Solid phase extraction column and its application in detecting and analyzing polycyclic aromatic hydrocarbons

Abstract

The present application relates to the field of environmental pollutant chemical detection and analysis technology, and particularly relates to a solid phase extraction column and application thereof. The present application adopts HLB, floresi silica and anhydrous sodium sulfate composite filler, combines the chemical structure characteristics of 16 polycyclic aromatic hydrocarbons contained in the sample to be purified, utilizes the specific surface area, polarity, adsorption capacity and other filler properties of different fillers, and plays a synergistic effect among each other, improves the purification recovery rate of 16 polycyclic aromatic hydrocarbons in the sample, improves the detection sensitivity and accuracy, and provides a standardized method for polycyclic aromatic hydrocarbon detection.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of environmental pollutant chemical detection and analysis, and particularly relates to a solid phase extraction column and application thereof. BACKGROUND

[0002] Polycyclic aromatic hydrocarbons (PAHs) are a class of compounds released in the process of thermal cracking and incomplete combustion of fossil energy and other organic matters. Due to its high biological activity, persistence, liposolubility and other characteristics, and can enter the human body through food, it causes harm to human health, and is listed as a typical persistent organic pollutant (PoPs). After PAHs enter mammalian cells and are metabolically activated, toxic intermediates are generated, which will irreversibly damage macromolecules (DNA, protein, lipid, etc.) in cells, and cause certain harm to human health. The PAHs commonly known as having significant teratogenic, carcinogenic and mutagenic effects include naphthalene, acenylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, benz[a]anthracene, benz[b]fluoranthene, benz[k]fluoranthene, benz[a]pyrene, indeno[1,2,3-c,d]pyrene, dibenzo[a,h]anthracene and benz[g,h,i]perylene.

[0003] The content of polycyclic aromatic hydrocarbons in the environment or biological samples is usually very low, which is called trace substance, and its detection usually needs a pretreatment method with high extraction rate and high recovery rate and an accurate qualitative and quantitative detection method. For the separation and detection of polycyclic aromatic hydrocarbons, paper chromatography and thin layer chromatography are traditionally used to separate PAHs, and then UV-vis and fluorescence are combined for detection. With the maturity of high performance liquid chromatography, gas chromatography, mass spectrometry and other technologies, the commonly used methods for separating and detecting polycyclic aromatic hydrocarbons at present include HPLC, GC, LC-MS and GC-MS. Even if modern analysis instruments are used, the pretreatment of biological samples with complex components still has some defects and deficiencies in the commonly used traditional and modern methods, such as complicated operation, excessive reagent consumption, long time consumption, low accuracy and sensitivity, etc., which still cannot meet the requirements of simplicity, speed, efficiency and accuracy for routine monitoring. SUMMARY

[0004] In order to overcome the defects of the prior art, the purpose of the present application is to provide a solid phase extraction column, which significantly improves the extraction and purification effect of polycyclic aromatic hydrocarbons in air, soil, water, blood (venous blood, umbilical cord blood), urine and other samples, and improves the sensitivity of analysis.

[0005] Meanwhile, another object of the present application is to provide the application of the solid phase extraction column in the extraction and separation of polycyclic aromatic hydrocarbons, after the sample is pretreated by using the ultrasonic rapid extraction technology, the sample is purified by the solid phase extraction column, and finally the polycyclic aromatic hydrocarbons are qualitatively and quantitatively analyzed, so that the detection accuracy and sensitivity are improved, and the solid phase extraction column can be used as a potential standard detection method for polycyclic aromatic hydrocarbons in different samples.

[0006] In order to achieve the above object, the technical scheme adopted by the present application is as follows:

[0007] A solid phase extraction column is prepared by filling the following fillers: HLB, FLORISIL and anhydrous sodium sulfate.

[0008] The HLB filler is a kind of polymer adsorbent with strong hydrophobicity and good water wettability, and the hard polystyrene molecules are used as the matrix, for example, the matrix is obtained by polymerization of N-vinylpyrrolidone and divinylbenzene in proportion.

[0009] Optionally, the mass ratio of HLB, FLORISIL and anhydrous sodium sulfate is 2:2:1. Optionally, the HLB is purchased from the brand: Copure (product number HLB-1-50, 50g / bottle, content: ≥100(%), material: granular powder).

