CN113109481A - Method for simultaneously detecting four types of 13 antibiotics in drinking water source water body by solid phase extraction-liquid chromatography tandem mass spectrometry - Google Patents
Method for simultaneously detecting four types of 13 antibiotics in drinking water source water body by solid phase extraction-liquid chromatography tandem mass spectrometry Download PDFInfo
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- CN113109481A CN113109481A CN202110475591.8A CN202110475591A CN113109481A CN 113109481 A CN113109481 A CN 113109481A CN 202110475591 A CN202110475591 A CN 202110475591A CN 113109481 A CN113109481 A CN 113109481A
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- 229960004099 azithromycin Drugs 0.000 claims description 2
- MQTOSJVFKKJCRP-BICOPXKESA-N azithromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)N(C)C[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 MQTOSJVFKKJCRP-BICOPXKESA-N 0.000 claims description 2
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- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/08—Preparation using an enricher
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/027—Liquid chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N2030/042—Standards
- G01N2030/047—Standards external
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
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Abstract
The invention discloses a method for simultaneously detecting four types of 13 antibiotics in drinking water source water body by solid phase extraction-liquid chromatography tandem mass spectrometry, which comprises the following steps: filtering a water sample by a glass fiber membrane, adding disodium ethylene diamine tetraacetate, and adjusting the pH value to be 3 by formic acid; activating the HLB solid-phase extraction column by using methanol and formic acid aqueous solution in sequence, passing the water sample treated in the step one through the HLB solid-phase extraction column, keeping the liquid level higher than the upper end of a filler of the HLB solid-phase extraction column all the time in the whole process, flushing by using formic acid aqueous solution after the water sample is treated, then performing vacuum drying, eluting by using methanol, collecting an analyte to be detected, drying by using nitrogen, finally performing volume fixing by using methanol, and performing detection after a filter membrane is filtered; and (3) determining the contents of four types of 13 antibiotics in the water environment by using a liquid chromatography-tandem mass spectrometry method, and carrying out quantitative analysis by using an external standard method. The method has the advantages of accuracy, high sensitivity, good reproducibility and high recovery rate, and is suitable for detecting antibiotics in drinking water sources.
Description
Technical Field
The invention belongs to the technical field of detection of trace organic pollutant residues in water environment, relates to a method for detecting trace organic pollutants in water, and particularly relates to a rapid detection method which combines a solid-phase extraction pretreatment with a liquid chromatography-mass spectrometry combined technology and can efficiently and simultaneously rapidly detect four types of 13 antibiotics in a drinking water source water body.
Background
Antibiotics are among the most widely used drugs, mainly for the prevention and treatment of bacterial and fungal diseases. China is a large country for producing and using antibiotics, the phenomenon of abuse of the antibiotics is serious, many antibiotics cannot be completely absorbed by organisms of people or animals after being used by the people or the animals, more than 80% of the antibiotics can be discharged out of the bodies of the people or the animals and enter the water environment, and therefore the water environment is polluted by the antibiotics. The four major classes of antibiotics, tetracyclines, quinolones, macrolides and sulfonamides, are often detected in aqueous environments. However, with the frequent detection of the antibiotics remained in the drinking water source water body, people pay more and more attention to the pollution condition of the antibiotics in the drinking water source water body.
The detection method of antibiotics mainly comprises enzyme-linked immunosorbent assay technology, gas chromatography-mass spectrometry combined technology, liquid chromatography technology and the like. The solid phase extraction-liquid chromatography/mass spectrometry combined method has the characteristics of wide application range, strong separation capability, high sensitivity, high analysis speed and the like, becomes an important detection and analysis method for antibiotics in environmental water, and has the detection limit reaching the ppb level. The currently reported determination methods involve relatively few types of antibiotics, mostly focus on a single type of antibiotic compound, have low sensitivity and recovery rate, and are difficult to perform detection on different types of antibiotics simultaneously. Therefore, the establishment of a method for rapidly determining the residues of multiple antibiotics in the drinking water source has important practical significance, and the inventor further researches the method and develops a method for simultaneously detecting four types of 13 antibiotics in the drinking water source water body by using a solid phase extraction-liquid chromatography tandem mass spectrometry method.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for simultaneously detecting four types of 13 antibiotics in a drinking water source water body by a solid phase extraction-liquid chromatography tandem mass spectrometry method, which has the advantages of accuracy, high sensitivity, good reproducibility and high recovery rate, is suitable for detecting the antibiotics in the drinking water source water body, and has strong practical application value.
