CN113607852A - Method for measuring turpentine in soil - Google Patents
Method for measuring turpentine in soil Download PDFInfo
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Abstract
The invention discloses a method for measuring turpentine in soil, which comprises the following steps: 1) preparing a calibration curve sample; 2) purging and trapping a calibration curve sample; 3) gas chromatography mass spectrometry (GC-MS) determination of the calibration curve sample; 4) drawing a calibration curve; 5) adding a soil sample to be detected; 6) extracting a soil sample to be detected in a vortex oscillator; 7) sweeping and trapping a soil sample to be detected; 8) measuring a gas chromatography mass spectrum (GC-MS) of a soil sample to be measured; 9) the result calculation shows that the method for measuring the turpentine in the soil adopts the mass spectrometry determination of purging and trapping-gas chromatography, the instrument parameters and the pretreatment method are deeply researched, and each parameter is set according to the characteristics of soil pollution and the characteristics of the turpentine.
Description
Technical Field
The invention relates to the determination of pollutants in soil, in particular to a determination method of turpentine in soil.
Background
Turpentine is an important chemical raw material, the main component of the turpentine is terpene (containing 64% of alpha-pinene and 33% of beta-pinene approximately), and the turpentine is an excellent organic solvent and is widely used in the industries of paint, adhesives and the like. Turpentine oil has volatility, is transferred into water and soil through environmental migration, causes pollution to the soil environment in industrial production and accidental splashing, has certain enrichment capacity as a pollutant receptor, and seriously harms the ecological environment and human health due to lasting pollution.
Due to the harmfulness of turpentine, the limit value of the turpentine in a drinking water source ground is 20 mug/L specified in GB 3838-2002 'surface water environment quality standard', the damage of the turpentine in soil is also worth paying attention to, but the establishment of the soil environment detection standard and the quality standard in China is slightly lagged compared with the surface water standard, and no detection method for the turpentine in the soil exists at present.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method solves the problem of measuring the turpentine in the polluted soil, and fills the blank in the method for detecting the turpentine in the soil.
In order to solve the technical problems, the technical scheme of the invention is as follows: the method for measuring turpentine in soil comprises the following steps:
1) configuring a calibration curve sample
The concentration of a curve prepared by using 20mg/L turpentine use solution and 20mg/L substitute use solution is as follows: standard series of 2.0, 5.0, 10.0, 50.0, 100 and 200 mug/L, the volume of constant volume is 10mL, the solvent is pure water, 50 mug/L of internal standard use solution of 20mg/L is added into each calibration series, the calibration curve sample is placed in an automatic sample injector after being prepared, and the calibration curve sample is subjected to purging and trapping by a computer;
2) purge capture of calibration curve samples
Purging and trapping: temperature was room temperature, purge tube 10mL, purge flow: 40-50mL/min, purging time of 10-15min, dry-blowing time: 2min, blowing high-purity helium gas as the blowing gas, wherein the analysis temperature is 210-250 ℃, the analysis time is 2-4 min, the baking temperature is 220 ℃, the baking time is 15min, blowing the turpentine in the calibration curve sample obtained in the step 1) into a trap, and blowing the turpentine in the trap into a gas chromatograph after the turpentine is released by heating;
3) gas chromatography-mass spectrometry (GC-MS) determination of calibration curve samples
Performing chromatographic and mass spectrometric measurement on the turpentine purged in the step 2) to obtain peak areas of alpha-pinene and beta-pinene and a peak area response ratio of the peak areas to an internal standard,
chromatographic parameters: and (2) a DB-624 chromatographic column, wherein carrier gas is high-purity helium, the flow is 1-2 mL/min, and the injection port temperature is as follows: the split ratio is 10: 1-20: 1 at 220-250 ℃; temperature programming: maintaining at 35 deg.C for 4min, increasing to 100 deg.C at 5 deg.C/min, maintaining for 0min, increasing to 150 deg.C at 20 deg.C/min, and maintaining for 0 min;
mass spectrum parameters: adopting an EI source, wherein the ion source temperature is 230 ℃, the quadrupole rod temperature is 150 ℃, the solvent delay is 1-2 min, and the full scanning mode (Scan) and the selective ion monitoring mode (SIM) are simultaneously acquired within the scanning range of 40-300;
4) plotting a calibration curve
Taking the peak areas of the alpha-pinene and the beta-pinene in the step 3) and the response ratio of the peak areas of the alpha-pinene and the beta-pinene to the peak area of the internal standard as vertical coordinates, and taking the concentration as horizontal coordinates to establish a calibration curve and drawing the calibration curve;
5) addition of soil sample to be tested
Weighing 10.00g of fresh soil sample, placing the fresh soil sample into a 40ml purge bottle, adding 50 muL of internal standard use solution and 50 muL of substitute use solution by using a micro-injector, wherein the concentrations of the internal standard use solution and the substitute use solution are both 20mg/L, injecting the internal standard use solution and the substitute use solution into the fresh soil sample by using the micro-injector, continuously adding 10ml of extractant into the fresh soil sample, so that the concentrations of the internal standard and the substitute in the extractant are both 100 mug/L, and screwing a bottle cap;
6) extraction of soil sample to be tested in vortex oscillator
And (3) placing the purging bottle filled with the sample in the step 5) in a vortex oscillator, oscillating for 5-10 min in a continuous dot-inversion mode until the soil sample is completely oscillated and loosened, standing for 10min, placing the oscillated sample bottle in an automatic sample injector, and performing purging and trapping on the sample bottle on a machine.