[0010] Optionally, the solid phase extraction column is prepared by sequentially wet filling HLB, FLORISIL and anhydrous sodium sulfate into an empty column.

[0011] Further, the solid phase extraction column is prepared by the following preparation method: 200mg HLB, 200mg FLORISIL and 100mg anhydrous sodium sulfate are sequentially added to a disposable empty column with an inner diameter of 20mm by wet filling method, and then compacted and activated. It should be explained that under the condition of determining the type of filler, the person skilled in the art can adjust the amount of each filler based on the above-mentioned inner diameter and the mass of each filler and the mass ratio, and the adjusted amount of each filler is an equivalent adjustment based on the technical concept of the present application and the general technical knowledge in the art, which is within the protection scope of the present application.

[0012] As a preferred, in some embodiments, the specific preparation method of the solid phase extraction column comprises: 200mg HLB, 200mg FLORISIL and 100mg anhydrous sodium sulfate are respectively weighed in three 10mL centrifuge tubes as suspension medium, 2mL treated anhydrous n-hexane is added to each tube as dispersion phase, and then ultrasonic treatment is carried out for 20 minutes, so that the microparticles are highly dispersed in the medium and in a suspended state, and then the homogenate is sequentially pressed into a 10ml disposable empty column under high pressure to prepare a solid phase extraction column with a uniform and compact packed bed.

[0013] The solid phase extraction column of the present application adopts HLB, Florisil and anhydrous sodium sulfate composite fillers, combines the chemical structure characteristics of 16 polycyclic aromatic hydrocarbons contained in the sample to be purified, utilizes the specific surface area, polarity, adsorption capacity and other filler properties of different fillers, and plays a synergistic effect among each other, thereby improving the purification recovery rate of the 16 polycyclic aromatic hydrocarbons in the sample, improving the detection sensitivity and accuracy, and providing a standardized method for the detection of polycyclic aromatic hydrocarbons.

[0014] A polycyclic aromatic hydrocarbon detection method sequentially comprises sampling, pre-extraction, purification extraction, quantitative and / or qualitative detection; wherein the polycyclic aromatic hydrocarbons in the sample are extracted through pre-extraction and purification extraction, and the purification extraction is performed by using the above-mentioned solid phase extraction column.

[0015] Optionally, the specific operation steps of the purification extraction include: pre-washing the solid phase extraction column with ultrapure water, activating the extraction column with an eluent, then injecting the pre-extracted sample into the solid phase extraction column, washing the solid phase extraction column with ultrapure water, discarding the effluent fraction, and then eluting and collecting the fraction with the eluent for standby.

[0016] Optionally, the eluent is a mixture of n-hexane and dichloromethane at a ratio of 1:1, and the elution flow rate is 2 ml / min.

[0017] Optionally, the sample is a blood sample; the specific steps of the pre-extraction include adding NaOH-ethanol aqueous solution to the blood sample, ultrasonic treatment, then adding an extractant, liquid-liquid extraction to collect the organic phase, repeating the above operation twice, combining the organic phases, adding a solvent to dissolve after concentrating to near dryness, and standby; the extractant is a mixture of n-hexane and diethyl ether at a volume ratio of 9:1. Further optionally, the ethanol aqueous solution is a 90% ethanol content aqueous solution; the ultrasonic treatment is ultrasonic treatment at 60℃ water bath for 30 min; and the liquid-liquid extraction is performed by using a shaker for 15 min.

[0018] Optionally, the sample is a urine sample or a water sample; the specific steps of the pre-extraction include adding an extractant to the blood sample, liquid-liquid extraction to collect the organic phase, repeating the above operation twice, combining the organic phases, adding a solvent to dissolve after concentrating to near dryness, and standby; the extractant is a mixture of n-hexane and diethyl ether at a volume ratio of 9:1. Further optionally, the liquid-liquid extraction is performed by using a shaker for 15 min.

[0019] Optionally, the sample is an air sample; the specific steps of the pre-extraction include taking the air sample sampling filter membrane, cutting it into pieces and putting it into a container, adding an extractant, ultrasonic extraction for 30-60 min, then adding a solvent to dissolve after concentrating to dryness, and standby.