In order to solve the technical problems, the technical solution of the invention is as follows:
a method for simultaneously detecting four types of 13 antibiotics in drinking water source water body by solid phase extraction-liquid chromatography tandem mass spectrometry is carried out according to the following steps: step one, filtering a water sample by a glass fiber membrane, adding ethylene diamine tetraacetic acid, and adjusting the pH value to be 3 by formic acid; activating an HLB solid-phase extraction column by using methanol and a formic acid aqueous solution in sequence, enabling the water sample treated in the step one to pass through the HLB solid-phase extraction column, keeping the liquid level higher than the upper end of a filler of the HLB solid-phase extraction column all the time in the whole process, flushing by using the formic acid aqueous solution after the water sample is treated, then performing vacuum drying, eluting by using methanol, collecting an analyte to be measured, drying by using nitrogen, finally performing constant volume by using methanol, and performing volume measurement by using a filtering membrane; step three, determining the content of four types of 13 antibiotics in the water environment by a liquid chromatography tandem mass spectrometry method, and carrying out quantitative analysis by adopting an external standard method, wherein the detection conditions of the chromatogram are as follows: the chromatographic column is C18 liquid chromatographic column, and the mobile phase A is 5 mmol.L-1Ammonium acetate in 0.1% aqueous formic acid, mobile phase B was pure methanol; the 13 antibiotics are terramycin, tetracycline, chlortetracycline, roxithromycin, azithromycin, erythromycin, sulfadiazine, sulfamethazine, sulfamethoxazole, ofloxacin, ciprofloxacin, enrofloxacin and difloxacin.
Further, equal volumes of methanol and aqueous formic acid.
Further, in the second step, the flow rate of the water sample passing through the HLB solid phase extraction column is 3-5 ml/min-1。
Further, in the first step, the filtering membrane used for filtering the water sample is a glass fiber membrane with the pore diameter of 0.45 μm.
Further, in the second step, the solid phase extraction column is an Oasis HLB column.
Further, in step two, the Oasis HLB solid phase extraction cartridge was activated sequentially with 6mL of methanol and 6mL of 0.5% aqueous formic acid, the methanol and 0.5% aqueous formic acid were each taken 3 times, 2mL each time, after the water sample treatment was completed, the cartridge was flushed with 6mL of 0.5% aqueous formic acid, and then vacuum-dried for 30min to remove the residual water from the cartridge, and then eluted with 6mL of methanol 3 times.
Further, in step three, the detection conditions of the chromatogram further include: the flow rate was 0.5 mL/min-1The sample volume was 10. mu.L, and the column temperature was 40 ℃.
Further, in step three, the detection conditions of the mass spectrum are as follows: the gas flow rates of the electrospray ion source, the positive ion mode, the ion source I and the ion source II are respectively 50 mL/min-1And 60 mL. min-1The ion source voltage is 5500V, and the auxiliary heating gas temperature is 550 ℃.
After the scheme is adopted, the invention carries out solid-phase extraction enrichment and purification by an HLB column, and methanol and 5 mmol.L are used-1Ammonium acetate in 0.1% formic acid solution as mobile phase through
And (4) carrying out triple four-stage tandem mass spectrometry multi-reaction monitoring mode analysis after chromatographic column separation. The detection limit of each target object is 0.05-1.66 ng/L, the quantification limit is 0.17-4.16 ng/L, the recovery rate is 60.2-120.1%, and the relative standard deviation is 1.1-14.9%.
Drawings
FIG. 1 is an MRM chromatogram of a tetracycline antibiotic of the invention;
FIG. 2 is an MRM chromatogram of a quinolone antibiotic of the present invention;
FIG. 3 is an MRM chromatogram of a sulfonamide antibiotic of the present invention;
FIG. 4 is a MRM chromatogram of a macrolide antibiotic of the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples. First, the apparatus and reagents used in this example were as follows:
the instrument comprises the following steps: glass fiber filter membrane (Shanghai peninsula industria ltd. purification equipment factory, pore diameter 0.45 μm), pH meter for acid and alkali (pH2100, China), solid phase extraction device (Waters, USA), OASIS HLB solid phase extraction column (200mg, 6mL, CNW), constant temperature water bath nitrogen blower (Organomation corporation, usa), vacuum drying oven (DZF-6050, China), chromatography column
Column (100 mm. times.4.6 mm, 2.6 μm, Phenomenex), Agilent high performance liquid chromatography-mass spectrometer (ABI 3200Q TRAP LC-MS/MS System, Agilent, USA). Reagent: methanol, formic acid and disodium ethylenediaminetetraacetate (Na2EDTA) were chromatographically pure (purity ≥ 99.0%) and purchased from the alatin group; the laboratory water is Milli-Q ultrapure water (less than or equal to 18.2M omega). The purity of the 13 antibiotic standard substances is more than or equal to 95 percent and is purchased from biological engineering (Shanghai) GmbH.
