CN115078601A - Method for rapidly and synchronously extracting and measuring semi-volatile organic compounds and petroleum hydrocarbons in soil - Google Patents
Method for rapidly and synchronously extracting and measuring semi-volatile organic compounds and petroleum hydrocarbons in soil Download PDFInfo
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Abstract
The invention relates to the technical field of soil harmful substance detection, in particular to a method for rapidly and synchronously extracting and determining semi-volatile organic compounds and petroleum hydrocarbon in soil, which comprises the following steps: adding quartz sand and anhydrous sodium sulfate into the bottom of a rapid solvent extraction tank, weighing a soil sample, mixing the soil sample with diatomite, putting the mixture into the rapid solvent extraction tank, adding a substitute, adding quartz sand into the top of the rapid solvent extraction tank, compacting and sealing two ends of the rapid solvent extraction tank, performing pressure extraction, collecting an extraction liquid after extraction is finished, concentrating the purified extraction liquid, determining semi-volatile organic matters in the extraction liquid by adopting a gas chromatography-mass spectrometry method, and determining petroleum hydrocarbon in the extraction liquid by adopting a gas chromatography. The invention optimizes the existing standard method, unifies the sample sampling amount and the extraction solvent of the quick solvent extraction of the semi-volatile organic compounds and the petroleum hydrocarbon in the soil, has the characteristics of accuracy, high efficiency, energy saving and environmental protection, and can be widely applied to the daily detection work with high flux.
Description
Technical Field
The invention relates to the technical field of soil harmful substance detection, in particular to a method for rapidly and synchronously extracting and determining semi-volatile organic matters and petroleum hydrocarbon in soil.
Background
As the social economy develops continuously, the pollution of the semi-volatile organic compounds and the petroleum hydrocarbons (C10-C40) to the environment is increased continuously, and the economic development cannot be realized at the cost of environmental pollution, so the pollution of the semi-volatile organic compounds and the petroleum hydrocarbons (C10-C40) to the environment cannot be ignored. Both semi-volatile organics and petroleum hydrocarbons (C10-C40) have a variety of different mixture compositions. GB36600-2018 'soil pollution risk control standard for soil environmental quality construction land' jointly issued by the department of ecological environmental protection and the general administration of market supervision and management in 2018 incorporates 21 medium-semi-volatile organic compounds and petroleum hydrocarbons (C10-C40) as pollutants. The environmental protection division issued 2017 standards for monitoring semi-volatile organic compounds in soils and sediments, and the ecotope division issued 2019 standards for monitoring petroleum hydrocarbons (C10-C40) in soils. Environmental pollution by semi-volatile organics and petroleum hydrocarbons (C10-C40) has been recognized socially.
Semi-volatile organic compounds and petroleum hydrocarbons (C10-C40) are carcinogenic, teratogenic, mutagenic, and the like. It also has a great hazard to plants, water and soil. In order to understand the potential risk of soil pollution and reasonably carry out the monitoring and repairing work of the soil polluted by semi-volatile organic compounds and petroleum hydrocarbon (C10-C40), an accurate, efficient and quick determination method needs to be established. In the existing sample processing technology, Soxhlet extraction is time-consuming (18 hours), and ultrasonic extraction is low in extraction efficiency, so that the high-efficiency and quick determination is not facilitated.
Disclosure of Invention
The invention provides a method for rapidly and synchronously extracting and measuring semi-volatile organic compounds and petroleum hydrocarbon in soil, overcomes the defects of the prior art, and can effectively solve the problems of low extraction efficiency and respective extraction of the semi-volatile organic compounds and the petroleum hydrocarbon by the prior extraction technology.
The technical scheme of the invention is realized by the following measures: a method for rapidly and synchronously extracting and measuring semi-volatile organic compounds and petroleum hydrocarbon in soil comprises the following steps:
step one, uniformly mixing collected soil samples, removing impurities in the soil samples, putting the soil samples into a vacuum freeze dryer for drying and dewatering, grinding and sieving the dried samples, and then sealing and storing the samples in a dark place;
secondly, adding quartz sand and anhydrous sodium sulfate into the bottom of the rapid solvent extraction tank, weighing 10.0-30.0 g of a soil sample, mixing the soil sample with 3-10 g of diatomite, putting the mixture into the rapid solvent extraction tank, adding a substitute, adding quartz sand into the top of the rapid solvent extraction tank, compacting and sealing two ends of the quartz sand, performing pressure extraction, and collecting an extract after extraction is finished;
thirdly, drying the extract, filtering, and concentrating the filtered extract to 1ml to 2 ml;
fourthly, purifying the concentrated extract liquor by using an activated Florisil solid phase column;
and fifthly, concentrating the purified extract, determining semi-volatile organic compounds in the extract by adopting a gas chromatography-mass spectrometry method, and determining petroleum hydrocarbon in the extract by adopting a gas chromatography method.
