of the polycyclic aromatic hydrocarbon compound of 1000, 400, 200, 100, 50 and 20ng/mL, wherein the internal standard concentration of each calibration point is 400 ng/mL;
b. initial calibration curve: performing data acquisition according to a set data acquisition method, and drawing a calibration curve by using the concentration of an internal standard/target compound as an abscissa and the response of an internal standard/target ion as an ordinate by using the internal standard method, wherein the correlation coefficient of the curve is more than 0.995, the Relative Standard Deviation (RSD) of response factors of each compound is not more than 30%, otherwise, drawing the calibration curve again;
c. drawing total ion flow diagram of standard sample
The mass spectrum calibration method comprises the following steps: after the starting is stable for 2 hours, tuning a mass spectrometer according to a TFAPP mode, and injecting 2 mu L of decafluorotriphenyl phosphine according to a set method; analyzing at least 5 calibration points according to a set method to draw a working curve; and (3) sample analysis: analyzing the processed sample under the same instrument condition according to the calibration curve; blank experiment: a blank test should be run to check for contamination during the analysis for each batch.
Data processing and result calculation:
calculating the concentration of the compound in the extracting solution: ions were extracted and the peak areas integrated and the compound content was calculated according to the formula Q ═ C × V/n, where: q-sample content, ng/g; c-concentration of the extracting solution calculated by the calibration curve, ng/mL; v-volume of test extract, mL; n-sample size, g.
Further comprising a repeat analysis: the number of repeated analysis samples is not less than 5%, the qualification rate of analysis items is more than 94%, and when the repeated measurement does not meet the requirement, the sampling proportion is enlarged until the requirement is met.
In order to meet the requirement of ecological environment protection in China, a GC-MS detection method for detecting 16 polycyclic aromatic hydrocarbons in atmospheric dry and wet sediments is established. The method is put forward for the first time, meets the requirements of relevant standards of national resources and ecological environment in China, and has no conflict with other standards. The implementation of the method provides a reliable technical section for detecting pollution of the polycyclic aromatic hydrocarbon compound in national laws and regulations of the republic of China, such as environmental protection laws, agricultural geological survey, urban geological survey and the like. According to the technical characteristics and the analysis and summary of the practical application condition of the method, the method has the following advantages:
(1) the detection process is short, the precision and the accuracy are good, and the method can be used for large-batch detection.
(2) When the sampling amount is 1.0g, the detection limit of the method is as follows: 0.30-0.60 ng/g, and meets the analysis requirements of actual samples.
(3) Provides a feasible method for analyzing the polycyclic aromatic hydrocarbon in the dry and wet sediments in the atmosphere, and fills up the technical blank of analyzing the polycyclic aromatic hydrocarbon in the dry and wet sediments in the atmosphere.
Drawings
FIG. 1 is a total ion flow graph of a standard sample of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. 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.
Example one
A method for determining polycyclic aromatic hydrocarbons in atmospheric dry and wet sediments by GC-MS comprises the following steps: and (3) performing Soxhlet extraction (or accelerated solvent extraction) on the atmospheric sediment sample, drying and concentrating the extract, purifying silica gel, and performing full-scan detection on the sample concentrated solution by using a gas chromatography-mass spectrometry (GC-MS). And performing qualitative determination by comparing the mass spectrum and retention time of the target component with those in a computer library, wherein the concentration of each determined component depends on the mass spectrum response ratio of the quantitative ion to the quantitative ion of the internal standard substance.
An internal standard compound is added to each sample at a known concentration and quantified by the internal standard method. The names of the 16 polycyclic aromatic hydrocarbons are shown in table 1.
TABLE 118 names of PAHs (two substitutes included)
Example two
Reagents and materials
The reagents used in the method should meet the national standard of pure chemical analysis unless otherwise noted.
1.1 Dichloromethane (CH)2Cl2): pesticide residue grade or equivalent grade.
1.2 n-Hexane (C)6H14): pesticide residue grade or equivalent grade.