7) Sweeping and trapping of soil sample to be detected
Sweeping the turpentine in the soil sample to be detected in the step 6) into a trap,
purging and trapping parameters: temperature was room temperature, purge tube 10mL, purge flow: 40-50mL/min, purging time of 10-15min, dry-blowing time: 2min, wherein the purge gas is high-purity helium, the desorption temperature is 210-250 ℃, the desorption time is 2-4 min, the baking temperature is 220 ℃, and the baking time is 15 min;
8) determination of gas chromatography mass spectrometry (GC-MS) of soil sample to be detected
Performing chromatographic and mass spectrometric measurement on the turpentine oil blown out in the step 7) to obtain the peak areas of alpha-pinene and beta-pinene of the soil sample to be detected and the response ratio of the peak areas of the alpha-pinene and the beta-pinene to the internal standard,
chromatographic parameters: and (2) a DB-624 chromatographic column, wherein carrier gas is high-purity helium, the flow is 1-2 mL/min, and the injection port temperature is as follows: the split ratio is 10: 1-20: 1 at 220-250 ℃; temperature programming: maintaining at 35 deg.C for 4min, increasing to 100 deg.C at 5 deg.C/min, maintaining for 0min, increasing to 150 deg.C at 20 deg.C/min, and maintaining for 0 min;
mass spectrum parameters: adopting an EI source, wherein the ion source temperature is 230 ℃, the quadrupole rod temperature is 150 ℃, the solvent delay is 1-2 min, and the full scanning mode (Scan) and the selective ion monitoring mode (SIM) are simultaneously acquired within the scanning range of 40-300;
9) calculation of results
The content W of turpentine in the soil is calculated according to the following formula:
in the formula: w is the content of turpentine in soil, mg/kg;
rho is the peak area of alpha-pinene and beta-pinene of the soil sample to be measured obtained in the step 8) and the response ratio of the peak area of the internal standard, and the turpentine concentration mu g/L can be obtained by combining the calibration curve in the step 4);
m is fresh sample weight g;
wdm-soil dry matter content,%.
wdmThe content of the turpentine is measured according to the method HJ 613-2011, and the content of the turpentine in the soil is obtained through the above calculation formula and is calculated on a dry basis.
Preferably, the internal standard used in step 5) is chlorobenzene D5.
Preferably, the substitute used liquid in the step 5) is one of dibromofluoromethane, toluene-D8 and 4-bromofluorobenzene.
Preferably, the extractant in step 5) is one of an aqueous hydrochloric acid solution having a pH of 5, an aqueous NaOH solution having a pH of 9, a pure aqueous solution, and a saturated aqueous sodium chloride solution.
Preferably, the purge trap parameters in step 2) and step 7): trapping temperature was room temperature, purge tube 10mL, purge flow: 40mL/min, purge time 15min, dry blow time: 2min, the purge gas is high-purity helium, the desorption temperature is 210 ℃, the desorption time is 2min, the baking temperature is 220 ℃, and the baking time is 15 min.
Preferably, the chromatographic parameters in steps 3) and 8): the carrier gas of a DB-624 chromatographic column (20m multiplied by 0.18mm multiplied by 1.0 μm) is high-purity helium, the flow rate is 1mL/min, the injection port temperature: the split ratio is 20:1 at 220 ℃; temperature programming: keeping at 35 deg.C for 4min, increasing to 100 deg.C at 5 deg.C/min, keeping for 0min, increasing to 150 deg.C at 20 deg.C/min, and keeping for 0 min.