The following is further optimization or/and improvement of the technical scheme of the invention:
in the first step, soil samples are ground, sieved and homogenized into 200um to 300um particles.
In the second step, 1g to 2g of quartz sand and 1g to 2g of anhydrous sodium sulfate are added to the bottom of the rapid solvent extraction tank, and 1g to 2g of quartz sand is added to the top of the rapid solvent extraction tank.
In the second step, the volume ratio of the extracting agent adopted for sample extraction is 1:1 dichloromethane-acetone mixture.
In the second step, the conditions of the rapid solvent extraction are as follows: the extraction preheating temperature is 80 ℃, the cleaning rate is 45.00ml/min, the cleaning time is 30s, the purging time is 60s, the leakage temperature is 100 ℃, the leakage pressure is 10.00MPa, the holding time is 180s, and the extraction is circulated for 1 to 3 times.
In the fifth step, the gas chromatography-mass spectrometry is used for determining the semi-volatile organic compounds, and an internal standard method is used for quantification, wherein the internal standard substances are 1, 4-dichlorobenzene-d 4, naphthalene, acenaphthene-d 8, phenanthrene-d 10, chrysene-d 12 and perylene-d 12.
In the fifth step, the conditions of the gas chromatography-mass spectrometry for determining the semi-volatile organic compounds in the solution are as follows: the sample inlet temperature is 280 ℃; the sample injection mode is not divided; the sample amount is 1.0 ul; the column flow rate is 1.89 ml/min; a chromatographic column DM-5MS 30m multiplied by 0.25mm multiplied by 0.25 um; the column temperature program is kept for 10min at 40 ℃, the temperature is increased to 120 ℃ at 10 ℃/min and kept for 1min, the temperature is increased to 250 ℃ at 25 ℃/min and is increased to 290 ℃ at 10 ℃/min and kept for 10 min; ionization mode EI of the mass spectrometer; the ion source temperature is 200 ℃; the interface temperature is 280 ℃, and the solvent is delayed for 3 min; data acquisition mode full scan; the mass range is 35amu-500 amu.
In the fifth step, the petroleum hydrocarbon is determined by gas chromatography and quantified by an external standard method.
In the fifth step, the chromatographic conditions for measuring the petroleum hydrocarbon by the gas chromatography are as follows: the temperature of a sample inlet of the gas chromatograph is 320 ℃; the sample feeding mode is not divided into separate sample feeding; chromatographic column DB-530 m × 0.35mm × 0.25 um; keeping the column temperature program at 60 ℃ for 1min, heating to 290 ℃ at 8 ℃/min for 1min, and heating to 320 ℃ at 30 ℃/min for 20 min; the gas flow rates are 1.32ml/min of nitrogen, 40ml/min of hydrogen and 400ml/min of air; the temperature of the detector is 325 ℃; the sample size was 1.0 ul.
The method optimizes the existing standard method, unifies the sample sampling amount and the extraction solvent of the quick solvent extraction of the semi-volatile organic compounds and the petroleum hydrocarbon (C10-C40) in the soil, has the characteristics of accuracy, high efficiency, energy conservation and environmental protection, provides a theoretical basis for establishing the standard method, and can be widely applied to high-flux daily detection work.
Drawings
FIG. 1 is a chromatogram of total ions of semi-volatile organic compounds in example 10 of the present invention.
FIG. 2 is a gas chromatogram of a petroleum hydrocarbon (C10-C40) according to example 10 of the present invention.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments may be determined according to the technical solutions and practical situations of the present invention. The various chemical reagents and chemical articles mentioned in the invention are all the chemical reagents and chemical articles which are well known and commonly used in the prior art, unless otherwise specified; the percentages in the invention are mass percentages unless otherwise specified; the solution in the present invention is an aqueous solution in which the solvent is water, for example, a hydrochloric acid solution is an aqueous hydrochloric acid solution, unless otherwise specified; the normal temperature and room temperature in the present invention generally mean a temperature of 15 ℃ to 25 ℃, and are generally defined as 25 ℃.
