CN113776906A - Method for improving detection rate of polycyclic aromatic hydrocarbons in high-water-content soil sample - Google Patents
Method for improving detection rate of polycyclic aromatic hydrocarbons in high-water-content soil sample Download PDFInfo
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Abstract
The invention discloses a method for improving the detection rate of polycyclic aromatic hydrocarbons in a high-water-content soil sample, which comprises the following steps: pretreating a soil sample; uniformly stirring the soil sample and diatomite, and adding a substitute and an extracting agent for extraction treatment to obtain a sample extracting solution; dehydrating the sample extracting solution; carrying out secondary dehydration treatment and purification treatment on the sample extracting solution after the dehydration treatment; concentrating the sample extracting solution to obtain a to-be-detected sample solution containing polycyclic aromatic hydrocarbons; and adding an internal standard substance into the sample solution to be detected, and detecting the content of the polycyclic aromatic hydrocarbon. The method can be used for measuring the soil sample with the water content of more than 15%, freeze-drying is not needed for 24 hours, energy can be saved, and the detection rate can be improved; by a physical and chemical dewatering method, the use amount of the anhydrous sodium sulfate is reduced, the anhydrous sodium sulfate is prevented from being hardened by water phase penetration, the polycyclic aromatic hydrocarbon elution pressure is reduced, and the qualification rate and the detection rate of polycyclic aromatic hydrocarbon detection in a soil sample are improved.
Description
Technical Field
The invention belongs to the technical field of polycyclic aromatic hydrocarbon determination, and particularly relates to a method for improving the detection rate of polycyclic aromatic hydrocarbon in a soil sample with high water content.
Background
The existing polycyclic aromatic hydrocarbon detection standards in soil, namely a gas chromatography-mass spectrometry for determining semi-volatile organic compounds in HJ834-2017 soil and sediments and a gas chromatography-mass spectrometry for determining polycyclic aromatic hydrocarbons in HJ805-2016 soil and sediments, adopt a freeze-drying method and an anhydrous sodium sulfate drying method as pretreatment methods for high-water-content soil samples.
The freeze-drying method comprises the following steps: soil samples are placed in a freeze dryer for freeze drying, typically for at least 24 hours. Long time consumption, large power consumption and difficult control of the recovery rate of the added standard.
Drying with anhydrous sodium sulfate: the soil sample is ground and extracted together with anhydrous sodium sulfate, or the extract is dehydrated by anhydrous sodium sulfate. The soil sample and the anhydrous sodium sulfate are ground together, so that the extraction method is not suitable for the extraction by a rapid solvent extraction method, and the anhydrous sodium sulfate can be separated out to block an extraction pipeline when the temperature of the pipeline is low; the extraction solution is dehydrated by using anhydrous sodium sulfate, the standard requirement of the extraction solution is that 20g of soil sample is taken, the using amount of the anhydrous sodium sulfate is about 5g, under the condition that a target is convenient to elute, water does not completely penetrate the anhydrous sodium sulfate, 2-3 mL of water can be removed, and the extraction solution is only suitable for the soil sample with the water content of less than 15%; if the water content of the soil sample is high, water can penetrate through anhydrous sodium sulfate to cause hardening of the anhydrous sodium sulfate, and a target cannot be eluted subsequently; if the extraction liquid which is not thoroughly dewatered is subjected to secondary treatment, the workload is increased for a moment, and the sample recovery rate is seriously reduced for the second moment; if the use amount of the anhydrous sodium sulfate is increased, the elution difficulty of the target substance and the use amount of the eluent are increased, and the recovery rate of the target substance is reduced.
Disclosure of Invention
Aiming at the problems, the invention discloses a method for improving the detection rate of polycyclic aromatic hydrocarbon in a high-water-content soil sample, which comprises the following steps:
pretreating a soil sample;
uniformly stirring the soil sample and diatomite, and adding a substitute and an extracting agent for extraction treatment to obtain a sample extracting solution;
dehydrating the sample extracting solution;
carrying out secondary dehydration treatment and purification treatment on the sample extracting solution after the dehydration treatment;
concentrating the sample extracting solution subjected to secondary dehydration and purification treatment to obtain a to-be-detected sample solution containing polycyclic aromatic hydrocarbons;
and adding an internal standard substance into the sample solution to be detected, and detecting the content of the polycyclic aromatic hydrocarbon.
