CN101995442A - Method for determining PPCPs (Pharmaceutical and Personal Care Products) in water by LPME (Liquid-phase Micro Extraction) technology - Google Patents

Abstract

The invention discloses a method for determining PPCPs (Pharmaceutical and Personal Care Products) in water by an LPME (Liquid-phase Micro Extraction) technology based on ionic liquid, wherein green solvent ion liquid takes the place of the traditional organic solvent, the PPCPs in environmental samples are extracted and separated by utilizing a single drop liquid phase micro extraction technology, and then the samples are detected by the high-performance liquid chromatography. The invention has the characteristics of small environmental pollution, good extraction effect, simple operation, low cost, easy combination with a chromatogram system and the like.

Description

A liquid phase microextraction method for measuring PPCPs in water

technical field

The invention belongs to the field of environmental protection and relates to a method for measuring pharmaceuticals and personal care products (PPCPs) in water.

Background technique

Environmental samples often have complex matrices, many interference factors in direct analysis, and the concentration of target analytes is very low. Pretreatment is required to achieve the separation and enrichment of target analytes, so as to meet the requirements of corresponding analytical instruments. Pretreatment is a crucial link in the analysis process of environmental samples, which is directly related to the accuracy of the measurement results. Traditional environmental sample pretreatment techniques, such as liquid-liquid extraction and Soxhlet extraction, often need to consume a large amount of volatile toxic organic solvents, and the processing costs are high, which is not conducive to the health of researchers, but also pollutes the environment. Concept of sustainable development.

Pharmaceuticals and personal care products PPCPs include therapeutic drugs, veterinary drugs, flavors and fragrances, cosmetics, sunscreens and sunscreens, diagnostics, nutraceuticals and some components added in their production such as excipients and preservatives. Some PPCPs are difficult to degrade and transform in the environment. The half-life of most PPCPs is not very long. Due to the imperfection of technology and other reasons, it has been continuously introduced into the environment, showing the phenomenon of "persistence". PPCPs will have certain toxic effects on organisms, such as inhibiting the reproduction and growth of microorganisms, and inhibiting plant chloroplasts and enzymes. activity, causing distortion in animals and posing potential risks to ecosystems and human health.

my country is one of the big countries in the production and use of drugs, and the use of personal care products is also very large. From this point of view, it is imperative to detect and evaluate the pollution level of PPCPs in the environment.

According to the current research and application, the pretreatment techniques of PPCPs in environmental samples mainly include liquid-liquid extraction (LLE), solid-phase extraction (SPE), solid-phase microextraction (SPME) and liquid-phase microextraction (LPME), among which SPE is The most commonly used preprocessing technique. Although SPE has a high enrichment effect, it requires a large sample volume (0.5-2L), and one SPE extraction column can only be used for the pretreatment of one sample, and the cost is relatively high; in addition, the method is cumbersome to operate, and the same Large quantities of toxic organic solvents are used. Solvent-free extraction technology SPME and micro-solvent extraction technology LPME have been very well used in the sample pretreatment of PPCPs because they integrate sampling, extraction and enrichment, and have the characteristics of simple and fast operation, high enrichment factor, and environmental friendliness. application. Due to the limited types of fiber coatings available for SPME (commercialized coatings are mainly hydrophobic PDMS and PA, etc.), it is only suitable for the determination of a few hydrophobic PPCPs (such as alkylphenols, etc.); It is fragile and easy to break, and the cost is high, which greatly limits its wide application in PPCP determination. Compared with SPME technology, LPME is especially suitable for the determination of polar and non-polar PPCPs in water because of its low cost and flexible selection of extraction agents according to target analytes.

Most of the existing LPME technology for the determination of PPCPs uses volatile and harmful traditional organic solvents as extraction agents. Due to the insufficient density and viscosity of traditional organic solvents and their poor solubility for most PPCPs, their ability to enrich PPCPs is very limited. , how to choose a suitable extractant is a key problem to be solved in this field.

Contents of the invention

In order to overcome the shortcomings of traditional organic solvents that are easy to volatilize and not have strong extraction ability for PPCPs, and solve the current problem of lack of methods for quickly and accurately detecting PPCPs in water environments, the purpose of the present invention is to provide an environmentally friendly, low-cost, simple and quick operation The analysis method of PPCPs in the local detection environment: replace the traditional organic solvent with green solvent ionic liquid, and apply the single drop liquid phase microextraction technology to extract and separate the drugs in the environmental samples on the basis of the existing research on the liquid phase microextraction device And personal care products; and use high performance liquid chromatography detection technology.

Ionic liquid is an environmentally friendly "green" solvent and catalyst. It refers to an ionic compound mainly composed of organic cations and various anions. They often exist in liquid form at room temperature. Therefore, they are also called room temperature ionic liquid. Ionic liquids have the characteristics of low vapor pressure, low volatility, high viscosity, large liquid temperature range, wide dissolution range, good thermal stability, and wide electrochemical window. Achieve optimal extraction of target substances and other effects. Since ionic liquid is a polar solvent, it is especially suitable for the determination of polar PPCPs according to the principle of "like dissolves like".