The invention is further described below with reference to the following examples:
example 1: the method for rapidly and synchronously extracting and measuring the semi-volatile organic compounds and the petroleum hydrocarbon in the soil comprises the following steps:
step one, uniformly mixing collected soil samples, removing impurities in the soil samples, putting the soil samples into a vacuum freeze dryer for drying and dewatering, grinding and sieving the dried samples, and then sealing and storing the samples in a dark place;
secondly, adding quartz sand and anhydrous sodium sulfate into the bottom of the rapid solvent extraction tank, weighing 10.0-30.0 g of a soil sample, mixing the soil sample with 3-10 g of diatomite, putting the mixture into the rapid solvent extraction tank, adding a substitute, adding quartz sand into the top of the rapid solvent extraction tank, compacting and sealing two ends of the quartz sand, performing pressure extraction, and collecting an extract after extraction is finished;
thirdly, drying the extract, filtering, and concentrating the filtered extract to 1ml to 2 ml;
fourthly, purifying the concentrated extract liquor by using an activated Florisil solid phase column;
and fifthly, concentrating the purified extract, determining semi-volatile organic compounds in the extract by adopting a gas chromatography-mass spectrometry method, and determining petroleum hydrocarbon in the extract by adopting a gas chromatography method.
In the third step of the invention, the extract liquor is dried and filtered by adopting anhydrous sodium sulfate, and is concentrated by a parallel concentrator, wherein the concentration conditions are as follows: the shaking speed was 200rpm, the temperature was 30 ℃ and the vacuum program was 800mbar (5min) → 700mbar (2min) → 350mbar (10min) → 300mbar (10 min).
In the fourth step, the concrete operation of purifying the concentrated extract liquor by adopting an activated Florisil solid phase column is as follows: washing the activated Flori silica solid phase column by using about 10ml of dichloromethane-acetone (1+1) mixed solution, keeping the column head in a wetting state after washing, then adding the extract liquid to the Flori silica solid column, keeping for 1min, turning on an air suction switch, starting to collect the effluent extract liquid, completely transferring the extract liquid to a purification column, leaching the purification column by using 10ml of dichloromethane, and collecting the leaching liquid to obtain the purified extract liquid.
According to the invention, gas chromatography-mass spectrometry is adopted to determine 65 semi-volatile organic compounds in the soil sample, including N-nitrosodimethylamine, phenol, 2-chlorophenol, bis (2-chloroethyl) ether, 1, 3-dichlorobenzene, 1, 4-dichlorobenzene, 1, 2-dichlorobenzene, 2-methylphenol, bis (2-chloroisopropyl) ether, hexachloroethane, N-nitrosodi-N-propylamine, 4-methylphenol, nitrobenzene, isophorone, 2-nitrophenol, 2, 4-dimethylphenol, bis (2-chloroethoxy) methane, 2, 4-dichlorophenol, 1,2, 4-trichlorobenzene, naphthalene, 4-chloroaniline, hexachloro-1, 3-butadiene, 4-chloro-3-methylphenol, 2-methylnaphthalene, hexachlorocyclopentadiene, 2,4, 6-trichlorophenol, 2,4, 5-trichlorophenol, 2-chloronaphthalene, 2-nitroaniline, dimethyl phthalate, 2, 6-dinitrotoluene, acenaphthylene, 3-nitroaniline, acenaphthylene, 2, 4-dinitrophenol, 4-nitrophenol, dibenzofuran, 2, 4-dinitrotoluene, diethyl phthalate, fluorene, 4-chlorophenyl-phenyl ether, 4-nitroaniline, 4, 6-dinitro-2-methylphenol, azobenzene, 4-bromophenyl-phenyl ether, hexachlorobenzene, pentachlorophenol, phenanthrene, anthracene, carbazole, di-n-butyl phthalate, fluoranthene, pyrene, 4' -terphenyl-d 14, butylbenzyl phthalate, perylene, 2,4, 5-trichlorobenzene, 2-chloronaphthalene, 2-nitroaniline, 2, 4-dinitrotoluene, diethyl phthalate, fluorene, 4-chlorophenyl-d 14, anthracene, perylene, and anthracene, Benzo [ a ] anthracene, chrysene, di (2-ethylhexyl) phthalate, di-n-octyl phthalate, benzo [ b ] fluoranthene, benzo [ k ] fluoranthene, benzo [ a ] pyrene, indeno [1,2,3, -cd ] pyrene, dibenzo [ a, h ] anthracene, benzo [ g, h, i ] perylene.