Still further, the pre-treating the soil sample comprises the steps of:
adopting a soil sample, removing weeds and stones in the soil sample, and sealing the soil sample in a brown glass bottle;
and (3) placing the soil sample in an enamel or glass tray, removing the branch rods and the blades, and fully and uniformly mixing.
Further, the extracting agent is a mixed solvent of n-hexane and acetone in a volume ratio of 1: 1.
Still further, the dehydration treatment of the sample extraction solution comprises the following steps:
step 1: blowing or rotary steaming the sample extraction liquid nitrogen to 3-5 mL;
step 2: adding 10-20 mL of n-hexane into the sample extracting solution, continuously blowing nitrogen or performing rotary evaporation to 3-5 mL, repeating the steps 1 and 2 for 2 times, and blowing or performing rotary evaporation to 1.5-2.5 mL of the sample extracting liquid nitrogen;
and step 3: and (3) removing water from the sample extracting solution obtained in the step (2) by using a separating funnel or a bus dropper.
Further, the second dehydration treatment and purification treatment of the sample extraction solution after the dehydration treatment comprises the following steps:
carrying out secondary dehydration treatment on the sample extracting solution after the dehydration treatment by using anhydrous sodium sulfate;
and purifying the sample extracting solution subjected to the secondary dehydration treatment.
Further, the concentration treatment conditions are as follows: the water temperature is 30-35 ℃, and the nitrogen blowing speed is 2-3 mL/min.
Further, the purification treatment uses a column of Flori silicon.
Further, the polycyclic aromatic hydrocarbon is acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo [ a ] a]Anthracene,
Benzo [ b ]]Fluoranthene, benzo [ k ]]Fluoranthene, benzo [ a ]]Pyrene, dibenzo [ a, h ]]Anthracene, indeno [1,2,3-cd]Pyrene and benzo [ g, h, i]A perylene.
Further, the inner partThe target substances are naphthalene-d 8, acenaphthene-d 10, phenanthrene-d 10,
-d12 and perylene-d 12.
Still further, the alternatives are 2-fluorobiphenyl and p-terphenyl-d 14.
Compared with the prior art, the invention has the beneficial effects that: the method can be used for measuring the soil sample with the water content of more than 15%, freeze-drying is not needed for 24 hours, energy can be saved, and the detection rate can be greatly improved; the mode of replacing the original pure chemical dewatering method by the mode of combining the physical dewatering method with the chemical dewatering method can reduce the using amount of the anhydrous sodium sulfate, prevent the anhydrous sodium sulfate from being penetrated and hardened by a water phase, reduce the elution pressure of the polycyclic aromatic hydrocarbon, improve the recovery rate of the polycyclic aromatic hydrocarbon and improve the qualification rate and the detection rate of polycyclic aromatic hydrocarbon detection in a soil sample.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and those skilled in the art can also obtain other drawings according to the drawings without creative efforts.
FIG. 1 shows a chromatogram of a soil sample 1 solution according to an embodiment of the invention;
FIG. 2 shows a chromatogram of a solution of a tagged soil sample 1 according to an embodiment of the invention;
FIG. 3 shows a chromatogram of a soil sample 2 solution according to an embodiment of the invention;
FIG. 4 shows a chromatogram of a solution of a tagged soil sample 2 according to an embodiment of the invention;
FIG. 5 shows a chromatogram of a soil sample 3 solution according to an embodiment of the invention;
FIG. 6 shows a chromatogram of a solution of a tagged soil sample 3 according to an embodiment of the invention;
fig. 7 shows a chromatogram of a quality control sample solution according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The reagents and equipment used in the examples of the present invention are as follows.