[0020] Or the sample is a soil sample; the specific steps of the pre-extraction include taking the soil sample into a container, adding an extractant, vortexing for 1 min and ultrasonic extraction for 15 min in sequence, centrifuging to take the supernatant, repeating the above operation twice, combining the extraction liquid, adding a solvent for redissolution after concentration to near dryness, and reserving for use; wherein the extractant is a mixture of n-hexane and diethyl ether 9:1.

[0021] Optionally, the redissolution solvent is n-hexane.

[0022] Optionally, in some embodiments of the present application, high performance liquid chromatography is used for qualitative and quantitative detection, and it should be understood that liquid chromatography-mass spectrometry and gas chromatography-mass spectrometry can also be used for qualitative and quantitative detection.

[0023] Further optionally, the liquid chromatography conditions are as follows: the chromatographic column is Supelcosil PAH, 250mmx4.6mm, 5um; the mobile phase is water and acetonitrile; the mobile phase flow rate is 1.5mL / min; the column temperature is 30℃; and the gradient elution program is set as follows: 65% acetonitrile+35% water, maintaining for 27min, increasing by 5% acetonitrile / min to 100% acetonitrile until the peak is finished.

[0024] The present application establishes a detection method for 16 kinds of polycyclic aromatic hydrocarbons according to the characteristics of 16 kinds of PAHs compounds with significant teratogenic, carcinogenic and mutagenic effects and the characteristics of different environmental samples and biological samples, especially the extraction and purification treatment method of polycyclic aromatic hydrocarbons in the sample. With n-hexane / ethyl ether as the extractant and ultrasonic extraction, the extraction process is simplified and the detection efficiency is improved; the application of HLB, floresil silica gel and anhydrous sodium sulfate composite solid phase extraction column can be applied to various environmental samples and biological samples, purify the impurities in the composition, and at the same time ensure a high recovery rate. The method is convenient, fast and high in sensitivity, and is suitable for content analysis of PAHs in different samples, and provides a good method basis for PAHs detection research work. BRIEF DESCRIPTION OF DRAWINGS

[0025] FIG. 1 is a comparison chart of extraction efficiency of different extractants in test example 1; Figure 1

[0026] FIG. 2 is a comparison chart of purification recovery rate of different solid phase extraction columns in test example 2. Figure 2 DETAILED DESCRIPTION

[0027] ​​The technical solutions of the present application are described in detail below through specific examples. The fillers HLB are all purchased from the brand: Copure (product code HLB-1-50, 50 g / bottle, content ≥: 100 (%), material: granular powder), and the Florisil silicas all refer to the commercially available FLORISIL magnesium silicate adsorbent.

[0028] Example 1

[0029] This example provides a solid phase extraction column prepared by using HLB, Florisil silica and anhydrous sodium sulfate as composite fillers:

[0030] The specific preparation method is as follows:

[0031] In three 10 mL centrifuge tubes, 200 mg of polystyrene divinylbenzene pyrrolidone HLB, 200 mg of Florisil silica, and 100 mg of anhydrous sodium sulfate were weighed as a suspension medium, 2 mL of treated anhydrous n-hexane was added to each tube as a dispersion phase, and then ultrasonic treatment was performed for 20 minutes to make the microparticles highly dispersed and suspended in the medium. Then, the polystyrene divinylbenzene pyrrolidone HLB, Florisil silica and anhydrous sodium sulfate were homogenously grinded and pressed into 10 ml column tubes under high pressure to prepare a solid phase extraction column with a uniform and compact packed bed.

[0032] Example 2

[0033] This example provides a standard solution for detecting polycyclic aromatic hydrocarbons, and the preparation method includes: using a mixed solution of n-hexane / acetone (1:1) to prepare 16 PAHs into a mixed standard stock solution with a concentration of 10 mg / L, and storing at -20℃. When used, it is diluted with acetonitrile into a mixed standard working solution as shown in Table 1. Seven concentrations of 0.0, 0.05, 0.1, 0.5, 1.0, 2.0 and 5.0 μg / mL are selected when preparing the standard series solution, and the linear correlation coefficients of the standard curve are all ≥0.999.