In the invention, the petroleum hydrocarbon in the soil sample is determined to be normal paraffin of petroleum hydrocarbon C10 to petroleum hydrocarbon C40 by adopting gas chromatography.
In the invention, the substitute is a mixed solution of phenol-d 5, 2-fluorophenol, 2,4, 6-tribromophenol, nitrobenzene-d 5, 2-fluorobiphenyl and 4', 4-trifluorobiphenyl, the concentration is 100mg/l, and the addition amount is 10 ul.
Example 2: as an optimization of the above example, in the first step, soil samples were ground, sieved and homogenized into 200um to 300um granules.
Example 3: as an optimization of the above embodiment, in the second step, 1g to 2g of quartz sand, 1g to 2g of anhydrous sodium sulfate and 1g to 2g of quartz sand are added to the bottom of the rapid solvent extraction tank, and 1g to 2g of quartz sand are added to the top of the rapid solvent extraction tank.
Example 4: as an optimization of the above embodiment, in the second step, the volume ratio of the extracting agent used for sample extraction is 1:1 dichloromethane-acetone mixture.
Example 5: as an optimization of the above example, in the second step, the conditions of the fast solvent extraction are: the extraction preheating temperature is 80 ℃, the cleaning rate is 45.00ml/min, the cleaning time is 30s, the purging time is 60s, the leakage temperature is 100 ℃, the leakage pressure is 10.00MPa, the holding time is 180s, and the extraction is circulated for 1 to 3 times.
Example 6: as an optimization of the above example, in the fifth step, the gas chromatography-mass spectrometry is used to measure the semi-volatile organic compounds, and the internal standard method is used to quantify, wherein the internal standard substances are 1, 4-dichlorobenzene-d 4, naphthalene, acenaphthene-d 8, phenanthrene-d 10, chrysene-d 12 and perylene-d 12.
The specific operation is as follows: concentrating the purified extract to 1ml, dividing 0.5ml into sample tubes, adding 10ul of 100mg/l internal standard substance solution (1, 4-dichlorobenzene-d 4, naphthalene, acenaphthene-d 8, phenanthrene-d 10, chrysene-d 12 and perylene-d 12) intermediate solution, mixing uniformly, and measuring the semi-volatile organic compounds in the mixture on a machine.
Example 7: as an optimization of the above embodiment, in the fifth step, the conditions of the gas chromatography-mass spectrometry for determining the mass spectrum of the semi-volatile organic compound therein are as follows: the sample inlet temperature is 280 ℃; the sample feeding mode is not divided into separate sample feeding; the sample amount is 1.0 ul; the column flow rate is 1.89 ml/min; a chromatographic column DM-5MS 30m multiplied by 0.25mm multiplied by 0.25 um; the column temperature program is kept for 10min at 40 ℃, the temperature is increased to 120 ℃ at 10 ℃/min and kept for 1min, the temperature is increased to 250 ℃ at 25 ℃/min and is increased to 290 ℃ at 10 ℃/min and kept for 10 min; ionization mode EI of the mass spectrometer; the ion source temperature is 200 ℃; the interface temperature is 280 ℃, and the solvent is delayed for 3 min; data acquisition mode full scan; the mass range is 35amu-500 amu.
Example 8: as an optimization of the above example, in the fifth step, the petroleum hydrocarbon is quantified by gas chromatography using an external standard method.
Example 9: as an optimization of the above embodiment, in the fifth step, the chromatographic conditions for measuring petroleum hydrocarbon by gas chromatography are as follows: the temperature of a sample inlet of the gas chromatograph is 320 ℃; the sample feeding mode is not divided into separate sample feeding; chromatographic column DB-530 m × 0.35mm × 0.25 um; keeping the column temperature program at 60 ℃ for 1min, heating to 290 ℃ at 8 ℃/min for 1min, and heating to 320 ℃ at 30 ℃/min for 20 min; the gas flow rate is 1.32ml/min of nitrogen, 40ml/min of hydrogen and 400ml/min of air; the temperature of the detector is 325 ℃; the sample size was 1.0 ul.