Reagent:
n-hexane: pesticide residue grade;
acetone: pesticide residue grade;
dichloromethane: pesticide residue grade;
diatomite: the top grade is pure;
florili silica column: the filler is Florisil silica, 1g, and the column volume is 6 mL;
anhydrous sodium sulfate: the top grade is pure;
internal standard substance: naphthalene-d 8, acenaphthene-d 10, phenanthrene-d 10,
-d12 and perylene-d 12, 1000 mg/L;
substitutes are as follows: 2-fluorobiphenyl and p-terphenyl-d 14, 1000 mg/L.
The instrument comprises the following steps:
a small funnel: tianjin sky glass Limited;
separating funnel: tianjin sky glass Limited;
a concentration cup: 250mL and 100mL of Beijing Laibutaike instruments GmbH;
brown glass bottle: tianjin sky glass Limited;
a parallel concentrator: MultiVap, beijing lebertaceae instruments ltd;
rotating the evaporator: BUCHI rotary evaporator R-300;
gas chromatography mass spectrometer: shimadzu GCMS-QP 2020.
The invention provides a method for improving the detection rate of polycyclic aromatic hydrocarbons in a high-water-content soil sample, which comprises the following steps:
pretreating a soil sample;
uniformly stirring the soil sample and diatomite, adding a substitute, adding a mixed solvent of n-hexane and acetone in a volume ratio of 1:1 as an extracting agent, and performing extraction treatment to obtain a sample extracting solution, wherein the sample extracting solution is an acetone-n-hexane-water polycyclic aromatic hydrocarbon extracting solution; illustratively, the mass of the soil sample is 20g, and the water content is 15-30%; uniformly stirring the soil sample and the diatomite, primarily dewatering the soil sample on one hand, and dispersing the soil sample on the other hand to increase the specific surface area of the soil sample; the substitutes are 2-fluorobiphenyl and p-terphenyl-d 14, and the loss or the contamination of the target object in the pretreatment operation of the soil sample can be monitored; the extraction treatment uses extraction equipment such as a rapid solvent instrument, a microwave extractor or a Soxhlet extractor; the usage amount of the extracting agent is related to the size of the extraction pool and the extraction times, and exemplarily, for a 40mL extraction pool, the extraction is carried out for 2 times, and the usage amount of the extracting agent is 80 mL;
converting the sample extracting solution into a normal hexane solvent system by normal hexane, and dehydrating; the dehydration treatment is physical dehydration;
carrying out secondary dehydration treatment and purification treatment on the sample extracting solution after the dehydration treatment; the secondary dehydration treatment is chemical dehydration, and anhydrous sodium sulfate is adopted to remove residual water in the sample extracting solution;
concentrating the sample extracting solution subjected to secondary dehydration and purification treatment to obtain a to-be-detected sample solution containing polycyclic aromatic hydrocarbons; the conditions of the concentration treatment were: the water temperature is 30-35 ℃, the nitrogen blowing speed is 2-3 mL/min, the water temperature is preferably 30 ℃, the nitrogen blowing speed is 3mL/min, and the detection limit of the target object can be reduced through concentration treatment;
and adding an internal standard substance into the sample solution to be detected, transferring the sample solution into a 2mL sample injection vial, and detecting the content of the polycyclic aromatic hydrocarbon by using a gas chromatography mass spectrometer. Wherein the internal standard substance is naphthalene-d 8, acenaphthene-d 10, phenanthrene-d 10, or naphthalene-d 10,
-d12 and perylene-d 12.
Polycyclic aromatic hydrocarbons include acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo [ a ] s]Anthracene,
Benzo [ b ]]Fluoranthene, benzo [ k ]]Fluoranthene, benzo [ a ]]Pyrene, dibenzo [ a, h ]]Anthracene, indeno [1,2,3-cd]Pyrene and benzo [ g, h, i]A perylene.