[0034] Table 1 Basic information table of 16 PAHs mixed standard working solution

[0035]

[0036]

[0037] Example 3

[0038] This example provides a method for detecting polycyclic aromatic hydrocarbons in blood samples, and the specific operation steps include:

[0039] 1. Sample pretreatment:

[0040] 1) Extraction: Take 2 mL blood in a 15 mL centrifuge tube, add 4 mL 0.4 mol / L NaOH-ethanol aqueous solution (ethanol: water = 9: 1), take out after ultrasonic treatment at 60°C for 30 min, add 3 mL extractant (9: 1 volume ratio of n-hexane / ether) (10% ether) to the centrifuge tube, mix well, and place on a shaker for liquid-liquid extraction for 15 min; collect the upper organic phase with a stoppered centrifuge tube, repeat the above experiment 2 times (10 min each time) with 3 mL n-hexane / ether (10% ether) and inject the collected organic phase into the first collected centrifuge tube; after concentration of the mixed organic phase to near dryness by a rotary evaporator, add 1 mL n-hexane and store in a refrigerator;

[0041] 2) Purification: Pre-wash the solid phase extraction column (500 mg, 6 mL) provided in Example 1 with ultrapure water, then activate with 10 mL of a mixture of n-hexane and dichloromethane (1:1), then inject the sample obtained after step 1) into the solid phase extraction column, load, and adjust the pressure regulator so that the flow rate does not exceed 2 mL / min; wash the adsorption column with 10 mL of ultrapure water, and finally elute with 15 mL of a mixture (n-hexane: dichloromethane) = 1:1). Concentrate the obtained extract to 1 mL; slowly blow dry under high-purity nitrogen, and finally add a quantitative internal standard and a recovery internal standard, and dilute to 500 μL with acetonitrile for testing;

[0042] 2. Qualitative and quantitative detection:

[0043] After sample pretreatment, the sample to be tested is detected qualitatively and quantitatively by high performance liquid chromatography, and the concentration standard curve is drawn using the standard solution provided in Example 2, and the concentration content of the detected polycyclic aromatic hydrocarbons in the sample is calculated; wherein the liquid chromatography conditions are: chromatographic column: Supelcosil PAH, 250 mm x 4.6 mm, 5 μm; mobile phase is water and acetonitrile; mobile phase flow rate is 1.5 mL / min; column temperature is 30°C; gradient elution program is set as: 65% acetonitrile + 35% water, maintained for 27 min, increased by 5% acetonitrile / min to 100% acetonitrile until the peak is out.

[0044] Example 4

[0045] The present embodiment provides a method for detecting polycyclic aromatic hydrocarbons in an air sample, and the specific operation steps include:

[0046] 1. Sample pretreatment:

[0047] 1) Extraction: Take a quarter of a 90 mm diameter sampling filter membrane, cut it into pieces, and put it into a 10 mL round-bottomed colorimetric tube, and add 2.5 mL of extractant (9: 1 volume ratio of n-hexane / ether) to the tube, cap it, and ultrasonic treat in a water bath for 30-60 min, and then purify;

[0048] 2) Purification: The solid phase extraction column (500 mg, 6 mL) provided in Example 1 was pre-rinsed with ultrapure water, then activated with 10 mL of a mixture of n-hexane and dichloromethane (n-hexane:dichloromethane) = 1:1, and then the sample obtained after the extraction in step 1) was injected into the solid phase extraction column, loaded, and the pressure regulator was adjusted so that the flow rate did not exceed 2 mL / min; the adsorption column was rinsed with 10 mL of ultrapure water, and finally eluted with 15 mL of a mixture (n-hexane:dichloromethane) = 1:1. The obtained extract was concentrated to 1 mL; slowly blown dry under high-purity nitrogen, and finally quantified with the addition of a quantitative internal standard and a recovery internal standard, and made up to 500 μL with acetonitrile for testing;

[0049] 2. Qualitative and quantitative detection:

[0050] The sample after sample pretreatment was detected qualitatively and quantitatively by high-performance liquid chromatography, and the concentration standard curve was drawn using the standard solution provided in Example 2, and the concentration content of the detected polycyclic aromatic hydrocarbons in the sample was calculated; wherein the liquid chromatography conditions are: the chromatographic column is Supelcosil PAH, 250 mm x 4.6 mm, 5 μm; the mobile phase is water and acetonitrile; the flow rate of the mobile phase is 1.5 mL / min; the column temperature is 30°C; and the gradient elution program is set as: 65% acetonitrile + 35% water, maintained for 27 min, increased by 5% acetonitrile / min to 100% acetonitrile until the peak is finished.