1.3 acetone (CH)3COCH3): pesticide residue grade or equivalent grade.
1.4 Standard solution
1.4.1 polycyclic aromatic hydrocarbons standard stock solutions: the concentration is 10mg/L, including 16 compounds in Table 1, diluted with n-hexane to 2mg/L, and stored at 4 deg.C or below.
1.4.2 internal standard stock solutions: at a concentration of 1000mg/L, comprising perylene-d12And bent-d12Acenaphthylene-d12Naphthalene-d8Phenanthrene-d10Diluting n-hexane to 20mg/L, and storing at below 4 deg.C.
1.4.3 substitute standard stock solutions: the concentration is 500mg/L, and the terphenyl-d is contained14Diluting 4-bromo-2-fluorobiphenyl with n-hexane to 20mg/L, and storing at below 4 deg.C.
1.5 tuning solution: decafluorotriphenylphosphonium (DFTPP) with n-hexane medium concentration of 2mg/L, and storing at 4 deg.C or below.
1.6 eluent: dichloromethane and n-hexane in a volume ratio of 1: 1 and mixing.
1.7 solid phase extraction column: 2.0g of 10mL silica gel column, which was verified using other specifications.
1.8 anhydrous sodium sulfate: (Na)2SO4) Baking at 400 deg.C for 4h, and storing in glass bottle.
Instrument and equipment
2.1 gas chromatography-Mass spectrometer (GC-MSD)
2.2 chromatographic column: DB-5MS, 30m, liquid film thickness of 0.25 μm, inner diameter of 0.25mm, and other chromatographic columns with similar performance can also be used.
2.3 concentration device: an automatic nitrogen-blowing concentrator, or a device with equivalent performance.
2.4 temperature-controllable rotary evaporator.
2.5 temperature-controllable constant-temperature water bath device.
2.6 general equipment for other laboratories.
Third, analysis step
3.1 treatment of the samples
3.1.1 extraction
An appropriate amount of the atmospheric sediment sample was mixed with 10.0g of anhydrous sodium sulfate, and an appropriate amount of the surrogate was added, which was placed in an extraction cannula. Using 100mL of n-hexane: extracting with acetone (v: v ═ 1: 1) extractive solution for 12 h. After the extract was cooled, it was transferred to a 500mL separatory funnel, and an appropriate amount of 2% sodium sulfate solution was added to wash off the acetone. Dehydrating, concentrating to about 1mL by rotary evaporation, and purifying.
3.1.3 purification
3.1.3.1 activation of solid phase extraction column: the upper end of the solid phase extraction column was filled with about 0.5cm of anhydrous sodium sulfate, the column was rinsed with 15mL of dichloromethane and 10mL of n-hexane in sequence, and the piston was closed when the anhydrous sodium sulfate was about to emerge.
This step did not allow exposure of the anhydrous sodium sulfate to air during the procedure, and if this occurred, the column needed to be re-conditioned.
3.1.3.2 transfer and clarification of samples
Transferring the concentrated sample to a solid phase extraction column without damage, completing the transfer of all compounds by using another 1mL of n-hexane, keeping for 5min after the transfer is completed, opening a piston, discarding the part of effluent liquid, and closing the piston when anhydrous sodium sulfate is about to be exposed.
3.1.3.3 elution of the sample
The solid phase extraction column was eluted several times with 20mL of eluent (1.6) and the effluent was loaded with 10mL nitrogen sparge tubes several times.
3.1.3.4 concentrating to constant volume
Blowing nitrogen at 40 deg.C to concentrate 3.1.3.3 effluent to slightly less than 500.00 μ L, metering volume to 500.00 μ L with micro syringe, adding internal standard 10.0 μ L, shaking, and measuring on machine.
3.2 chromatographic conditions
3.2.1 injection port temperature: 280 ℃; the sample is injected without shunting, and the sample injection amount is 2 mu L; the sample inlet pressure was 9.95psi, the purge flow was 11.0mL/min, and the purge time was 2 min.