Example 10: the method for rapidly and synchronously extracting and measuring the semi-volatile organic compounds and the petroleum hydrocarbon in the soil comprises the following steps:
firstly, mixing soil samples evenly, removing foreign matters such as branch rods, leaves, stones and the like, and taking a proper amount of samples to put into a vacuum freeze dryer for drying and dewatering. Grinding the dried sample, sieving with a 0.25mm sieve, homogenizing to obtain 250um granules, and sealing in a brown glass bottle;
and secondly, adding 2g of quartz sand and 2g of anhydrous sodium sulfate into the bottom of a quick solvent extraction tank, weighing 20.0g of a soil sample, mixing the soil sample with 5g of diatomite, putting the mixture into the quick solvent extraction tank, adding 10ul of 100mg/l substitute, adding 2g of quartz sand into the top of the quick solvent extraction tank, compacting and sealing two ends of the quick solvent extraction tank, performing pressure extraction by using dichloromethane-acetone (volume ratio is 1:1), and collecting extract liquor after extraction is finished. The conditions for rapid solvent extraction were: extracting at preheating temperature of 80 deg.C, cleaning rate of 45.00ml/min, cleaning time of 30s, purging time of 60s, leakage temperature of 100 deg.C, leakage pressure of 10.00MPa, holding time of 180s, and circulating for 2 times, and collecting extractive solution.
In the third step, the extract was dried over anhydrous sodium sulfate, filtered, and concentrated to about 1.0ml using a parallel concentrator.
Fourthly, using the volume ratio of 1:1, washing and activating the florisil solid phase column by using about 10ml of dichloromethane-acetone mixed solution, keeping the column head in an infiltration state after washing, adding the extracting solution to the florisil solid phase column, keeping for 1min, turning on an air suction switch, and beginning to collect the effluent liquid. The concentration flask was washed several times with 5ml dichloromethane, transferred to the purification column, rinsed with 10ml dichloromethane, and the rinse was collected and concentrated to 1.0 ml.
Fifthly, 0.5ml of collected leacheate is taken and put into a sample injection liner tube, 10ul of 100mg/l of internal standard (1, 4-dichlorobenzene-d 4, naphthalene, acenaphthene-d 8, phenanthrene-d 10, chrysene-d 12 and perylene-d 12) intermediate liquid is added and mixed evenly to measure semi-volatile organic matters; 0.5mL of collection leacheate is separated and put into a sample injection vial, 0.5mL of dichloromethane is added to the sample injection vial to be constant volume of 1.0mL, and petroleum hydrocarbon (C10-C40) is measured by mixing uniformly.
The chromatographic mass spectrometry conditions for determining the semi-volatile organic compounds by the gas chromatography-mass spectrometry method are as follows:
the sample inlet temperature is 280 ℃; the sample feeding mode is not divided into separate sample feeding; the sample amount is 1.0 ul; the column flow rate is 1.89 ml/min; a chromatographic column DM-5MS 30m multiplied by 0.25mm multiplied by 0.25 um; the column temperature program is kept for 10min at 40 ℃, the temperature is increased to 120 ℃ at 10 ℃/min and kept for 1min, the temperature is increased to 250 ℃ at 25 ℃/min and is increased to 290 ℃ at 10 ℃/min and kept for 10 min; ionization mode EI of the mass spectrometer; the ion source temperature is 200 ℃; the interface temperature is 280 ℃, and the solvent is delayed for 3 min; data acquisition mode full scan; the mass range is 35amu-500 amu.
The chromatographic conditions for determining petroleum hydrocarbon by gas chromatography are as follows: the temperature of a sample inlet of the gas chromatograph is 320 ℃; the sample feeding mode is not divided into separate sample feeding; chromatographic column DB-530 m × 0.35mm × 0.25 um; keeping the column temperature program at 60 ℃ for 1min, heating to 290 ℃ at 8 ℃/min for 1min, and heating to 320 ℃ at 30 ℃/min for 20 min; the gas flow rates are 1.32ml/min of nitrogen, 40ml/min of hydrogen and 400ml/min of air; the temperature of the detector is 325 ℃; the sample size was 1.0 ul.
