CN114019059A - Method for simultaneously determining 50 semi-volatile organic compounds in soil through GC-MS (gas chromatography-Mass spectrometer) - Google Patents
Method for simultaneously determining 50 semi-volatile organic compounds in soil through GC-MS (gas chromatography-Mass spectrometer) Download PDFInfo
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- G—PHYSICS
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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
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- G—PHYSICS
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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
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
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- G—PHYSICS
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- G01N30/02—Column chromatography
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Abstract
The invention belongs to the technical field of detection of semi-volatile organic compounds, and discloses a method for simultaneously determining 50 semi-volatile organic compounds in soil by GC-MS. The method comprises the following steps: (1) taking a soil sample, dehydrating and grinding diatomite, adding a dichloromethane solvent, then performing ultrasonic extraction, and dehydrating through anhydrous sodium sulfate to obtain an extracting solution; extracting repeatedly for 1 time; (2) blowing and concentrating the extracted liquid nitrogen obtained in the step (1) to obtain a concentrated solution; (3) and (3) selecting a plastic magnesium silicate column as a solid phase extraction column, using a normal hexane/dichloromethane mixed solvent with the volume ratio of 1:9 as an eluent, purifying the concentrated solution obtained in the step (2), and carrying out detection and analysis on the obtained eluent through a gas chromatography-mass spectrometry combined system after nitrogen blowing concentration. The method simultaneously measures 50 semi-volatile organic compounds in the soil, solves the problems existing in the prior art, reduces the use of reagents, reduces the labor input and greatly improves the detection efficiency.
Description
Technical Field
The invention belongs to the technical field of detection of semi-volatile organic compounds, and particularly relates to a method for simultaneously determining 50 semi-volatile organic compounds in soil by GC-MS.
Background
The semi-volatile organic pollutants (SVOCs) are organic matters with boiling points of 170-350 ℃ and steam pressures of 13.3-10 < -5 > Pa. Mainly comprises dioxins, polycyclic aromatic hydrocarbons, organic pesticides, chlorobenzene, polychlorinated biphenyl, pyridine, quinoline, nitrobenzene, phthalate, nitrosoamine, aniline, phenol, polychlorinated naphthalene, polybrominated biphenyl and other compounds. Some semi-volatile organic compounds, such as benzo (a) pyrene, nitrobenzene, etc., have reproductive toxicity, mutagenic, teratogenic, carcinogenic effects.
China has few measurement items aiming at semi-volatile organic compounds, and the measurement of the semi-volatile organic compounds of different classes in soil has the following standards: most of semi-volatile organic compounds are determined without independent standards in gas chromatography for determination of phenolic compounds in HJ 703-2014 soil and sediments, gas chromatography mass spectrometry for determination of polychlorinated biphenyl in HJ 743-2015 soil and sediments, and gas chromatography mass spectrometry for determination of polycyclic aromatic hydrocarbons in HJ 805-2016 soil and sediments, and samples are not required to be respectively pretreated, so that the cost of manpower and material resources is greatly increased. The standard belongs to gas chromatography-mass spectrometry for measuring semi-volatile organic compounds of HJ834-2017 soil and sediment, relates to a measuring method with complete types and comprising 64 SVOCs, but has different purification modes for different types of semi-volatile organic compounds, and the purification mode comprising 5 types is complicated, so that the method is not beneficial to processing samples in large batch. The method is suitable for testing various (50) semi-volatile organic compounds in soil in a laboratory, reduces the purification times and reagent use by using the existing instruments and equipment, improves the analysis efficiency, and has important significance for guiding the semi-volatile organic compounds in the soil.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the invention provides a method for simultaneously determining 50 semi-volatile organic compounds in soil by GC-MS.