[0051] Example 5

[0052] The present embodiment provides a method for detecting polycyclic aromatic hydrocarbons in soil samples, and the specific operation steps include:

[0053] 1. Sample pretreatment:

[0054] 1) Extraction: Take 10 g of soil sample (oven dried and homogenized into powder), add to a 50 mL centrifuge tube, add 25 mL of n-hexane / ether (10% ether), vortex extract for 1 min, and ultrasonic for 15 min; centrifuge at 4000 rpm for 6 min, pour the supernatant into a 250 mL round-bottom flask, and then add 15 mL of the extraction agent (n-hexane / ether in a volume ratio of 9:1) in turn, repeat the above operation 2 times, combine the extract, and concentrate to near dryness by rotary evaporation, then dissolve with 2 mL of n-hexane for purification;

[0055] 2) Purification: The solid phase extraction column (500 mg, 6 mL) provided in Example 1 was pre-rinsed with ultrapure water, then activated with 10 mL of a mixture of n-hexane and dichloromethane (n-hexane:dichloromethane) = 1:1, and then the sample obtained after the extraction in step 1) was injected into the solid phase extraction column, loaded, and the pressure regulator was adjusted so that the flow rate did not exceed 2 mL / min; the adsorption column was rinsed with 10 mL of ultrapure water, and finally eluted with 15 mL of a mixture (n-hexane:dichloromethane) = 1:1. The obtained extract was concentrated to 1 mL; slowly blown dry under high-purity nitrogen, and finally quantified with the addition of a quantitative internal standard and a recovery internal standard, and made up to 500 μL with acetonitrile for testing;

[0056] 2. Qualitative and quantitative detection:

[0057] The sample after sample pretreatment was detected by high performance liquid chromatography for qualitative and quantitative detection, and the concentration standard curve was drawn using the standard solution provided in Example 2, and the concentration content of the detected polycyclic aromatic hydrocarbons in the sample was calculated; wherein the liquid chromatography conditions are: chromatographic column: Supelcosil PAH, 250 mm x 4.6 mm, 5 μm; the mobile phase is water and acetonitrile; the flow rate of the mobile phase is 1.5 mL / min; the column temperature is 30°C; and the gradient elution program is set as: 65% acetonitrile + 35% water, maintained for 27 min, increased by 5% acetonitrile / min to 100% acetonitrile until the peak is finished.

[0058] Example 6

[0059] The present embodiment provides a method for detecting polycyclic aromatic hydrocarbons in urine samples, and the specific operation steps include:

[0060] 1. Sample pretreatment:

[0061] 1) Extraction: Take 10 mL of urine sample and add it to a 50 mL centrifuge tube, add 15 mL of extractant (n-hexane / ether at a volume ratio of 9:1), shake for 5 min, stand for stratification, collect the organic phase, and place it in a 250 mL receiving bottle, repeat the extraction twice, combine the organic phase, and stand for 30 min, then concentrate to near dryness by rotary evaporation, dissolve with 2 mL of n-hexane, and then purify;

[0062] 2) Purification: The solid phase extraction column (500 mg, 6 mL) provided in Example 1 was pre-rinsed with ultrapure water, then activated with 10 mL of a mixture of n-hexane and dichloromethane (n-hexane:dichloromethane) = 1:1, and then the sample obtained after the extraction in step 1) was injected into the solid phase extraction column, loaded, and the pressure regulator was adjusted so that the flow rate did not exceed 2 mL / min; the adsorption column was rinsed with 10 mL of ultrapure water, and finally eluted with 15 mL of a mixture (n-hexane:dichloromethane) = 1:1. The obtained extract was concentrated to 1 mL; slowly blown dry under high-purity nitrogen, and finally quantified with the addition of a quantitative internal standard and a recovery internal standard, and made up to 500 μL with acetonitrile;

[0063] 2. Qualitative and quantitative detection:

[0064] The sample after sample pretreatment was detected by high performance liquid chromatography for qualitative and quantitative detection, and the concentration standard curve was drawn using the standard solution provided in Example 2, and the concentration content of the detected polycyclic aromatic hydrocarbons in the sample was calculated; wherein the liquid chromatography conditions are: chromatographic column: Supelcosil PAH, 250 mm x 4.6 mm, 5 μm; the mobile phase is water and acetonitrile; the flow rate of the mobile phase is 1.5 mL / min; the column temperature is 30°C; and the gradient elution program is set as: 65% acetonitrile + 35% water, maintained for 27 min, increased by 5% acetonitrile / min to 100% acetonitrile until the peak is out.