And (3) standard curve preparation:
standard curve of semi-volatile organic compounds: respectively sucking 10ul, 20ul, 50ul, 100ul, 200ul and 400ul of semi-volatile organic target substance + substitute substance standard mixed liquid into 2.0ml of sample injection vials, sequentially adding 50ul of internal standard substance standard intermediate liquid, and keeping the volume to 1.0ml by using dichlorohexane. The mass concentrations of the semi-volatile organic target substance and the substitute substance are 1.0mg/L, 2.0mg/L, 5.0mg/L, 10.0mg/L, 20.0mg/L and 40.0mg/L in sequence, and the mass concentrations of the internal standard substance are 5.0mg/L standard series. According to the instrument conditions of the method, samples are sequentially injected from low concentration to high concentration for analysis. And (3) drawing a standard curve by taking the ratio of the peak response value of the target substance-substitute substance to the peak response value of the internal standard substance as a vertical coordinate and the concentration ratio of the target substance to the internal standard substance as a horizontal coordinate, wherein specific results are shown in table 1.
Standard Curve for petroleum hydrocarbons (C10-C40): respectively sucking 0ul, 12.5ul, 25ul, 50ul, 100ul and 300ul of standard mixed solution of petroleum hydrocarbon (C10-C40 normal paraffin) in 2.0ml sample injection vials, and configuring into standard series of petroleum hydrocarbon (C10-C40) with mass concentrations of 0mg/L, 248mg/L, 775mg/L, 1550mg/L, 3100.0mg/L and 9300.0mg/L in sequence. According to the instrument conditions of the method, samples are sequentially injected from low concentration to high concentration for analysis. The results are shown in Table 2, with the total peak area within the defined retention time window as ordinate and the concentration as abscissa, plotted against a standard curve.
Typical chromatograms of semi-volatile organics and petroleum hydrocarbons (C10-C40) are shown in FIGS. 1 and 2.
Example 11: comparative experiment of extraction solvent
Acetone-dichloromethane (volume ratio 1:1) and acetone-n-hexane (volume ratio 1:1) are respectively adopted as extraction solvents, and the extraction efficiencies of different solvents are compared.
And (3) uniformly mixing 20g of 12 parts of the same soil sample with 5g of diatomite, adding the mixture into an extraction tank, and adding the substitute mixed solution with the concentration above the middle point of the calibration curve.
The extraction efficiency of different solvents of semi-volatile organic compounds in soil is compared: six soil samples are accurately weighed, wherein the standard concentration of 2 parts is 0mg/kg, the standard concentration of 2 parts is 0.1mg/kg, and the standard concentration of 2 parts is 0.5 mg/kg. The extraction efficiency of 6 parts of soil samples subjected to standard addition was measured by dividing the soil samples into 2 groups of standard addition concentrations of 0mg/kg, 0.1mg/kg and 0.5mg/kg, one group using acetone-n-hexane (1+1) as an extraction solvent, and the other group using acetone-dichloromethane (1+1) as an extraction solvent, and the results are shown in table 1. As can be seen from table 1, when the semi-volatile organic compounds in the soil sample are extracted with the fast solvent, the extraction efficiency using acetone-dichloromethane (1+1) as the solvent is higher than that using acetone-n-hexane (1+1) as the solvent.
Comparison of extraction efficiencies of different solvents for petroleum hydrocarbons (C10-C40) in soil: six samples are accurately weighed, 2 parts of standard addition concentration is 0mg/kg, 2 parts of standard addition concentration is 46.5mg/kg, and 2 parts of standard addition concentration is 310 mg/kg. The extraction efficiency was measured by dividing 6 samples subjected to the labeling into 2 groups of 0mg/kg, 46.5mg/kg and 310mg/kg, one group using acetone-n-hexane (1+1) as the extraction solvent, and the other group using acetone-dichloromethane (1+1) as the extraction solvent, and the results are shown in Table 2. As shown in Table 2, the extraction efficiency of acetone-dichloromethane (1+1) as a solvent is higher than that of acetone-n-hexane (1+1) as a solvent when petroleum hydrocarbons (C10-C40) in a soil sample are extracted by a rapid solvent.
Example 12: detection limit, precision and accuracy
Detection limit: the 20g blank samples were labeled and 11 replicates were performed following all steps of sample analysis.