The purpose of the invention is realized by the following scheme:
a method for simultaneously determining 50 semi-volatile organic compounds in soil by GC-MS, comprising the steps of:
(1) taking a soil sample, dehydrating and grinding the soil sample by using diatomite, adding a dichloromethane solvent, then carrying out ultrasonic extraction to obtain an extracting solution A, and dehydrating the extracting solution A by using anhydrous sodium sulfate to obtain an extracting solution B; repeating the above steps, and mixing the obtained extractive solutions;
(2) blowing and concentrating the extracted liquid nitrogen obtained in the step (1) to obtain a concentrated solution;
(3) and (3) selecting a plastic magnesium silicate column as a solid phase extraction column, using a normal hexane/dichloromethane mixed solvent with a volume ratio of 1:9 as an eluent, purifying the concentrated solution obtained in the step (2), carrying out nitrogen blowing concentration on the obtained eluent, and then carrying out detection analysis through a gas chromatography-mass spectrometry combined system.
Preferably, the mass volume of the soil sample and the dichloromethane solvent in the step (1) is 15-25 g: 50mL, preferably 20 g: 50 mL.
Preferably, the ultrasonic frequency in the ultrasonic extraction in the step (1) is 20KHZ, and the intensity is 500W-1800W, more preferably 1080W; the liquid temperature does not exceed 35 ℃; the ultrasonic time is 3-8 min, preferably 3 min.
Preferably, the number of times of repeating the above steps in the step (1) is 1 to 3.
Preferably, the nitrogen pressure is 0.4-0.8 psi when the nitrogen is blown and concentrated in the step (2); more preferably 0.5psi, and the bath temperature is 35 ℃.
Preferably, the gas chromatography conditions in step (3) are: sample inlet temperature: 280 ℃; and (3) sample introduction mode: no shunt sampling; temperature programming: 35 ℃ (2min) → 15 ℃/min → 150 ℃ (5min) → 10 ℃/min → 300 ℃ (5 min); flow rate: 1.0 ml/min;
the mass spectrum conditions are as follows: an ion source: an EI source; ion source temperature: 230 ℃; ionization energy: 70eV, scanning range: m/z 35-500 u; solvent delay 3.0 min; electron multiplication voltage: consistent with the tuning voltage; interface temperature: 280 ℃.
The 50 semi-volatile organic compounds are as follows: n-nitrosodimethylamine, bis (2-chloroethyl) ether, 1, 3-dichlorobenzene, 1, 4-dichlorobenzene, 1, 2-dichlorobenzene, bis (2-chloroisopropyl) ether, hexachloroethane, N-nitrosodi-N-propylamine, nitrobenzene, isophorone, bis (2-chloroethoxy) methane, 1,2, 4-trichlorobenzene, naphthalene, 4-chloroaniline, hexachlorobutadiene, 2-methylnaphthalene, hexachlorocyclopentadiene, 2-chloronaphthalene, 2-nitroaniline, dimethyl phthalate, acenaphthylene, 2, 6-dinitrotoluene, acenaphthylene, 3-nitroaniline, dibenzofuran, 2, 4-dinitrotoluene, fluorene, 4-chlorophenyl phenyl ether, diethyl phthalate, 4-nitroaniline, azobenzene, 4-bromodiphenyl ether, Hexachlorobenzene, phenanthrene, anthracene, carbazole, di-n-butyl phthalate, fluoranthene, pyrene, dibutyl benzyl phthalate, benzo (a) anthracene,
Di (2-diethylhexyl) phthalate, di-n-octyl phthalate, benzo (b) fluoranthene, benzo (k) fluoranthene, benzo (a) pyrene, indeno (1,2,3-cd) pyrene, dibenzo (ah) anthracene, benzo (ghi) perylene.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention simultaneously measures 50 semi-volatile organic compounds such as isophorone, phthalate, nitrosamines, nitroaromatics, polycyclic aromatics, chlorohydrocarbons and the like in soil by GC-MS, and determines the measuring method by ultrasonic extraction, nitrogen blowing concentration, plastic magnesium silicate small column purification, normal hexane + dichloromethane (1+9) leaching and gas chromatography-mass spectrometry. The problem of prior art standard existence is solved, reagent use is reduced, the human input is reduced, has improved detection efficiency greatly.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference. Gas chromatography-mass spectrometer: having an Electron Impact (EI) ionization source; an ultrasonic processor: SXSONIC, FS-1800N; pressurized fluid extraction apparatus: thermo, ASE-350; nitrogen-blown concentrator: ANPEL, DC-24; plastic magnesium silicate purification Column (CNW): 1g/6 ml; glass magnesium silicate purifying column: 2g/6 ml; silica gel purifying column: 1g/6 ml; a chromatographic column: quartz capillary column, HP-5ms, 30 m.times.250. mu.m.times.0.25. mu.m. Semi-volatile organic standard solution intermediate: rho is 100 mg/L; internal standard stock solution: rho 1000mg/L, commercially available standard solution, 1, 4-dichlorobenzene-d 4, naphthalene-d 8, acenaphthene-d 10, phenanthrene-d 10,
-d12, perylene-d 12; internal standard intermediate solution: rho is 100 mg/L; substitute stock solution: ρ 1000mg/L, commercially available standard solution, phenol-d 6, 2-fluorophenol, 2,4, 6-tribromophenol, nitrobenzene-d 5, 2-fluorobiphenyl, 4' 4-terphenyl-d 4; substitute intermediate liquid: rho is 100 mg/L.