Since the first few substances in the 15 polycyclic aromatic hydrocarbons have low boiling points and volatility, and cross contamination is easily caused when the soil is dried in the shade, wet sample detection is recommended. However, water in the soil sample can form a water film to wrap the soil sample, and the n-hexane can dissolve the polycyclic aromatic hydrocarbon in the soil sample and is incompatible with water, so that the n-hexane is directly adopted for extraction, and the extraction efficiency is low. The acetone and the water are mutually soluble in any ratio, a water film can be destroyed, so that the extractant directly contacts with the polycyclic aromatic hydrocarbon in the soil, and the extraction efficiency is greatly improved, therefore, the extractant must adopt a mixed solvent of normal hexane and acetone in a volume ratio of 1: 1.
Meanwhile, when a wet soil sample is prepared, the dispersing agent cannot adopt anhydrous sodium sulfate, a small amount of water contained in the wet sample can dissolve part of the anhydrous sodium sulfate at high temperature and high pressure, the anhydrous sodium sulfate can be separated out to block a pipeline when the temperature is reduced, and an ASE pressure valve in a pipeline of the rapid solvent extraction instrument is abraded.
The pretreatment of the soil sample comprises the following steps:
adopting a soil sample, removing weeds and stones in the soil sample, and sealing the soil sample in a brown glass bottle;
and (3) placing the soil sample in an enamel or glass tray, removing the branch rods and the blades, and fully and uniformly mixing.
The dehydration treatment of the sample extracting solution comprises the following steps:
step 1: blowing or rotary steaming the sample extraction liquid nitrogen to 3-5 mL; at the moment, the solution is a small amount of acetone, normal hexane and water, the amount of water is basically not reduced due to high boiling point, the solution is in a turbid state, and the water and the acetone are mutually soluble and are insoluble in the normal hexane;
step 2: adding 10-20 mL of n-hexane into the sample extracting solution, continuously blowing nitrogen or performing rotary evaporation to 3-5 mL, repeating the steps 1 and 2 for 2 times, and blowing or performing rotary evaporation to 1.5-2.5 mL of the sample extracting liquid nitrogen; the boiling point of acetone is lower than that of normal hexane, normal hexane is added for multiple times to carry out nitrogen blowing or rotary evaporation operation, the acetone is basically volatilized, the residual solution is normal hexane and water which are not mutually soluble, and the solution is in a vertically layered state;
and step 3: and (3) removing moisture from the sample extracting solution obtained in the step (2) by using a separating funnel or a bus dropper, and waiting for purification treatment. At this point, a small amount of water remains in the solution, requiring secondary chemical removal of water.
Adding normal hexane into the acetone-normal hexane-water polycyclic aromatic hydrocarbon extraction solution for replacing a solvent system from acetone-normal hexane-water into normal hexane-water to obtain a normal hexane-water polycyclic aromatic hydrocarbon solution, wherein the normal hexane has a density of 0.66g/mL and a water density of 1.0g/mL due to the different densities of the normal hexane and the water, the lower layer is water, and the upper layer is a sample extraction solution of the normal hexane system.
Wherein, the existence of acetone can influence the dehydration effect, and the existence of moisture can influence purification efficiency, and sample solution purifies not well can influence polycyclic aromatic hydrocarbon's testing result, so this one step of dehydration is crucial.
The secondary dehydration treatment and purification treatment of the sample extracting solution after the dehydration treatment comprises the following steps:
carrying out secondary dehydration treatment on the sample extracting solution after the dehydration treatment by using anhydrous sodium sulfate;
and purifying the sample extracting solution subjected to secondary dehydration treatment by using a Flori silicon column.