[0065] Example 7

[0066] The present embodiment provides a method for detecting polycyclic aromatic hydrocarbons in a water sample, and the specific operation steps include:

[0067] 1. Sample pretreatment:

[0068] 1) Extraction: Take 1 L of water sample into a 2 L separatory funnel, add 30 g of NaCl to dissolve, then add 50 mL of extractant (n-hexane / ether at a volume ratio of 9:1), shake for 5 min, stand for separation, collect the organic phase, and put it into a 250 ml receiving bottle, repeat the extraction twice, combine the organic phase, and stand for 30 min. After the extract is concentrated to near dryness by rotary evaporation, dissolve it with 2 mL of n-hexane and then purify it;

[0069] 2) Purification: The solid phase extraction column (500 mg, 6 mL) provided in Example 1 was pre-rinsed with ultrapure water, then activated with 10 mL of a mixture of n-hexane and dichloromethane (n-hexane:dichloromethane) = 1:1, and then the sample obtained after the extraction in step 1) was injected into the solid phase extraction column, loaded, and the pressure regulator was adjusted so that the flow rate did not exceed 2 mL / min; the adsorption column was rinsed with 10 mL of ultrapure water, and finally eluted with 15 mL of a mixture (n-hexane:dichloromethane) = 1:1. The obtained extract was concentrated to 1 mL; under high-purity nitrogen, it was slowly blown dry, and finally, quantitative internal standards and recovery internal standards were added, and the volume was made up to 500 μL with acetonitrile for testing;

[0070] 2. Qualitative and quantitative detection:

[0071] The sample after pretreatment was detected qualitatively and quantitatively by high-performance liquid chromatography, and the concentration standard curve was drawn using the standard solution provided in Example 2, and the concentration content of the detected polycyclic aromatic hydrocarbons in the sample was calculated; wherein the liquid chromatography conditions are: the chromatographic column is Supelcosil PAH, 250 mm x 4.6 mm, 5 μm; the mobile phase is water and acetonitrile; the flow rate of the mobile phase is 1.5 mL / min; the column temperature is 30°C; and the gradient elution program is set as: 65% acetonitrile + 35% water, maintained for 27 min, with an increase of 5% acetonitrile / min to 100% acetonitrile until the peak is finished.

[0072] The standard sample detection and standard curve drawing in the qualitative and quantitative detection of polycyclic aromatic hydrocarbons in the above-mentioned sample are as follows:

[0073] Linear range and detection limit:

[0074] A series of standard solutions with concentrations of 0.0, 0.05, 0.1, 0.5, 1.0, 2.0, and 5.0 μg / mL were prepared, and the instrument conditions were optimized to start the analysis. The concentration of each component was taken as the abscissa, and the peak area was taken as the ordinate, and the linear equation of the 16 PAHs standard curve was measured (Table 2). Each component has a good linear relationship in the linear range, and the correlation coefficient reaches 0.9999.

[0075] Table 2 Linear range, linear equation, and correlation coefficient of 16 PAHs

[0076]

[0077]

[0078] Effect comparison parallel test 1

[0079] Test method:

[0080] 1. Experimental sample preparation: take the blank air sampling filter membrane, drop the standard solution provided in Example 2 on the filter membrane, prepare A, B, C, D four groups of parallel test samples;

[0081] 2. Data detection: for the extractant, group A uses acetonitrile as the extractant, group B uses n-hexane as the extractant, group C uses methanol as the extractant, and group D uses n-hexane / ether with a volume ratio of 9:1 as the extractant, other steps completely refer to the detection method and parameters provided in Example 4, and the detection data of each group of experimental samples is calculated according to the detection data, and the extraction efficiency = actual detection sample concentration / standard sample concentration.