Standard curve
Preparing a standard curve by using the intermediate solution of the semi-volatile organic matter standard solution, wherein 6 concentration points are respectively 0.5mg/L, 1.0mg/L, 2.0mg/L, 5.0mg/L, 10mg/L and 20mg/L, and performing on-machine analysis on the 6 concentration points according to the above instrument conditions to obtain the standard curve, wherein the related series of each substance curve can reach more than 0.995, and the table 1 shows.
TABLE 1 Linear regression equation, correlation coefficient
Example 1
(1) Taking 20g of quartz sand, dehydrating and grinding the quartz sand, accurately transferring 50 mu L of semi-volatile organic matter standard solution with the concentration of 100mg/L and 50 mu L of substitute intermediate solution into the quartz sand by using a liquid transfer gun. About 50ml of methylene chloride solvent was added to the beaker containing the sample to ensure that the surface of the solvent was about 2cm above the surface of the solid sample, and the probe of the ultrasonic extractor was inserted 1cm below the surface of the solid sample, but above the surface of the solid sample (the amount of solvent added may be increased or decreased as appropriate depending on the volume of the sample). The ultrasonic frequency of the ultrasonic processor is 20KHZ, the maximum intensity is 1800W, the intensity of the ultrasonic processor is adjusted to 60%, the maximum temperature of liquid is set to be not more than 35 ℃, ice blocks are used for cooling in a water bath, the depth of a probe is adjusted, the sample can be completely turned when being extracted, and the ultrasonic extraction is carried out for 3 min. Adding appropriate amount of anhydrous sodium sulfate into funnel, and drying and filtering the extractive solution via funnel. Extracting for 1 time, mixing the extractive solutions for 2 times, and concentrating.
(2) And (2) carrying out blowing concentration on the extracted liquid nitrogen obtained in the step (1), wherein the concentration instrument condition is as follows: nitrogen pressure 0.5psi, water bath temperature 35 ℃; obtaining 1mL of concentrated solution;
(3) and (3) selecting a plastic magnesium silicate column as a solid phase extraction column, using normal hexane/dichloromethane with the volume ratio of 1:9 as eluent, purifying the concentrated solution obtained in the step (2), then carrying out nitrogen blowing concentration on the obtained eluent (the conditions are as in the step (2)) to 1mL, and then carrying out detection analysis through a gas chromatography-mass spectrometry combined system.
Method detection limit
Weighing 20g of blank soil sample, adding 50 semi-volatile organic standard solutions, preparing 8 parts of soil sample with the concentration of 0.25mg/kg, pretreating and analyzing according to an experimental method, and quantifying by adopting an internal standard method. And the method detection limit was calculated according to the formula MDL ═ sxt (n-1, 0.99). The results are shown in Table 2
Method precision and recovery test
Weighing 20g of actual soil sample, respectively adding the actual soil sample into the target mixed standard solution to perform a standard addition experiment, wherein the standard addition levels are 0.25mg/kg, 0.5mg/kg and 1mg/kg respectively, extracting, concentrating, purifying and analyzing according to the experiment method, performing parallel determination on each concentration level for 3 times, quantifying by adopting an internal standard method, and calculating the average recovery rate and the relative standard deviation. The results are shown in Table 2
A blank sample (20 g) was weighed and subjected to blank test.