Preferably, the mass spectrum parameters in steps 3) and 8): the EI source is adopted, the ion source temperature is 230 ℃, the quadrupole rod temperature is 150 ℃, the solvent delay is 1min, the full scanning mode (Scan) and the selective ion monitoring mode (SIM) are simultaneously acquired, and the scanning range is 40-270.
Preferably, the purge trap parameters in step 2) and step 7): trapping temperature was room temperature, purge tube 10mL, purge flow: 50mL/min, purge time 10min, dry-blow time: 2min, the purge gas is high-purity helium, the desorption temperature is 250 ℃, the desorption time is 4min, the baking temperature is 220 ℃, and the baking time is 15 min.
Preferably, the chromatographic parameters in steps 3) and 8): the carrier gas of a DB-624 chromatographic column (20m multiplied by 0.18mm multiplied by 1.0 μm) is high-purity helium, the flow rate is 2mL/min, the injection port temperature: the split ratio is 10:1 at 250 ℃; temperature programming: keeping at 35 deg.C for 4min, increasing to 100 deg.C at 5 deg.C/min, keeping for 0min, increasing to 150 deg.C at 20 deg.C/min, and keeping for 0 min.
Preferably, the mass spectrum parameters in steps 3) and 8): the method comprises the steps of adopting an EI source, enabling the ion source temperature to be 230 ℃, the quadrupole rod temperature to be 150 ℃, enabling a solvent to delay for 2min, and simultaneously collecting in a full scanning mode (Scan) and a selective ion monitoring mode (SIM), wherein the scanning range is 50-300.
After the technical scheme is adopted, the invention has the effects that: the method for measuring the turpentine in the soil adopts the sweeping and trapping-gas chromatography-mass spectrometry method for measurement, and each parameter is set according to the characteristics of the soil pollution and the characteristics of the turpentine.
Drawings
FIG. 1 is a full Scan (Scan) mass spectrum of a column after optimization;
FIG. 2 is a full Scan (Scan) mass spectrum before column optimization;
FIG. 3 is a Selected Ion Monitoring (SIM) mass spectrum after optimization of the chromatography column;
FIG. 4 is a Selected Ion Monitoring (SIM) mass spectrum before column optimization;
FIG. 5 shows different extractant recovery;
fig. 6 is a calibration curve.
Detailed Description
The present invention will be described in further detail below by way of specific experiments.
1.1 instruments and reagents
7890-5977 gas chromatography mass spectrometer (Agilent, USA), purge and trap sample injector TEKMAR Atomx (TEKMAR, USA), vortex oscillator (SI, USA), magnetic stirrer (Bonne science and technology, MS-1), ultrasonic cleaner (Kunshan Seawa, HCS 5404).
Turpentine oil standard stock solution (100mg/L, solvent methanol) was purchased from Tan ink quality testing science and technology Co., Ltd,
turpentine use solution (20mg/L, solvent methanol): diluting 100mg/L oleum Terebinthinae stock solution with methanol to 20mg/L,
stock solutions of 3 substitutes (2000mg/L, solvent methanol): dibromofluoromethane, toluene-D8, 4-bromofluorobenzene were purchased from Tan ink quality testing science and technology Co., Ltd,
3 alternative use solutions (20mg/L, solvent methanol): diluting 2000mg/L stock solution with methanol to 20mg/L,
internal standard stock solution: chlorobenzene D5(2000mg/L, solvent methanol) was purchased from Tanzer ink quality testing, science, Inc.,
internal standard use solution: chlorobenzene D5(20mg/L, solvent methanol) 2000mg/L of the stock solution of the internal standard was diluted to 20mg/L with methanol,
methanol (chromatographic purity) and test water are used as the chen-troostite purified ultrapure water.
1.3 pretreatment of the samples
Weighing 10.00g of fresh soil sample, placing in a 40ml purging trap bottle, adding 50 μ L of internal standard use solution (20mg/L) and 50 μ L of substitute use solution (20mg/L) by using a micro-syringe, adding 10ml of pure water extractant to make the concentrations of the internal standard and the substitute in the extractant both 100 μ g/L, and screwing the bottle cap. And (3) placing the sample bottle filled with the sample in a vortex oscillator to oscillate for about 10min to ensure that the soil sample is completely oscillated and loosened, and measuring the prepared sample according to the reference conditions of the instrument.