3.2.2 chromatographic column flow 1.1mL/min, flow rate 39 cm/sec.
3.2.3 temperature program: keeping at 70 deg.C for 4min, heating to 300 deg.C at a rate of 10 deg.C/min, keeping for 2min, and heating to 340 deg.C at a rate of 5 deg.C/min until all components flow out.
3.2.4 interface temperature: 285 deg.C.
3.3 Mass Spectrometry conditions
3.3.1 tuning mode: DFTTP
3.3.2 scanning mode: full scan, scan range 50-450 amu.
3.3.3 ion source temperature: 230 ℃; the quadrupole rod temperature was 150 ℃.
3.3.4 ionization energy: 70 ev.
3.4 drawing of Standard Curve
3.4.1 preparation of calibration series
And (3) sucking a proper amount of standard stock solution and internal standard stock solution, metering the volume to 10mL by using normal hexane, preparing calibration points with the concentration of the polycyclic aromatic hydrocarbon compound of 1000, 400, 200, 100, 50 and 20ng/mL, and setting the internal standard concentration of each calibration point to 400 ng/mL.
3.4.2 initial calibration Curve
And (3) performing data acquisition according to a set data acquisition method, and drawing a calibration curve by using the concentration of the internal standard/target compound as an abscissa and the response of the internal standard/target ion as an ordinate by using the internal standard method, wherein the correlation coefficient of the curve is more than 0.995, the Relative Standard Deviation (RSD) of response factors of the compounds is not more than 30%, otherwise, drawing the calibration curve again.
Preferably, an internal polycyclic aromatic hydrocarbon is used as shown in Table 2. The compound quantification and ion limitation are shown in Table 3.
TABLE 2 internal standards for polycyclic aromatic hydrocarbons
TABLE 3 quantification of Compounds, limiting ions
3.4.3 Total ion flowsheet of Standard sample as shown in FIG. 1
And (3) peak appearance sequence: 1) D8-NA-9.473) D10-AC-13.8812) D10-PHE-17.4016) D12-CHR-23.7521) D12-PYL-26.922) NA-9.514) ACL-13.505) AC-13.966) FL-15.187) Bghip-29.968) IP-29.339) DBahA-29.4110) BbFA-26.5511) 4-Br-2F-15.6913) PHE-17.4614) AN-17.5615) FA-20.3117) BaA-23.7218) CHR-23.8119) PY-20.8222) BaP-26.8020) Ter-D14-21.3623) BkFA-26.20.
3.5 determination of the samples
3.5.1 calibration of Mass Spectrometry
After the start-up is stable for 2 hours, the mass spectrometer is tuned according to the TFAPP mode, 2 mu L of decafluorotriphenyl phosphine is injected according to a set method, and the ion abundance of the decafluorotriphenyl phosphine can meet the requirements of the table 4.
TABLE 4 DFTPP Key ion and ion abundance index
| Mass number | Ion abundance index | Mass number | Ion abundance index |
| 51 | 198 the mass number of the powder is 30-60% | 199 | 198 the mass number of which is 5 to 9 percent |
| 68 | Less than 2% of 69 mass number | 275 | 198 the mass number of which is 10 to 30 percent |
| 70 | Less than 2% of 69 mass number | 365 | More than 1 percent of the mass number of 198 |
| 127 | 198 the mass number of which is 40 to 60 percent | 441 | Abundance of present, but less than 443 mass numbers |
| 197 | Less than 1% of the mass number of 198 | 442 | More than 40 percent of the mass number of 198 |
| 198 | Basic peak, relative abundance 100% | 443 | 17 to 23 percent of 442 mass number |
3.5.2 analyzing at least 5 calibration points according to the set method to draw a working curve (3.4.2).
3.5.3 sample analysis: the treated sample was analyzed under the same instrument conditions as the calibration curve (3.1.3.4).