TABLE 2 method precision, accuracy and detection limits
Example 2 Effect of concentration mode
Preparing 60ml of target solution with a certain concentration, respectively concentrating by nitrogen blowing, rotary evaporation and 3 modes of firstly rotary evaporation and then nitrogen blowing, and then testing on a machine.
(1) Taking 60ml of dichloromethane solvent into a test tube, accurately transferring 100 mu L of semi-volatile organic matter standard solution with the concentration of 100mg/L and 100 mu L of substitute intermediate solution into the test tube by using a liquid transfer gun, uniformly mixing, preparing sample solution with the content of 10 mu g, and preparing 6 samples in parallel;
(2) the concentration test is carried out by a rotary evaporator in the 1 st group, and the concentration test is carried out by a rotary evaporator in the 3 rd group, wherein the concentration test is carried out by a mode of firstly carrying out rotary evaporation to 20ml and then carrying out nitrogen blowing.
(3) And (3) concentrating the above 3 groups of samples, adding the internal standard intermediate solution, fixing the volume to 1ml, transferring to a 2ml sample bottle, and detecting. The results of target recovery are shown in table 3.
TABLE 3 mean recoveries and relative standard deviations of different sample concentration modes
Group 1 in the table: nitrogen blowing and concentrating; group 2: rotary evaporation and concentration; group 3: rotary evaporation concentration is carried out firstly, and then nitrogen blowing concentration is carried out.
The data result shows that the recovery rate of the rotary evaporation concentration mode is lower than that of the nitrogen blowing concentration mode and the rotary evaporation and nitrogen blowing concentration mode, the recovery rates of the nitrogen blowing concentration mode and the rotary evaporation and nitrogen blowing concentration mode are not different, but the parallel repeatability of the nitrogen blowing concentration mode is better, and the relative standard deviation is between 1.5% and 10.0%, so that the concentration mode finally selects the nitrogen blowing concentration mode, and the concentration instrument condition is as follows: nitrogen pressure was 0.5psi and bath temperature was 35 ℃.
Example 3 Effect of extraction mode
Selecting a blank labeling mode, respectively extracting by using an ultrasonic extraction mode and a pressurized fluid extraction mode, and finally performing concentration on-machine test according to an optimized concentration mode.
(1) Ultrasonic extraction: weighing 20g of quartz sand, placing the quartz sand in a 250ml beaker, transferring 50 μ L of a semi-volatile organic standard solution with the concentration of 100mg/L and 50 μ L of a substitute intermediate solution, adding the quartz sand, adding about 50ml of dichloromethane solvent into the beaker with the sample, ensuring that the liquid level of the added solvent is about 2cm higher than the surface of the solid sample, and inserting an ultrasonic extractor probe into the position 1cm below the liquid level but above the surface of the solid sample (the adding amount of the solvent can be increased or reduced properly according to the volume of the sample). The maximum intensity of the ultrasonic processor is 1800W, the intensity of the ultrasonic processor is adjusted to 60%, the maximum temperature of liquid is set to be not more than 35 ℃, ice blocks are used for cooling in a water bath, the depth of a probe is adjusted, the sample can be completely turned over during extraction, and ultrasonic extraction is carried out for 3 min. Adding appropriate amount of anhydrous sodium sulfate into funnel, and drying and filtering the extractive solution via funnel. Extracting for 1 time, mixing the extractive solutions for 2 times, and concentrating; 2 samples were prepared in parallel using the same procedure. The results of target recovery are shown in table 4.