Accurately measuring 500mL of water sample, filtering by a 0.45-micron glass fiber membrane, and adding 0.5g of disodium ethylene diamine tetraacetate; with 5 mol. L-1Formic acid adjusts the pH to about 3. The formic acid selected in the step can not only adjust the pH value, but also protect the chromatographic column in the subsequent liquid sample injection process, which is an advantage that other commonly selected inorganic acids (such as hydrochloric acid, sulfuric acid and the like) do not have. The disodium ethylene diamine tetraacetate is added mainly for complexing heavy metal ions in water and improving the recovery rate of tetracycline antibiotics.
The Oasis HLB solid phase extraction cartridge was activated sequentially with 6mL methanol and 6mL 0.5% aqueous formic acid (2 mL each taken 3 times with methanol and 0.5% aqueous formic acid). The methanol can activate the HLB solid phase extraction column, and then the concentration of the HLB solid phase extraction column is 3-5 ml/min-1The flow rate is used for loading the water sample, and the purpose of limiting the flow rate is to prolong the contact time between the target and the filler in the extraction column, so that the retention effect of the target is improved. The liquid level is always kept higher than the upper end of the small column packing in the whole process, and the aim is to keep the liquid in a filling state without cutoff. After the water sample is treated, 6mL of 0.5% formic acid aqueous solution is used for flushing, then vacuum drying is carried out for 30min to remove the residual water in the column body, 6mL of methanol is used for eluting for 3 times, the activated elution amount is selected according to the adsorption capacity of the target object, the volume of the methanol can be limited to optimize and obtain the optimal elution amount, and the highest recovery rate is obtained under the condition of the minimum solvent consumption. The eluate was collected in a 10mL brown glass tube and blown dry with mild nitrogenFinally, the volume is adjusted to 1.0mL by methanol, and the solution is measured by HPLC-MS/MS analysis after passing through a 0.22 mu m filter membrane.
Chromatographic conditions are as follows: the mobile phase A is 5 mmol. L-1Ammonium acetate in 0.1% aqueous formic acid, mobile phase B was pure methanol; the flow rate was 0.5 mL/min-1Sample introduction volume is 10 mu L; the column temperature was 40 ℃. The specific elution procedure is shown in table 1.
TABLE 1 gradient elution procedure
Mass spectrum conditions: electrospray ion Source (ESI), Positive ion mode, ion sources I (GSI) and II (GS2) gas flows were 50mL min, respectively-1And 60 mL. min-1The ion source voltage is 5500V, and the auxiliary heating gas temperature is 550 ℃. Ion source conditions were optimized for each compound using Multiple Reaction Monitoring (MRM) mode scanning, mass spectral parameters for each target are shown in table 2, and MRM chromatograms for each target are detailed in fig. 1, 2, 3, and 4.
TABLE 2 Mass Spectrometry parameters of 13 antibiotics in MRM mode
The good chromatographic separation effect is the guarantee of the quantification and the qualification of the target object, and in order to improve the separation effect of various antibiotics and improve the analysis efficiency, the invention respectively optimizes chromatographic conditions such as chromatographic mobile phase, chromatographic column temperature and the like.
The composition of the chromatographic mobile phase affects the ionization efficiency and thus the detection sensitivity of the target in addition to the retention time and the peak shape. When acetonitrile is used as an organic mobile phase, the peak shape is poor, and when methanol is used as the organic mobile phase in an experiment, the peak shape is good; at the same time, 0 is added into the water phase5% formic acid (containing 5 mmol. L)-1Ammonium acetate) is effective in improving the peak shape, increasing the ionization efficiency of the substance, and increasing the response intensity. This is because formic acid and ammonium acetate are common reagents for enhancing the ionization degree of a target chemical in a positive ion mode, and can effectively improve the peak shape, so that the peak shape is sharper and more symmetrical, and the two have a combined action influence.