3.6 blank experiment
A blank test should be run to check for contamination during the analysis for each batch.
Fourthly, data processing and result calculation
Calculating the concentration of the compound in the extracting solution: the ions were extracted and the peak areas integrated as in table 3, and the compound content was calculated as follows.
Q＝C*V/n
In the formula: q-sample content, ng/g.
C-concentration of the extract calculated from the calibration curve, ng/mL.
V-volume of extract tested, mL.
n-sample size, g.
Fifthly, quality control and quality guarantee
5.1 blank: all blank test results should be below the method detection limit
5.2 reagent blank: analysis of at least one blank per reagent batch
5.3 blank test: analyzing at least one blank per batch of samples
5.4 control range of standard recovery rate: 60 to 130 percent.
5.5 the relative error of the continuous calibration does not exceed 20%.
5.6 DFTPP validation frequency: once in 15 working days.
5.7 repeat analysis
The number of repeated analysis samples is not less than 5%, the qualification rate of analysis items is more than 94%, and when the repeated measurement does not meet the requirement, the sampling proportion is enlarged until the requirement is met.
The points to be finally explained are: first, in the description of the present application, it should be noted that, unless otherwise specified and limited, the terms "mounted," "connected," and "connected" should be understood broadly, and may be a mechanical connection or an electrical connection, or a communication between two elements, and may be a direct connection, and "upper," "lower," "left," and "right" are only used to indicate a relative positional relationship, and when the absolute position of the object to be described is changed, the relative positional relationship may be changed;
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 are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
Claims (8)
1. A method for determining polycyclic aromatic hydrocarbons in atmospheric dry and wet sediments by GC-MS is characterized by comprising the following steps: performing Soxhlet extraction or accelerated solvent extraction on an atmospheric sediment sample, drying, concentrating and purifying silica gel on an extract, performing full-scan detection on a sample concentrated solution by using gas chromatography-mass spectrometry (GC-MS), and then performing qualitative determination by using a mass spectrogram and retention time of a target component and a mass spectrogram and retention time in a computer library as references, wherein the concentration of each determined component depends on the mass spectrum response ratio of a quantitative ion and an internal standard substance quantitative ion; finally, an internal standard compound with known concentration is added into each sample, and the quantitative analysis is carried out by an internal standard method.
2. The method for determining polycyclic aromatic hydrocarbons in atmospheric dry and wet sediments by GC-MS as claimed in claim 1, wherein: the extraction method comprises the following steps: mixing a proper amount of atmospheric sediment sample and 10.0g of anhydrous sodium sulfate, adding a proper amount of substitute, and placing the mixture into an extraction sleeve; using 100mL of n-hexane: extracting with acetone (v: v ═ 1: 1) for 12 h; after the extract was cooled, it was transferred to a 500mL separatory funnel, and an appropriate amount of 2% sodium sulfate solution was added to wash off the acetone. Dehydrating, concentrating to about 1mL by rotary evaporation, and purifying.
3. The method for determining polycyclic aromatic hydrocarbons in atmospheric dry and wet sediments by GC-MS as claimed in claim 1, wherein: the purification method comprises the following steps:
a. activation of solid phase extraction column
Filling 0.5cm of anhydrous sodium sulfate at the upper end of the solid phase extraction column, leaching the small column with 15mL of dichloromethane and 10mL of n-hexane in sequence, and closing the piston when the anhydrous sodium sulfate is about to be exposed; the anhydrous sodium sulfate can not be exposed in the air during the operation of the step, and the small column needs to be conditioned again if the situation occurs;
b. sample transfer and decontamination
Transferring the concentrated sample to a solid phase extraction column without damage, finishing the transfer of all compounds by using another 1mL of n-hexane, keeping for 5min after the transfer is finished, opening a piston, discarding the part of effluent liquid, and closing the piston when anhydrous sodium sulfate is about to be exposed;
c. elution of the sample
Eluting the solid phase extraction column with 20mL of eluent (1.6) for several times, and filling the eluent with 10mL of nitrogen blowing tubes for several times;
d. concentrating to constant volume
Blowing nitrogen at 40 deg.C to concentrate 3.1.3.3 effluent to slightly less than 500.00 μ L, metering volume to 500.00 μ L with micro syringe, adding internal standard 10.0 μ L, shaking, and measuring on machine.