(2) ASE extraction: weighing 20g of quartz sand, placing the quartz sand in a 22ml ASE extraction pool, transferring 50 mu L of semi-volatile organic matter standard solution with the concentration of 100mg/L and 50 mu L of substitute intermediate solution into the quartz sand, covering and screwing down, and then extracting; the extraction conditions were:
carrier gas pressure: 0.8 MPa; heating temperature: 100 ℃; pressure of the extraction tank: 1200 and 2000 psi; preheating and balancing: 5 min; static extraction time: 5 min; the leaching volume of the solvent is as follows: 100% of the cell volume; nitrogen purging time: 60S; the number of static extraction times is as follows: 1 time. After extraction, adding a proper amount of anhydrous sodium sulfate into a funnel, drying and filtering an extracting solution through a funnel, and concentrating; 2 samples were prepared in parallel using the same procedure. The results of target recovery are shown in table 4.
TABLE 4 mean recovery and relative standard deviation of the different instrument extractions
The data result shows that compared with the ultrasonic extraction mode, the ASE extraction mode has low recovery rate, high instrument material cost and long extraction time, the ASE extraction recovery rate is 31.5 percent at the lowest, the ultrasonic extraction recovery rate can reach 69.3 percent at the lowest, and the relative standard deviation is 0-26.7 percent, so the ultrasonic extraction mode is selected finally.
Example 4 Effect of extraction conditions
(1) Ultrasonic extraction 1: weighing 20g of quartz sand, placing the quartz sand in a 250ml beaker, accurately transferring 50 mul of semi-volatile organic standard solution with the concentration of 100mg/L and 50 mul of substitute intermediate solution to the quartz sand, adding about 50ml of dichloromethane solvent into the beaker with the sample, ensuring that the liquid level of the added solvent is about 2cm higher than the surface of the solid sample, and inserting an ultrasonic extractor probe into the position 1cm below the liquid level, but the probe is required to be above the surface of the solid sample (the adding amount of the solvent can be properly increased or reduced according to the volume of the sample). The maximum intensity of the ultrasonic processor is 1800W, the intensity of the ultrasonic processor is adjusted to 60%, the maximum temperature of liquid is set to be not more than 35 ℃, ice blocks are used for cooling in a water bath, the depth of a probe is adjusted, the sample can be completely turned over during extraction, and ultrasonic extraction is carried out for 3 min. Adding appropriate amount of anhydrous sodium sulfate into funnel, and drying and filtering the extractive solution via funnel. Extracting for 1 time, mixing the extractive solutions for 2 times, and concentrating; 2 samples were prepared in parallel using the same procedure. The results of target recovery are shown in table 5.
(2) Ultrasonic extraction 2: the difference from the ultrasonic extraction 1 is that the adding amount of the solvent is changed to 60ml, the ultrasonic extraction time is 5min, the extraction times are changed to 1 time, and the rest steps are the same as the ultrasonic extraction 1. The results of target recovery are shown in table 5.
TABLE 5 mean recovery and relative standard deviation for different extraction conditions
Condition 1 in table: ultrasonic extracting 50ml dichloromethane solvent for 3min, repeating extracting for 1 time, mixing 2 times extractive solutions; condition 2: extracting with 60ml dichloromethane solvent under ultrasound for 5min for 1 time.
The data result shows that the recovery rate of the sample measured under the ultrasonic condition 1(50ml of dichloromethane solvent, ultrasonic extraction for 3min, repeated extraction for 1 time, and combination of 2 extraction solutions) is higher than that measured under the ultrasonic condition 2(60ml of dichloromethane solvent, ultrasonic extraction for 5min, and extraction for 1 time), the recovery rate under the condition 1 is 69.3% at the lowest, and the recovery rate under the condition 2 is 40.8% at the lowest, so that the condition 1(50ml of dichloromethane solvent, the maximum strength of an ultrasonic processor is 1800W, the strength of the ultrasonic processor is adjusted to 60%, the highest liquid temperature is set to be not more than 35 ℃, an ice water bath is used for cooling, the ultrasonic extraction is performed for 3min, the repeated extraction is performed for 1 time, and the extraction solutions are combined for 2 times).