Illustratively, the specific steps of the secondary dehydration treatment and the purification treatment of the sample extracting solution are as follows: fixing a Flori silica column on a solid phase extraction device, closing a control valve, plugging a small funnel by using glass wool, putting anhydrous sodium sulfate into the small funnel, and putting the small funnel on the Flori silica column; pouring 5mL of dichloromethane and 5mL of normal hexane into a small funnel, sequentially washing the small funnel, anhydrous sodium sulfate and a Flori silica column (the step is used for cleaning a vessel, the anhydrous sodium sulfate and the activated Flori silica column), opening a control valve to discard an effluent liquid, closing the control valve before the anhydrous sodium sulfate and the Flori silica column filler are exposed to air, uniformly transferring a sample extracting solution subjected to physical dehydration treatment onto the small funnel for secondary dehydration treatment, and allowing the effluent liquid to enter the Flori silica column to remove impurities. The concentrating vessel was washed three times with 2mL of n-hexane, the whole washing liquid was transferred to a small funnel, the control valve was slowly opened, and the sample extract purified by the Florisil column was received in a 100mL concentrating cup. Before exposing the filler to the air, adding 5-10 mL of dichloromethane with a volume ratio of 1: 4: eluting anhydrous sodium sulfate and Florisil column with n-hexane solvent, closing control valve after the Florisil column is soaked with the eluate for 2min, slowly opening control valve, and continuously collecting with the above 100mL concentration cup for concentration.
Wherein, it is when need notice washing anhydrous sodium sulfate with n-hexane or dichloromethane solvent and activation florisil silica post, need keep anhydrous sodium sulfate moist, there is n-hexane or dichloromethane solvent above the florisil silica post sieve, can not let the whole volatilization of solvent to prevent that the air from entering into the filler, and then block polycyclic aromatic hydrocarbon solution and flow out, can increase purification treatment's time to a certain extent, can lose certain polycyclic aromatic hydrocarbon moreover. And the anhydrous sodium sulfate in the purification treatment step is used for removing a small amount of residual moisture in the polycyclic aromatic hydrocarbon solution in the normal hexane system to obtain the moisture-free normal hexane polycyclic aromatic hydrocarbon solution. Because the dehydration treatment removes most of water, when the anhydrous sodium sulfate is used for removing a small amount of residual water in the polycyclic aromatic hydrocarbon solution in a normal hexane system, the water cannot penetrate through the anhydrous sodium sulfate to cause anhydrous sodium sulfate hardening, the subsequent elution of polycyclic aromatic hydrocarbon target objects is facilitated, the recovery rate of the target objects is improved, the usage amount of the anhydrous sodium sulfate can be saved, and the detection cost is reduced.
The method comprises the following steps of concentrating the sample extracting solution subjected to secondary dehydration and purification treatment to obtain a to-be-detected sample solution containing polycyclic aromatic hydrocarbon:
and concentrating the sample extracting solution into 1mL by using a parallel concentrator or a nitrogen blower to obtain a sample solution to be detected.
Chromatographic conditions are as follows:
sample inlet temperature: no split flow is carried out at 280 ℃, or split flow sample injection (when the sample concentration is higher or the instrument sensitivity is enough);
sample introduction amount: 1.0 μ L;
column flow rate: 1.0mL/min (constant flow);
column temperature: maintaining at 80 deg.C for 2min, increasing to 180 deg.C at 20 deg.C/min rate, maintaining for 5min, increasing to 300 deg.C at 10 deg.C/min rate, and maintaining for 10 min;
mass spectrum reference conditions:
an electron impact source (EI);
ion source temperature: 230 ℃;
ionization energy: 70 eV;
interface temperature: 280 ℃;
quadrupole temperature: 150 ℃;
mass scan range: 45amu to 450 amu;
solvent delay time: 5 min;
scanning mode: full Scan or ion mode (SIM).
Example 1:
according to the experimental process, 18.40g (accurate to 0.01g) of soil sample 1 (ninth package W20180710-007) is taken to measure the background concentration, and 18.29g (accurate to 0.01g) of the same soil sample is taken and added with 300ng of polycyclic aromatic hydrocarbon standard solution to be used as the standard-added soil sample 1 (ninth package JB-W20180710-007), and the standard-added recovery rate is measured.As shown in fig. 1 and fig. 2, the retention time and the quantitative ion of 15 polycyclic aromatic hydrocarbon targets can be measured by the method of the present invention, which are shown in table 1. Naphthalene-d 8, acenaphthene-d 10, phenanthrene-d 10,
The-d 12 and the perylene-d 12 are used as internal standard substances, so that the injection error of the instrument can be eliminated. The experimental results of the standard recovery rate are shown in table 1, and the standard recovery rates of 15 polycyclic aromatic hydrocarbon targets meet the requirements.