The internal standard used in this example was chlorobenzene D5, and the substitute used was 4-bromofluorobenzene.
1.2 working conditions of the apparatus
Chromatographic parameters: the carrier gas of a DB-624 chromatographic column (20m multiplied by 0.18mm multiplied by 1.0 μm) is high-purity helium, the flow rate is 1mL/min, the injection port temperature: the split ratio of 20:1 is 220 ℃. Temperature programming; keeping at 35 deg.C for 4min, increasing to 100 deg.C at 5 deg.C/min, keeping for 0min, increasing to 150 deg.C at 20 deg.C/min, and keeping for 0 min.
Mass spectrum parameters: and (3) adopting an EI source, wherein the ion source temperature is 230 ℃, the quadrupole rod temperature is 150 ℃, the solvent delay is 1min, and the full scanning mode (Scan) and the selective ion monitoring mode (SIM) are simultaneously acquired. The scan range was 40 to 270 and the ion parameters were selected as detailed in table 1.
Table 1: selection of ion parameters
Purging and trapping parameters: trapping temperature was room temperature, purge tube 10mL, purge flow: 40mL/min, purge time 15min, dry blow time: 2min, the purge gas is high-purity helium, the desorption temperature is 210 ℃, the desorption time is 2min, the baking temperature is 220 ℃, and the baking time is 15 min.
2.1 column selection
Considering that the peak time is closer to turpentine (alpha-pinene and beta-pinene), chlorobenzene D5 is selected as an internal standard substance and 4-bromofluorobenzene is selected as a substitute substance, in order to realize the separation of the four target substances, a chromatographic column DB-624(60m multiplied by 250 mu m multiplied by 1.4 mu m) commonly used for soil VOC detection is selected firstly, the chromatographic column can realize the complete separation of the four target substances, however, the running time is longer, one sample takes 35min, in order to shorten the detection time and improve the detection efficiency, a short column DB-624(20m multiplied by 0.18mm multiplied by 1.0 mu m) is selected, the sampling time is shortened to be within 20min through the optimization of chromatographic conditions, and the target substances are well separated. The Scan spectrum and the SIM spectrum of the target object after optimization are shown in figures 1 and 3, and the Scan spectrum and the SIM spectrum of the target object before optimization are shown in figures 2 and 4.
The column may also be selected to have a VF-624ms (20 m.times.0.15 mm.times.0.84 μm).
2.2 selection of extractant
4 extractants were investigated: the influence of hydrochloric acid aqueous solution at pH 5, NaOH aqueous solution at pH 9, pure water solution and saturated sodium chloride aqueous solution on the extraction effect of turpentine in soil, the addition amount of turpentine in soil was 1.0ug, and the measurement was performed in parallel for 3 times.
The results show that the recovery rates of turpentine in different extracting agents have no obvious change, the economic and practical principles are considered, pure water is finally selected as the extracting agent in the experiment, and the recovery rates of different extracting agents are shown in the figure 5.
2.3 selection of extraction mode
In order to examine the influence of different extraction modes on the extraction efficiency of turpentine in soil, 3 pretreatment modes of ultrasonic extraction, vortex oscillation extraction and magnetic stirring are selected for comparative test, 10.0g of fresh soil sample is respectively weighed and placed in a 40mL blowing bottle, 50 mu L of substitute using solution and 50 mu L of turpentine standard solution are added by a micro-injector, and the contents of the substitute and the turpentine in the sample are enabled to be 1.0 ug.
The fresh soil sample is usually blocky, and in order to make the standard adding test more representative, when the syringe is injected, the needle point should be pricked into the fresh soil, and can not be injected on the surface of the soil sample. And adding 10mL of pure water into the labeled sample bottle, and tightly covering the bottle cap.
Ultrasonic extracting with water at 20 deg.C for 30min, standing for 10min, and measuring; vortex oscillation adopts a continuous point rotation mode, oscillation is carried out for 10min, the soil sample is completely loosened, and the machine is operated for measurement after standing for 10 min; during magnetic stirring, a rotor is placed in a sample bottle, the stirring speed of the instrument is set to be 500rmp, stirring is carried out for 30min, and the machine is used for measuring after standing for 10 min. Each treatment was done 3 times in parallel and the results are shown in table 2.