EXAMPLE 5 Effect of solid phase extraction column
(1) 50 mu L of semi-volatile organic matter standard solution with the concentration of 100mg/L is accurately transferred into a sample bottle which is added with 950 mu L of dichloromethane solvent in advance by using a liquid transfer gun, 6 standard samples are prepared in parallel and divided into 3 groups, each group comprises 3 samples, and each group is respectively subjected to column passing tests by using a plastic magnesium silicate column, a silica gel column and a glass magnesium silicate column.
(2) Activating different small columns by using 6ml of (normal hexane + dichloromethane (1+1)), then leaching by using 30ml of (normal hexane + dichloromethane (1+9)), collecting leacheate, concentrating the leacheate, adding internal standard intermediate solution, fixing the volume to 1ml, transferring to a 2ml sample bottle for detection. The results of target recovery are shown in Table 6.
TABLE 6 average recovery and relative standard deviation for different columns
Column 1 in table: plastic magnesium silicate purifying columns; column 2: a glass magnesium silicate purifying column; column 3: and (5) purifying the silica gel column.
The data result shows that the minimum recovery rate of the other 49 semi-volatile organic compounds can reach 43.4 percent after being purified by a plastic magnesium silicate column except that hexachlorocyclopentadiene is easy to generate thermal decomposition at a chromatographic sample inlet and the recovery rate is unstable, and the minimum recovery rate is higher than that of a glass magnesium silicate column and a silica gel column, so the purification column is selected from the plastic magnesium silicate column.
Example 6; effect of leacheate
50 mu L of semi-volatile organic standard solution with the concentration of 100mg/L is accurately transferred to a sample bottle in which 950 mu L of dichloromethane solvent is added in advance, 6 standard samples are prepared in parallel and divided into 3 groups, and each group comprises 3 samples, and a purification elution test is carried out by using a silica gel column. The column was first activated with 6ml (n-hexane + dichloromethane (1+1)) and then tested with the following 3 elution sequences:
(1) transferring the prepared standard solution to a small column, and rinsing the standard solution container with a rinsing solution respectively before each stage of rinsing. Leaching with 10ml of n-hexane, leaching with 10ml of (dichloromethane + petroleum ether (5+95)), and leaching with 10ml of dichloromethane; the results of target recovery are shown in Table 7.
(2) Transferring the prepared standard solution to a small column, and rinsing the standard solution container with a rinsing solution respectively before each stage of rinsing. Then, 30ml (n-hexane + dichloromethane (1+9)) is used for leaching; the results of target recovery are shown in Table 7.
(3) Transferring the prepared standard solution to a small column, and rinsing the standard solution container with a rinsing solution respectively before each stage of rinsing. Leaching with 10ml of n-hexane, and leaching with 20ml of petroleum ether and dichloromethane (1+ 9)); the results of target recovery are shown in Table 7.
TABLE 7 average recovery and relative standard deviation of different leachates
Leacheate 1 in table: 10ml of n-hexane-10 ml (dichloromethane + petroleum ether (5+95)) -10ml of dichloromethane; eluent 2: 30ml (n-hexane + dichloromethane (1+ 9)); eluent 3: 10ml of n-hexane to 20ml (petroleum ether + dichloromethane (1+ 9)).
The above data results show that the elution rate through eluent 1: the recovery rate of the sample after being washed by 10ml of normal hexane-10 ml (dichloromethane + petroleum ether (5+95)) -10ml of dichloromethane is 44.5 percent at the lowest; passing through an eluent 2: the recovery rate of a sample after 30ml (n-hexane + dichloromethane (1+9)) of washing is 64.2 percent at the lowest; passing through eluent 3: the minimum recovery of the sample after washing with 10ml n-hexane to 20ml (petroleum ether + dichloromethane (1+9)) was 44.1%. Eluent 2: recovery was higher for 30ml (n-hexane + dichloromethane (1+9)), so the purge rinse was selected as rinse 2: 30ml (n-hexane + dichloromethane (1+ 9)).