Compare with
Separation effect of column (100 mm. times.4.6 mm, 2.6 μm, Phenomenex) and Kromasil 100-5C 18 column (150 mm. times.4.6 mm, 3.5 μm, Akzo Nobel) on 13 antibiotics. The results showed that the length was slightly shorter
The chromatographic column can shorten the analysis time, realize the mutual noninterference of ion peaks of all target substances to a certain extent, and the separated antibiotic peak has a relatively better shape.
The present example also examined the effect of column temperature (30 ℃, 40 ℃ and 50 ℃) on the separation of components, and the results showed that the peak shape was the best at 40 ℃ and the separation of components was better, because the proper column temperature reduced the viscosity of the mobile phase and shortened the equilibration time.
In summary, the MRM chromatograms of the compounds are shown in fig. 1 to 4 by optimizing the chromatographic and mass spectrometric conditions according to the properties of the target and the ion mode obtained after ionization.
In the invention, the influence of factors such as solid-phase extraction small columns, pH, sample loading volume, eluent volume and the like on water sample extraction is also considered, and the solid-phase extraction conditions are optimized.
And selecting Oasis HLB and C18 solid phase extraction small columns, and comparatively investigating the influence of different types of extraction columns on the recovery rate. The results show that the extraction efficiency of Oasis HLB on four antibiotics is 65-120%, while the extraction efficiency of C18 column on sulfanilamide antibiotics is lower than 50%. This is probably because the Oasis HLB solid phase extraction cartridge is filled with a reversed phase adsorbent with hydrophilic-lipophilic balance and water-infiltrability, which is a universal type extraction cartridge applicable to acidic, neutral and basic compounds; and the C18 small column is reverse bonded silica gel with octadecyl on the silica gel, and mainly has better retention to compounds with weaker polarity. Meanwhile, the specific surface area of the HLB column is larger than that of the C18 column. Therefore, the Oasis HLB solid phase extraction cartridge was chosen to enrich and purify the sample.
The acidity of the sample is also an important factor influencing the extraction efficiency, and the experiment adopts formic acid and ammonia water to adjust the water sample to different pH values (pH is 3.0, 5.0 and 7.0) and examines the influence on the recovery rate of antibiotics. The result shows that when the pH value is 7.0, the recovery rate of tetracycline and sulfonamide antibiotics is low, and is 40-75%; the target compound recovery was above 65% at both pH 3.0 and 5.0, with no significant difference. Comprehensively considering that the pKa value of the tetracycline antibiotics is 2.3-3.3, and adjusting the pH value of the water sample to 3.0 before the column is too small to ensure the recovery rate of the four antibiotics.
Selecting different sample water volumes (500mL and 1000mL) for standard addition of 100 ng.L-1Recovery experiments (see table 3 for details). The result shows that the recovery rate of 500mL is 67.5-124.8%; the recovery rate of 1000mL is reduced to 40.1% -87.4%, because the overlarge volume of the water sample can cause the overloading of the solid phase extraction column, thereby influencing the recovery rate, and the recovery rate is consistent with the research result reported in the literature. Therefore, the volume of the sample water to be loaded was 500 mL.
The effect of eluent volumes (4, 6, 8 and 10mL) on the recovery of antibiotics was examined (see table 3). The recovery rate of each target compound was 39.1% to 86.1% when the volume of the eluent was 4mL, and the recovery rate of each target compound was 70.4% to 117.8% when the volume of the eluent was 6, 8 and 10mL, which was high and did not vary much. This is probably because when the amount of the solvent is small, the contact time of the eluting solution with the packing is short and the desorption is insufficient. Considering that increasing the volume of the eluent may cause impurities to be eluted to affect purification efficiency, the volume of the eluent was determined to be 6 mL.
TABLE 3 recovery of 13 antibiotics at different loading volumes and eluent volumes
The linear range, detection limit, recovery rate and precision were investigated according to the optimized SPE-HPLC-MS/MS method described above. Quantitative analysis is carried out by adopting an external standard method, the concentration of a linear equation consists of 6 concentration values of 10, 20, 50, 100, 200 and 250 mu g/L, and the correlation coefficient R of the concentration values2Are both greater than 0.99. According to the conversion of the enrichment factor, the method has good linear relation within the range of 0.02-0.5 ng/L. And (4) drawing a standard working curve according to the measurement result to obtain the linear relation between the concentration (x) of the 13 antibiotics and the peak area (Y), wherein the linear relation between the 13 antibiotics is shown in the table 4. The detection limit of antibiotic concentration is 3 times the signal-to-noise ratio, and the limit of quantitation is 10 times the signal-to-noise ratio.