TABLE 2 recovery of different extraction modes
As can be seen from the data in Table 2, the recovery rate of the magnetic stirring extraction is the lowest, and the sample parallelism is poor, compared with the magnetic stirring extraction, the recovery rate of the ultrasonic extraction is improved, but the treatment time of 30min is not advantageous. In the process of measuring the fresh soil sample, when the sample is blocky and has a compact structure, the ultrasonic extraction and the magnetic stirring extraction cannot realize the complete dispersion of the soil sample, and the turpentine cannot be completely released in the soil. Compared with the two treatment modes, the vortex oscillation extraction recovery rate is up to more than 90%, the result parallelism is good, the treatment time is only 10min, the vortex oscillation extraction frequency is high, the acting force is large, the soil sample can be rapidly dispersed, and the turpentine is fully contacted with the extractant. Therefore, vortex oscillation is selected as an extraction mode of turpentine in soil in the experiment.
2.3 method test
2.3.1 calibration Curve and detection Limit
The quartz sand blank standard-added sample is subjected to 7 times of parallel measurement, the added quantity is 10 mu g/kg, and the detection limit and the measurement lower limit of the method are calculated according to the revised guide of environmental monitoring and analysis method Standard (HJ 168-. The detection limit of the turpentine in the soil measured by the method is 2 mug/kg, and the lower limit of the measurement is 8 mug/kg.
The concentration of the curve prepared by using 20mg/L of the use solution is as follows: 2.0, 5.0, 10.0, 50.0, 100 and 200 μ g/L, and the solvent is methanol. And (3) establishing a calibration curve by taking the peak areas of the alpha-pinene and the beta-pinene and the response ratio of the peak areas of the alpha-pinene and the beta-pinene to the peak area of an internal standard as vertical coordinates and concentration as horizontal coordinates, wherein the correlation coefficient of the drawn calibration curve is 0.999.
The calibration curve is shown in figure 6. The linear equation, correlation coefficient, linear range, detection limit and quantitative limit of turpentine are shown in table 3.
TABLE 3 Linear equation, correlation coefficient, linear range, detection limit and quantification limit for turpentine
2.3.2 precision and accuracy testing
The method comprises the steps of continuously measuring the soil standard adding samples of 25.0 mu g/kg and 100 mu g/kg for 6 times, calculating the recovery rate and the precision of the standard adding samples, and as can be seen from the table 4, the standard adding recovery rate of the actual soil samples is 94.3-106%, the standard deviation is 1.5-2.6%, and the precision and the accuracy of the method can meet the requirements of soil environment monitoring.
TABLE 4 results of analysis of actual samples, recovery by adding standard and relative deviation
3. Calculation of results
The content W of turpentine in the soil is calculated according to the following formula:
in the formula: w is the content of turpentine in soil, mg/kg;
rho is the turpentine concentration obtained from the calibration curve, μ g/L;
m is fresh sample weight g;
wdm-soil dry matter content,%.
wdmThe content of the turpentine is measured according to the method HJ 613-2011, and the content W of the turpentine in the soil is obtained through the above calculation formula and is calculated on a dry basis.
In the embodiment, the content of the turpentine in the soil is determined by using the purging and trapping-gas chromatography-mass spectrometry, and the instrument parameters and the pretreatment conditions are optimized and improved.
Compared with the method for measuring turpentine in water, the method disclosed by the invention has the advantages that the measured object, the sample pretreatment method and the instrument detection parameters are different. The turpentine in the water quality is detected as water, a sample can be directly placed into a purge bottle, and is measured on a computer after an internal standard is added, but the measuring object of the invention is soil, the soil has a certain adsorption effect on organic matters, and an extracting agent is required to be added for extraction. In addition, the calculation formulas of the water concentration and the dry soil concentration are different, one is the water concentration, and the concentration of the dry soil is calculated.
The above examples are only descriptions of the preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and various modifications and alterations made to the technical solution of the present invention without departing from the spirit of the present invention are intended to fall within the protection scope defined by the claims of the present invention.