TABLE 1 soil sample 1 Standard recovery test results
Example 2:
according to the above experimental process, 15.18g (accurate to 0.01g) of soil sample 2 (package 10W 20180712-069) is taken to measure the background concentration, and 15.20g (accurate to 0.01g) of the same soil sample is taken and added with 300ng of polycyclic aromatic hydrocarbon standard solution to be used as the standard-added soil sample 2 (package 10 JB-W20180712-069) to measure the standard-added recovery rate. As shown in fig. 3 and 4, the retention time and the quantitative ion of the 15 polycyclic aromatic hydrocarbon targets are shown in table 2, and the experimental results prove that the standard recovery rates of the 15 polycyclic aromatic hydrocarbon targets meet the requirements.
TABLE 2 soil sample 2 standard recovery test results
Example 3:
according to the experimental process, 15.43g (accurate to 0.01g) of soil sample 3 (the ninth package W20180710-005) is taken to measure the background concentration, and 15.11g (accurate to 0.01g) of the same soil sample is taken and added with 300ng of polycyclic aromatic hydrocarbon standard solution to be used as the standard-added soil sample 3 (the ninth package JB-W20180710-005) to measure the standard-added recovery rate. As shown in fig. 5 and 6, the retention time and the quantitative ion of the 15 polycyclic aromatic hydrocarbon targets are shown in table 3, and the experimental results prove that the standard recovery rates of the 15 polycyclic aromatic hydrocarbon targets meet the requirements.
TABLE 3 soil sample 3 Standard recovery test results
The extraction and concentration process can be monitored by using 2-fluorobiphenyl and p-terphenyl-d 14 as substitutes, and the recovery rate of the substitutes in the soil sample is shown in table 4. It can be seen from table 4 that the recovery rate of the substitute is between 40% and 97%, and the requirement of 40% to 150% is met, thus proving the effectiveness of the invention.
TABLE 4 results of recovery of surrogate in soil samples
Quality control of the sample:
taking 4.02g of 1 part of quality control sample (10 th package W20180712-224, brand: carbofuran S0218), measuring the concentration of the polycyclic aromatic hydrocarbon according to the steps, and fig. 7 shows a chromatogram of the quality control sample solution, wherein the results are shown in the following table 5, and the concentrations of 15 polycyclic aromatic hydrocarbons in the quality control sample are all in the quality control range, thereby proving the effectiveness of the invention.
TABLE 5 quality control sample test results
According to the embodiments, the method for improving the detection rate of the polycyclic aromatic hydrocarbon in the high-water-content soil sample can be used for determining the standard recovery rate of the polycyclic aromatic hydrocarbon in the high-water-content soil sample, and can meet the standard requirements of gas chromatography-mass spectrometry for determining semi-volatile organic compounds of HJ834-2017 soil and sediments and the standard requirements of gas chromatography-mass spectrometry for determining polycyclic aromatic hydrocarbon in HJ805-2016 soil and sediments, and the determined quality control sample can meet the requirement of a quality control range, so that the effectiveness of the method is proved.