Precision and accuracy: the results of seven measurements were performed on each of the 20g samples using the standard, and are shown in tables 3 and 4. As can be seen from Table 3, the correlation coefficient of the standard curve of the semi-volatile organic compounds is 0.990-0.999, the detection limit is 0.01 mg/kg-0.09 mg/kg, the lower limit of the measurement is 0.04 mg/kg-0.36 mg/kg, the normalized recovery rates are 60.0% -105% and 59.3% -126%, respectively, and the RSD is 1.1% -12.0% and 0.8% -5.1%, respectively, which all satisfy the standard requirements. As can be seen from Table 4, the linear standard curve of 0.9998, the detection limit of 2.0mg/kg, the lower determination limit of 8.0mg/kg, the normalized recovery rates of 85.4% and 89.2% respectively, and the RSD of 1.5% and 2.0% respectively of the petroleum hydrocarbon (C10-C40) all satisfy the requirements of the relevant standards.
The invention has the following advantages:
1. the invention unifies the sample sampling amount and the extraction solvent of the quick solvent extraction of semi-volatile organic compounds and petroleum hydrocarbon (C10-C40) in soil.
2. Compared with other extraction technologies, such as ultrasonic extraction, traditional Soxhlet extraction, automatic Soxhlet extraction and microwave extraction, HJ834-2017 and HJ1021-2019 rapid solvent extraction and the like, the same solvent rapid extraction method is used for synchronous extraction, and semi-volatile organic matters and petroleum hydrocarbon (C10-C40) in soil are respectively measured, so that the dosage of the used solvent is the minimum in the process of extracting a sample, the extraction cost is saved, and the practicability is higher.
3. Compared with the traditional Soxhlet extraction technology (the extraction time generally needs 4-48 h) and the microwave extraction technology (the extraction time is 0.5-1 h), the extraction time of the rapid solvent extraction technology only needs about 15 min. Compared with the method that the rapid solvent extraction is carried out separately for HJ834-2017 and HJ1021-2019, the rapid solvent extraction method provided by the invention has the advantages that the extraction efficiency is improved and the extraction time is effectively reduced when the semi-volatile organic compounds and the petroleum hydrocarbon (C10-C40) in the soil are respectively measured.
4. The same extraction conditions can be used for different matrixes, and because the extraction process is vertical static extraction, a filter layer or an adsorption medium can be added at the bottom in advance when a sample is filled.
5. The automation degree is high, the rapid solvent extraction can be used for extracting the same sample for multiple times according to the requirement, or the solvent extraction is changed, and all the operations can be programmed by a user and controlled automatically.
6. The invention can reduce the dosage of organic solvent and the harm to operators; the secondary pollution to the environment is small; therefore, the method is more energy-saving and environment-friendly compared with other methods.
In conclusion, the method optimizes the existing standard method, unifies the sample sampling amount and the extraction solvent of the quick solvent extraction of the semi-volatile organic compounds and the petroleum hydrocarbons (C10-C40) in the soil, has the characteristics of accuracy, high efficiency, energy conservation and environmental protection, provides a theoretical basis for establishing the standard method, and can be widely applied to high-flux daily detection work.
The technical characteristics form an embodiment of the invention, which has strong adaptability and implementation effect, and unnecessary technical characteristics can be increased or decreased according to actual needs to meet the requirements of different situations.
TABLE 1
TABLE 2
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Claims (9)
1. A method for rapidly and synchronously extracting and measuring semi-volatile organic compounds and petroleum hydrocarbons in soil is characterized by comprising the following steps:
step one, uniformly mixing collected soil samples, removing impurities in the soil samples, putting the soil samples into a vacuum freeze dryer for drying and dewatering, grinding and sieving the dried samples, and then sealing and storing the samples in a dark place;
secondly, adding quartz sand and anhydrous sodium sulfate into the bottom of the rapid solvent extraction tank, weighing 10.0-30.0 g of a soil sample, mixing the soil sample with 3-10 g of diatomite, putting the mixture into the rapid solvent extraction tank, adding a substitute, adding quartz sand into the top of the rapid solvent extraction tank, compacting and sealing two ends of the quartz sand, performing pressure extraction, and collecting an extract after extraction is finished;
thirdly, drying the extract, filtering, and concentrating the filtered extract to 1ml to 2 ml;
fourthly, purifying the concentrated extract liquor by using an activated Florisil solid phase column;
and fifthly, concentrating the purified extract, determining semi-volatile organic compounds in the extract by adopting a gas chromatography-mass spectrometry method, and determining petroleum hydrocarbon in the extract by adopting a gas chromatography method.