Claims (10)
1. The method for measuring turpentine in soil is characterized by comprising the following steps: the method comprises the following steps:
1) configuring a calibration curve sample
The concentration of a curve prepared by using 20mg/L turpentine use solution and 20mg/L substitute use solution is as follows: standard series of 2.0, 5.0, 10.0, 50.0, 100 and 200 mug/L, the volume of constant volume is 10mL, the solvent is pure water, 50 mug/L of internal standard use solution of 20mg/L is added into each calibration series, the calibration curve sample is placed in an automatic sample injector after being prepared, and the calibration curve sample is subjected to purging and trapping by a computer;
2) purge capture of calibration curve samples
Purging and trapping: temperature was room temperature, purge tube 10mL, purge flow: 40-50mL/min, purging time of 10-15min, dry-blowing time: 2min, blowing high-purity helium gas as the blowing gas, wherein the analysis temperature is 210-250 ℃, the analysis time is 2-4 min, the baking temperature is 220 ℃, the baking time is 15min, blowing the turpentine in the calibration curve sample obtained in the step 1) into a trap, and blowing the turpentine in the trap into a gas chromatograph after the turpentine is released by heating;
3) gas chromatography-mass spectrometry (GC-MS) determination of calibration curve samples
Performing chromatographic and mass spectrometric measurement on the turpentine purged in the step 2) to obtain peak areas of alpha-pinene and beta-pinene and a peak area response ratio of the peak areas to an internal standard,
chromatographic parameters: and (2) a DB-624 chromatographic column, wherein carrier gas is high-purity helium, the flow is 1-2 mL/min, and the injection port temperature is as follows: the split ratio is 10: 1-20: 1 at 220-250 ℃; temperature programming: maintaining at 35 deg.C for 4min, increasing to 100 deg.C at 5 deg.C/min, maintaining for 0min, increasing to 150 deg.C at 20 deg.C/min, and maintaining for 0 min;
mass spectrum parameters: adopting an EI source, wherein the ion source temperature is 230 ℃, the quadrupole rod temperature is 150 ℃, the solvent delay is 1-2 min, and the full scanning mode (Scan) and the selective ion monitoring mode (SIM) are simultaneously acquired within the scanning range of 40-300;
4) plotting a calibration curve
Taking the peak areas of the alpha-pinene and the beta-pinene in the step 3) and the response ratio of the peak areas of the alpha-pinene and the beta-pinene to the peak area of the internal standard as vertical coordinates, and taking the concentration as horizontal coordinates to establish a calibration curve and drawing the calibration curve;
5) addition of soil sample to be tested
Weighing 10.00g of fresh soil sample, placing the fresh soil sample into a 40ml purge bottle, adding 50 muL of internal standard use solution and 50 muL of substitute use solution by using a micro-injector, wherein the concentrations of the internal standard use solution and the substitute use solution are both 20mg/L, injecting the internal standard use solution and the substitute use solution into the fresh soil sample by using the micro-injector, continuously adding 10ml of extractant into the fresh soil sample, so that the concentrations of the internal standard and the substitute in the extractant are both 100 mug/L, and screwing a bottle cap;
6) extraction of soil sample to be tested in vortex oscillator
And (3) placing the purging bottle filled with the sample in the step 5) in a vortex oscillator, oscillating for 5-10 min in a continuous dot-inversion mode until the soil sample is completely oscillated and loosened, standing for 10min, placing the oscillated sample bottle in an automatic sample injector, and performing purging and trapping on the sample bottle on a machine.
7) Sweeping and trapping of soil sample to be detected
Sweeping the turpentine in the soil sample to be detected in the step 6) into a trap,
purging and trapping parameters: temperature was room temperature, purge tube 10mL, purge flow: 40-50mL/min, purging time of 10-15min, dry-blowing time: 2min, wherein the purge gas is high-purity helium, the desorption temperature is 210-250 ℃, the desorption time is 2-4 min, the baking temperature is 220 ℃, and the baking time is 15 min;
8) determination of gas chromatography mass spectrometry (GC-MS) of soil sample to be detected
Performing chromatographic and mass spectrometric measurement on the turpentine oil blown out in the step 7) to obtain the peak areas of alpha-pinene and beta-pinene of the soil sample to be detected and the response ratio of the peak areas of the alpha-pinene and the beta-pinene to the internal standard,
chromatographic parameters: and (2) a DB-624 chromatographic column, wherein carrier gas is high-purity helium, the flow is 1-2 mL/min, and the injection port temperature is as follows: the split ratio is 10: 1-20: 1 at 220-250 ℃; temperature programming: maintaining at 35 deg.C for 4min, increasing to 100 deg.C at 5 deg.C/min, maintaining for 0min, increasing to 150 deg.C at 20 deg.C/min, and maintaining for 0 min;
mass spectrum parameters: adopting an EI source, wherein the ion source temperature is 230 ℃, the quadrupole rod temperature is 150 ℃, the solvent delay is 1-2 min, and the full scanning mode (Scan) and the selective ion monitoring mode (SIM) are simultaneously acquired within the scanning range of 40-300;
9) calculation of results
The content W of turpentine in the soil is calculated according to the following formula:
in the formula: w is the content of turpentine in soil, mg/kg;
rho is the peak area of alpha-pinene and beta-pinene of the soil sample to be measured obtained in the step 8) and the response ratio of the peak area of the internal standard, and the turpentine concentration mu g/L can be obtained by combining the calibration curve in the step 4);
m is fresh sample weight g;
wdm-soil dry matter content,%.