[0082] In this test, the extraction effects of acetonitrile, n-hexane, methanol, and n-hexane / ether with a volume ratio of 9:1 are compared, as shown in Table 1 (the specific names of PAHs referred to by numbers 1-16 in the figure are listed in Table 1 above), and the results show that n-hexane / ether with a volume ratio of 9:1 as the extractant has good extraction efficiency for 16 kinds of PAHs, and the parallelism is good, which is significantly better than the other three extractants. Figure 1

[0083] Effect parallel comparison test 2

[0084] Test method:

[0085] 1. Experimental sample preparation: take the blank air sampling filter membrane, drop the standard solution provided in Example 2 on the filter membrane, prepare A, B, C, D four groups of parallel test samples, and set up a non-purification blank control group for each group;

[0086] 2. Data detection: group A samples are purified by the solid phase extraction column of Example 1 of the application, group B samples are purified by Bond Elut ENV, group C samples are purified by Florisil silica, and group D samples are purified by HLB, wherein the diameter size and total weight of the solid phase extraction column used in each group are the same, and other steps are detected according to the detection method provided in Example 4. The detection data of each group of experimental samples is calculated according to the detection data, and the purification recovery rate = (actual detection sample concentration-sample background concentration) / standard sample concentration, wherein the sample background concentration is the sample detection concentration without purification treatment.

[0087] This test investigates the purification effect of the HLB-Florisil silica-anhydrous sodium sulfate composite solid phase extraction column, Bond Elut ENV, Florisil silica, and HLB four kinds of solid phase extraction columns on the sample, as shown in Table 2 (the specific names of PAHs referred to by numbers 1-16 in the figure are listed in Table 1 above), and the results show that the HLB-Florisil silica-anhydrous sodium sulfate composite solid phase extraction column has good purification effect for 16 kinds of PAHs, and the parallelism is good, which is significantly better than the other three kinds of solid phase extraction columns. Figure 2 ​The results show that the HLB-Florisil-anhydrous sodium sulfate composite solid phase extraction column of the application has a synergistic effect in purification, the recovery rate of each target substance can reach more than 90%, the purification method is more simple, the amount of reagent consumed is less, the experiment has good repeatability, and a good recovery effect can be achieved.

[0088] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the present application, but not to limit them; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacement for part of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A solid-phase extraction column for qualitative and / or quantitative detection of polycyclic aromatic hydrocarbons (PAHs) in a sample, wherein the sample is derived from an environmental or biological source, the column comprising an HLB packing layer, a Florisic silica layer, and an anhydrous sodium sulfate layer, wherein the Florisic silica layer is packed between the HLB packing layer and the anhydrous sodium sulfate layer, and the anhydrous sodium sulfate layer is packed at one end near the inlet of the solid-phase extraction column, wherein the mass ratio of HLB to Florisic silica is 2:2, and the mass ratio of HLB to anhydrous sodium sulfate is 2:1, characterized in that... Based on Florisi silica, the loading of packing material in the solid-phase extraction column is 200 mg of Florisi silica for a column tube with an inner diameter of 20 mm; the packing material HLB, Florisi silica, and / or anhydrous sodium sulfate are filled into the solid-phase extraction column by wet packing; the polycyclic aromatic hydrocarbons include at least one of the following polycyclic aromatic hydrocarbons: naphthalene, acenaphthene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysoprase, benzo[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indo[1,2,3-c,d]pyrene, dibenzo[a,h]anthracene, benzo[g,h,i]perylene.

2. The solid-phase extraction column as described in claim 1, characterized in that, The HLB packing material is Copure HLB-1-50.

3. The solid-phase extraction column as described in claim 1 or 2, characterized in that, The dispersed phase used in the wet packing process is n-hexane.

4. A method for extracting polycyclic aromatic hydrocarbons from a sample, comprising sequentially sampling, pre-extraction, and purification extraction, wherein a hexane:ethyl ether mixture with a volume ratio of 9:1 is used for pre-extraction, the polycyclic aromatic hydrocarbons are purified and extracted using the solid-phase extraction column described in claim 1, 2, or 3, and the polycyclic aromatic hydrocarbons are obtained by elution with a hexane:dichloromethane mixture with a volume ratio of 1:

1.

5. The method as described in claim 4, characterized in that, The method further includes activating the solid-phase extraction column before sample loading.

6. The method as described in claim 5, characterized in that, The activator components used are the same as those in the eluent.

7. The method as described in claim 4, characterized in that, The method further includes rinsing the solid-phase extraction column with water before loading the sample.

8. The method as described in claim 4, characterized in that, The solvent used for purifying and extracting the sample was n-hexane.

9. The application of the method according to any one of claims 4-8 in the qualitative and / or quantitative detection of polycyclic aromatic hydrocarbons in a sample derived from blood, air, soil, urine, and / or water.

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