2. The method for rapid simultaneous extraction and determination of semi-volatile organic compounds and petroleum hydrocarbons in soil according to claim 1, wherein in the first step, the soil sample is ground, sieved and homogenized into 200um to 300um particles.
3. The method for rapid and synchronous extraction and determination of semi-volatile organic compounds and petroleum hydrocarbons in soil according to claim 1 or 2, wherein in the second step, 1g to 2g of quartz sand, 1g to 2g of anhydrous sodium sulfate and 1g to 2g of quartz sand are added to the bottom of the rapid solvent extraction tank and the top of the rapid solvent extraction tank.
4. The method for rapid and synchronous extraction and determination of semi-volatile organic compounds and petroleum hydrocarbons in soil according to any one of claims 1 to 3, wherein in the second step, the volume ratio of the extracting agent used for sample extraction is 1:1 dichloromethane-acetone mixture.
5. The method for the rapid simultaneous extraction and determination of semi-volatile organic compounds and petroleum hydrocarbons in soil according to any one of claims 1 to 4, characterized in that in the second step, the conditions of the rapid solvent extraction are: the extraction preheating temperature is 80 ℃, the cleaning rate is 45.00ml/min, the cleaning time is 30s, the purging time is 60s, the leakage temperature is 100 ℃, the leakage pressure is 10.00MPa, the holding time is 180s, and the extraction is circulated for 1 to 3 times.
6. The method for rapid and synchronous extraction and determination of semi-volatile organic compounds and petroleum hydrocarbons in soil according to any one of claims 1 to 5, characterized in that in the fifth step, gas chromatography-mass spectrometry is used for determination of semi-volatile organic compounds, and an internal standard method is adopted for quantification, wherein the internal standard substances are 1, 4-dichlorobenzene-d 4, naphthalene, acenaphthene-d 8, phenanthrene-d 10, chrysene-d 12 and perylene-d 12.
7. The method for the rapid simultaneous extraction and determination of semi-volatile organic compounds and petroleum hydrocarbons in soil according to any one of claims 1 to 6, wherein in the fifth step, the gas chromatography-mass spectrometry is used for determining the chromatographic mass spectrometry conditions of the semi-volatile organic compounds: the sample inlet temperature is 280 ℃; the sample feeding mode is not divided into separate sample feeding; the sample injection amount is 1.0 ul; the column flow rate is 1.89 ml/min; a chromatographic column DM-5MS 30m multiplied by 0.25mm multiplied by 0.25 um; the column temperature program is kept for 10min at 40 ℃, the temperature is increased to 120 ℃ at 10 ℃/min and kept for 1min, the temperature is increased to 250 ℃ at 25 ℃/min and is increased to 290 ℃ at 10 ℃/min and kept for 10 min; ionization mode EI of the mass spectrometer; the ion source temperature is 200 ℃; the interface temperature is 280 ℃, and the solvent is delayed for 3 min; data acquisition mode full scan; the mass range is 35amu-500 amu.
8. The method for the rapid simultaneous extraction and determination of semi-volatile organic compounds and petroleum hydrocarbons in soil according to any one of claims 1 to 7, wherein in the fifth step, the petroleum hydrocarbons are determined quantitatively by gas chromatography using an external standard method.
9. The method for the rapid simultaneous extraction and determination of semi-volatile organic compounds and petroleum hydrocarbons in soil according to any one of claims 1 to 8, wherein in the fifth step, the chromatographic conditions for the gas chromatography for the determination of the petroleum hydrocarbons are as follows: the temperature of a sample inlet of the gas chromatograph is 320 ℃; the sample feeding mode is not divided into separate sample feeding; chromatographic column DB-530 m × 0.35mm × 0.25 um; the column temperature program is kept for 1min at 60 ℃, the temperature is increased to 290 ℃ at 8 ℃/min and kept for 1min, and the temperature is increased to 320 ℃ at 30 ℃/min and kept for 20 min; the gas flow rate is 1.32ml/min of nitrogen, 40ml/min of hydrogen and 400ml/min of air; the temperature of the detector is 325 ℃; the sample size was 1.0 ul.
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