4. The method for determining polycyclic aromatic hydrocarbons in atmospheric dry and wet sediments by GC-MS as claimed in claim 1, wherein: the chromatographic conditions are as follows:
sample inlet temperature: 280 ℃; the sample is injected without shunting, and the sample injection amount is 2 mu L; the pressure of a sample inlet is 9.95psi, the purging flow is 11.0mL/min, and the purging time is 2 min; the flow rate of the chromatographic column is 1.1mL/min, and the flow rate is 39 cm/sec; temperature rising procedure: keeping at 70 deg.C for 4min, heating to 300 deg.C at a rate of 10 deg.C/min, keeping for 2min, heating to 340 deg.C at a rate of 5 deg.C/min, and keeping until all components flow out; interface temperature: 285 deg.C.
5. The method for determining polycyclic aromatic hydrocarbons in atmospheric dry and wet sediments by GC-MS as claimed in claim 1, wherein: the mass spectrum conditions are as follows:
the tuning mode is as follows: DFTTP; the scanning mode is as follows: full scanning, wherein the scanning range is 50-450 amu; ion source temperature: 230 ℃; the temperature of the quadrupole rods is 150 ℃; ionization energy: 70 ev.
6. The method for determining polycyclic aromatic hydrocarbons in atmospheric dry and wet sediments by GC-MS as claimed in claim 1, wherein: the method also comprises the following steps of drawing a standard curve:
a. preparation of the calibration series: sucking a proper amount of standard stock solution and internal standard stock solution, fixing the volume to 10mL by using normal hexane, preparing calibration points with the concentration of the polycyclic aromatic hydrocarbon compound of 1000, 400, 200, 100, 50 and 20ng/mL, wherein the internal standard concentration of each calibration point is 400 ng/mL;
b. initial calibration curve: performing data acquisition according to a set data acquisition method, and drawing a calibration curve by using the concentration of an internal standard/target compound as an abscissa and the response of an internal standard/target ion as an ordinate by using the internal standard method, wherein the correlation coefficient of the curve is more than 0.995, the Relative Standard Deviation (RSD) of response factors of each compound is not more than 30%, otherwise, drawing the calibration curve again;
c. drawing total ion flow diagram of standard sample
The mass spectrum calibration method comprises the following steps: after the starting is stable for 2 hours, tuning a mass spectrometer according to a TFAPP mode, and injecting 2 mu L of decafluorotriphenyl phosphine according to a set method; analyzing at least 5 calibration points according to a set method to draw a working curve; and (3) sample analysis: analyzing the processed sample under the same instrument condition according to the calibration curve; blank experiment: a blank test should be run to check for contamination during the analysis for each batch.
7. The method for determining polycyclic aromatic hydrocarbons in atmospheric dry and wet sediments by GC-MS as claimed in claim 1, wherein: the method for calculating the concentration of the compound in the extracting solution comprises the following steps: ions were extracted and the peak areas integrated and the compound content was calculated according to the formula Q ═ C × V/n, where: q-sample content, ng/g; c-concentration of the extracting solution calculated by the calibration curve, ng/mL; v-volume of test extract, mL; n-sample size, g.
8. The method for determining polycyclic aromatic hydrocarbons in atmospheric dry and wet sediments by GC-MS as claimed in claim 1, wherein: further comprising a repeat analysis: the number of repeated analysis samples is not less than 5%, the qualification rate of analysis items is more than 94%, and when the repeated measurement does not meet the requirement, the sampling proportion is enlarged until the requirement is met.
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