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. A method for simultaneously determining 50 semi-volatile organic compounds in soil by GC-MS is characterized by comprising the following steps:
(1) taking a soil sample, dehydrating and grinding diatomite, adding a dichloromethane solvent, then carrying out ultrasonic extraction to obtain an extracting solution A, and dehydrating through sodium sulfate to obtain an extracting solution B; repeating the above steps, and mixing the obtained extractive solutions;
(2) blowing and concentrating the extracted liquid nitrogen obtained in the step (1) to obtain a concentrated solution;
(3) selecting a plastic magnesium silicate column as a solid phase extraction column, using a mixed solvent of n-hexane and dichloromethane with a volume ratio of 1:9 as an eluent, purifying the concentrated solution obtained in the step (2), carrying out nitrogen blowing concentration on the obtained eluent, and carrying out detection analysis through a gas chromatography-mass spectrometry system;
the 50 semi-volatile organic compounds are: n-nitrosodimethylamine, bis (2-chloroethyl) ether, 1, 3-dichlorobenzene, 1, 4-dichlorobenzene, 1, 2-dichlorobenzene, bis (2-chloroisopropyl) ether, hexachloroethane, N-nitrosodi-N-propylamine, nitrobenzene, isophorone, bis (2-chloroethoxy) methane, 1,2, 4-trichlorobenzene, naphthalene, 4-chloroaniline, hexachlorobutadiene, 2-methylnaphthalene, hexachlorocyclopentadiene, 2-chloronaphthalene, 2-nitroaniline, dimethyl phthalate, acenaphthylene, 2, 6-dinitrotoluene, acenaphthylene, 3-nitroaniline, dibenzofuran, 2, 4-dinitrotoluene, fluorene, 4-chlorophenyl phenyl ether, diethyl phthalate, 4-nitroaniline, azobenzene, 4-bromodiphenyl ether, Hexachlorobenzene, phenanthrene, anthracene, carbazole, di-n-butyl phthalate, fluoranthene, pyrene, dibutyl benzyl phthalate, benzo (a) anthracene,
Di (2-diethylhexyl) phthalate, di-n-octyl phthalate, benzo (b) fluoranthene, benzo (k) fluoranthene, benzo (a) pyrene, indeno (1,2,3-cd) pyrene, dibenzo (ah) anthracene, benzo (ghi) perylene.
2. The method of claim 1, wherein: the mass volume of the soil sample and the dichloromethane solvent in the step (1) is 15-25 g: 50 mL.
3. The method of claim 1, wherein: the mass volume of the soil sample and the dichloromethane solvent in the step (1) is 20 g: 50 mL.
4. The method of claim 1, wherein: the ultrasonic frequency in the ultrasonic extraction in the step (1) is 20KHZ, the ultrasonic intensity is 500-1800W, and the liquid temperature is not more than 35 ℃; the ultrasonic time is 3-8 min.
5. The method of claim 1, wherein: and (3) during nitrogen blowing concentration in the step (2), controlling the nitrogen pressure to be 0.4-0.8 psi and the water bath temperature to be 35 ℃.
6. The method of claim 1, wherein: the gas chromatography conditions in the step (3) are as follows: sample inlet temperature: 280 ℃; and (3) sample introduction mode: no shunt sampling; temperature programming: 35 ℃ (2min) → 15 ℃/min → 150 ℃ (5min) → 10 ℃/min → 300 ℃ (5 min); flow rate: 1.0 ml/min; the mass spectrum conditions are as follows: an ion source: an EI source; ion source temperature: 230 ℃; ionization energy: 70eV, scanning range: m/z 35-500 u; solvent delay 3.0 min; electron multiplication voltage: consistent with the tuning voltage; interface temperature: 280 ℃.
7. The method of claim 1, wherein: the number of times of repeating the steps in the step (1) is 1-3.
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| CN115078601A (en) * | 2022-05-07 | 2022-09-20 | 新疆水清清环境监测技术服务有限公司 | Method for rapidly and synchronously extracting and measuring semi-volatile organic compounds and petroleum hydrocarbons in soil |
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