Linear equation, detection limits and quantitation limits for 413 antibiotics in Table
And (4) carrying out a labeling experiment on the ultrapure water and the water sample of the water source, and inspecting the precision and recovery rate of the method. The results of experiments were performed with three levels of low, medium and high concentrations of 20ng/L, 200ng/L and 1000ng/L, and the recovery and Relative Standard Deviation (RSD) were calculated as 3 replicates, and are shown in Table 5. The recovery rate of 3 different standard adding concentrations is 60.2-120.1%, and the RSD is 1.1-14.9%, which shows that the method is accurate and reliable, and can be used for simultaneous determination and analysis of 13 antibiotics in an environmental water sample.
TABLE 513 antibiotics recovery and relative standard deviation (n ═ 3) in pure water and source water samples
The above-mentioned embodiments are only preferred embodiments of the present invention, and do not limit the technical scope of the present invention, so that the changes and modifications made by the claims and the specification of the present invention should fall within the scope of the present invention.
Claims (8)
1. A method for simultaneously detecting four types of 13 antibiotics in drinking water source water by solid phase extraction-liquid chromatography tandem mass spectrometry is characterized in that: the method comprises the following steps: step one, filtering a water sample by a glass fiber membrane, adding ethylene diamine tetraacetic acid, and adjusting the pH value to be 3 by formic acid; activating an HLB solid-phase extraction column by using methanol and a formic acid aqueous solution in sequence, enabling the water sample treated in the step one to pass through the HLB solid-phase extraction column, keeping the liquid level higher than the upper end of a filler of the HLB solid-phase extraction column all the time in the whole process, flushing by using the formic acid aqueous solution after the water sample is treated, then performing vacuum drying, eluting by using methanol, collecting an analyte to be measured, drying by using nitrogen, finally performing constant volume by using methanol, and performing volume measurement by using a filtering membrane; step three, determining the content of four types of 13 antibiotics in the water environment by a liquid chromatography tandem mass spectrometry method, and carrying out quantitative analysis by adopting an external standard method, wherein the detection conditions of the chromatogram are as follows: the chromatographic column is C18 liquid chromatographic column, and the mobile phase A is 5 mmol.L-1Ammonium acetate in 0.1% aqueous formic acid, mobile phase B was pure methanol; the 13 antibiotics are terramycin, tetracycline, chlortetracycline, roxithromycin, azithromycin, erythromycin, sulfadiazine, sulfamethazine, sulfamethoxazole, ofloxacin, ciprofloxacin, enrofloxacin and difloxacin.
2. The method of claim 1, wherein: in step two, equal volumes of methanol and aqueous formic acid solution.
3. The method of claim 1, wherein: in the second step, the flow rate of the water sample passing through the HLB solid-phase extraction column is 3-5 ml/min-1。
4. The method of claim 1, wherein: in the first step, the filtering membrane used for filtering the water sample is a glass fiber membrane with the pore diameter of 0.45 μm.
5. The method of claim 1, wherein: in the second step, the solid phase extraction column is an Oasis HLB column.
6. The method of claim 1, wherein: in the second step, the Oasis HLB solid phase extraction cartridge is activated sequentially with 6mL methanol and 6mL 0.5% formic acid aqueous solution, the methanol and 0.5% formic acid aqueous solution are each taken 3 times, 2mL each time, after the water sample treatment is completed, the cartridge is flushed with 6mL 0.5% formic acid aqueous solution, and then vacuum dried for 30min to remove the residual water in the cartridge, and then eluted with 6mL methanol 3 times.
7. The method of claim 1, wherein: in step three, the detection conditions of the chromatogram further comprise: the flow rate was 0.5 mL/min-1The sample volume was 10. mu.L, and the column temperature was 40 ℃.
8. The method of claim 1, wherein: in step three, the detection conditions of the mass spectrum are as follows: the gas flow rates of the electrospray ion source, the positive ion mode, the ion source I and the ion source II are respectively 50 mL/min-1And 60 mL. min-1The ion source voltage is 5500V, and the auxiliary heating gas temperature is 550 ℃.
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