wdmThe content of the turpentine is measured according to the method HJ 613-2011, and the content of the turpentine in the soil is obtained through the above calculation formula and is calculated on a dry basis.
2. The method for determining turpentine in soil according to claim 1, characterized in that: the internal standard using liquid in the step 5) is chlorobenzene D5.
3. The method for determining turpentine in soil according to claim 1, characterized in that: the substitute using liquid in the step 5) is one of dibromofluoromethane, toluene-D8 and 4-bromofluorobenzene.
4. The method for determining turpentine in soil according to claim 1, characterized in that: the extractant in the step 5) is one of a hydrochloric acid aqueous solution with the pH value of 5, a NaOH aqueous solution with the pH value of 9, a pure water solution and a saturated sodium chloride aqueous solution.
5. The method for determining turpentine in soil according to claim 1, characterized in that: purging and trapping parameters in the step 2) and the step 7): trapping temperature was room temperature, purge tube 10mL, purge flow: 40mL/min, purge time 15min, dry blow time: 2min, the purge gas is high-purity helium, the desorption temperature is 210 ℃, the desorption time is 2min, the baking temperature is 220 ℃, and the baking time is 15 min.
6. The method for determining turpentine in soil according to claim 1, characterized in that: the chromatographic parameters in steps 3) and 8): the carrier gas of a DB-624 chromatographic column (20m multiplied by 0.18mm multiplied by 1.0 μm) is high-purity helium, the flow rate is 1mL/min, the injection port temperature: the split ratio is 20:1 at 220 ℃; temperature programming: keeping at 35 deg.C for 4min, increasing to 100 deg.C at 5 deg.C/min, keeping for 0min, increasing to 150 deg.C at 20 deg.C/min, and keeping for 0 min.
7. The method for determining turpentine in soil according to claim 1, characterized in that: the mass spectrum parameters in the steps 3) and 8): the EI source is adopted, the ion source temperature is 230 ℃, the quadrupole rod temperature is 150 ℃, the solvent delay is 1min, the full scanning mode (Scan) and the selective ion monitoring mode (SIM) are simultaneously acquired, and the scanning range is 40-270.
8. The method for determining turpentine in soil according to claim 1, characterized in that: purging and trapping parameters in the step 2) and the step 7): trapping temperature was room temperature, purge tube 10mL, purge flow: 50mL/min, purge time 10min, dry-blow time: 2min, the purge gas is high-purity helium, the desorption temperature is 250 ℃, the desorption time is 4min, the baking temperature is 220 ℃, and the baking time is 15 min.
9. The method for determining turpentine in soil according to claim 1, characterized in that: the chromatographic parameters in steps 3) and 8): the carrier gas of a DB-624 chromatographic column (20m multiplied by 0.18mm multiplied by 1.0 μm) is high-purity helium, the flow rate is 2mL/min, the injection port temperature: the split ratio is 10:1 at 250 ℃; temperature programming: keeping at 35 deg.C for 4min, increasing to 100 deg.C at 5 deg.C/min, keeping for 0min, increasing to 150 deg.C at 20 deg.C/min, and keeping for 0 min.
10. The method for determining turpentine in soil according to claim 1, characterized in that: the mass spectrum parameters in the steps 3) and 8): the method comprises the steps of adopting an EI source, enabling the ion source temperature to be 230 ℃, the quadrupole rod temperature to be 150 ℃, enabling a solvent to delay for 2min, and simultaneously collecting in a full scanning mode (Scan) and a selective ion monitoring mode (SIM), wherein the scanning range is 50-300.
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| CN115236239A (en) * | 2022-08-09 | 2022-10-25 | 多特瑞(上海)商贸有限公司 | Method for detecting content of alpha-copal in schisandra essential oil |
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