According to the method for improving the detection rate of the polycyclic aromatic hydrocarbon in the high-water-content soil sample, the soil sample with the water content of more than 15% can be measured, freeze-drying is not needed for 24 hours, energy can be saved, and the detection rate can be greatly improved; the mode of replacing the original pure chemical dewatering method by the mode of combining the physical dewatering method with the chemical dewatering method can reduce the using amount of the anhydrous sodium sulfate, prevent the anhydrous sodium sulfate from being penetrated and hardened by a water phase, reduce the elution pressure of the polycyclic aromatic hydrocarbon, improve the recovery rate of the polycyclic aromatic hydrocarbon and improve the qualification rate and the detection rate of polycyclic aromatic hydrocarbon detection in a soil sample.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for improving the detection rate of polycyclic aromatic hydrocarbons in a high-water-content soil sample is characterized by comprising the following steps:
pretreating a soil sample;
uniformly stirring the soil sample and diatomite, and adding a substitute and an extracting agent for extraction treatment to obtain a sample extracting solution;
dehydrating the sample extracting solution;
carrying out secondary dehydration treatment and purification treatment on the sample extracting solution after the dehydration treatment;
concentrating the sample extracting solution subjected to secondary dehydration and purification treatment to obtain a to-be-detected sample solution containing polycyclic aromatic hydrocarbons;
and adding an internal standard substance into the sample solution to be detected, and detecting the content of the polycyclic aromatic hydrocarbon.
2. The method for improving the detection rate of the polycyclic aromatic hydrocarbons in the soil sample with high water content according to claim 1, wherein the pretreatment of the soil sample comprises the following steps:
adopting a soil sample, removing weeds and stones in the soil sample, and sealing the soil sample in a brown glass bottle;
and (3) placing the soil sample in an enamel or glass tray, removing the branch rods and the blades, and fully and uniformly mixing.
3. The method for improving the detection rate of the polycyclic aromatic hydrocarbon in the soil sample with high water content according to claim 1, wherein the extracting agent is a mixed solvent of n-hexane and acetone with a volume ratio of 1: 1.
4. The method for improving the detection rate of the polycyclic aromatic hydrocarbon in the soil sample with high water content according to claim 1, wherein the step of dehydrating the sample extracting solution comprises the following steps:
step 1: blowing or rotary steaming the sample extraction liquid nitrogen to 3-5 mL;
step 2: adding 10-20 mL of n-hexane into the sample extracting solution, continuously blowing nitrogen or performing rotary evaporation to 3-5 mL, repeating the steps 1 and 2 for 2 times, and blowing or performing rotary evaporation to 1.5-2.5 mL of the sample extracting liquid nitrogen;
and step 3: and (3) removing water from the sample extracting solution obtained in the step (2) by using a separating funnel or a bus dropper.
5. The method for improving the detection rate of the polycyclic aromatic hydrocarbon in the soil sample with high water content according to claim 1, wherein the secondary dehydration treatment and purification treatment of the sample extracting solution after the dehydration treatment comprises the following steps:
carrying out secondary dehydration treatment on the sample extracting solution after the dehydration treatment by using anhydrous sodium sulfate;
and purifying the sample extracting solution subjected to the secondary dehydration treatment.
6. The method for improving the detection rate of the polycyclic aromatic hydrocarbon in the soil sample with high water content according to claim 1, wherein the concentration treatment conditions are as follows: the water temperature is 30-35 ℃, and the nitrogen blowing speed is 2-3 mL/min.
7. The method for increasing the detection rate of polycyclic aromatic hydrocarbons in a soil sample with high water content according to claim 1 or 5, wherein the purification treatment uses a Flori silicon soil column.
8. The method for increasing the detection rate of polycyclic aromatic hydrocarbons in the soil sample with high water content according to claim 1, wherein the polycyclic aromatic hydrocarbons are acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo [ a ]]Anthracene,
Benzo [ b ]]Fluoranthene, benzo [ k ]]Fluoranthene, benzo [ a ]]Pyrene, dibenzo [ a, h ]]Anthracene, indeno [1,2,3-cd]Pyrene and benzo [ g, h, i]A perylene.
9. The method for improving the polycyclic aromatic hydrocarbon detection rate in the soil sample with high water content as claimed in claim 1, wherein the internal standard substance is naphthalene-d 8, acenaphthene-d 10, phenanthrene-d 10,
-d12 and perylene-d 12.
10. The method for increasing the detection rate of polycyclic aromatic hydrocarbons in a soil sample with high water content as claimed in claim 1, wherein the substitute is 2-fluorobiphenyl and p-terphenyl-d 14.
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