The technical solution adopted by the present invention to solve its technical problems is:

A method for measuring PPCPs in water by liquid phase microextraction, comprising steps:

(1) first use a pH regulator to adjust the pH value of the sample solution, and use an inorganic salt to adjust the concentration of the salt in the sample solution;

(2) The sample solution is packed in the sample bottle, put into the stirring magnet, the liquid phase sampling needle absorbs the ionic liquid, passes through the sealing cap, and puts a small tube with a trumpet-shaped opening on the needle head, so that the droplet can be suspended; then Immerse the sampling needle into the solution in the sample bottle, tighten the bottle cap, place the sample bottle on the magnetic stirrer, and fix the sampler with a bracket;

(3) After fixing, push the push rod of the injector to push out all the ionic liquid in the injection needle, so that the ionic liquid forms droplets on the needle of the injector, and start the magnetic stirrer at the same time;

(4) After extracting for a certain period of time, turn off the magnetic stirrer, suck the remaining liquid droplets back into the injector, take out the injector, suck the extractant, and mix evenly;

(5) Then directly enter the liquid chromatography analysis and detection.

The salinity is 0-36g/L; the inorganic salts are sodium chloride, potassium chloride and anhydrous sodium sulfate.

The pH value stated is the pH value at which the target analyte is most likely to be in the molecular form rather than the ionic form; for basic target analytes, the pH needs to be adjusted to basic conditions; The pH is adjusted to be acidic; for neutral target analytes, the pH is neutral. Adjusting the sample solution to an appropriate pH value is an important factor for the present invention to exert its maximum effectiveness. Target analytes are maximally in molecular rather than ionic form at an optimal pH. According to the principle of this liquid phase microextraction, the target analyte in molecular form is easily extracted into the extractant ionic liquid.

The small tube is a polytetrafluoroethylene tube or a polypropylene tube.

The liquid chromatography micro-sampler is 10 μL or 25 μL, and is cleaned with methanol or acetonitrile for more than 5 times before each extraction.

The pH regulator comes from hydrochloric acid (or sulfuric acid, phosphoric acid), sodium hydroxide (or potassium hydroxide) or phosphate buffer solution.

The stirring rate can be adjusted between zero and the maximum possible rotational speed, and the maximum possible rotational speed is the maximum rotational speed at which the needle tip of the injector does not fall off; the extraction time is 0-60 minutes.

The detection conditions of the described high-performance liquid chromatography are: chromatographic column, TC-C18, inner diameter 5 μ m, 4.6 * 150mm; mobile phase ratio, acetonitrile/water=20/80; column thermostat temperature, 25 ℃; flow velocity is set to 1.0 ml/min; VWD ultraviolet detector and FLD fluorescence detector.

The sample bottle is a brown sample bottle.

The volume ratio of the sample solution to the ionic liquid is 1:5000˜1:1000.

15 mL of the sample solution is placed in a sample bottle, put into a stirring magnet, the liquid-phase sampling needle draws 10 μL of ionic liquid, passes through the sealing cap, and covers the needle with a polytetrafluoroethylene tube to make the droplet more stable. hanging on. Then dip the sampling needle into the solution in the sample bottle, tighten the bottle cap, place the sample bottle on the magnetic stirrer, and fix the sample injector at a specific position with a bracket.

The ionic liquid single-drop liquid-phase micro-extraction device includes a stirring device and a support, a 20mL brown sample bottle with a sealed bottle cap, a stirring bar, a polytetrafluoroethylene (PTFE) tube and a liquid chromatography micro-sampler. Drill a small hole in the center of the brown vial cap to allow the LC needle to pass through.

The beneficial effects of the present invention are:

(1) The present invention uses ionic liquid as the extraction agent, which has the characteristics of high viscosity and difficult water solubility, so it can suspend a larger volume of liquid droplets than ordinary organic solvents, and the sustainable analysis time is longer, Improve the extraction effect;

(2) the ionic liquid adopted in the present invention is a green solvent, which is less polluting to the environment than traditional organic solvents;

(3) The device of the present invention is simple, easy to operate, easy to clean, and the method can be reused except for the extractant, so that the generation of waste is minimized;

(4) Add appropriate amount of inorganic salt (sodium chloride, potassium chloride and anhydrous sodium sulfate) to the sample solution to adjust the salinity, on the one hand, it can reduce the dissolution of the ionic liquid and improve the reproducibility of the analysis; extraction of liquids;

(5) The analysis and detection steps of the present invention are simple and fast, and can realize rapid analysis and testing of PPCPs.

Description of drawings

Figure 1 shows the impact of different extraction times on the enrichment effect of the target substance;

Figure 2 shows the effect of different pH on the enrichment effect of the target substance.

Detailed ways

Example 1

A single drop liquid phase microextraction device was used.

The ionic liquid [C ₈ MIM]PF ₆ (1-octyl-3-methylimidazolium hexafluorophosphate) was used as the extractant.

The sample solution is a mixed solution of 5 kinds of sulfonamides, sulfadiazine, sulfamethazine, sulfamethazine, sulfamethoxine and sulfachloropyridazine prepared in the laboratory, and the concentration is 1 ppm respectively.

(1) Adjust the pH of the sample solution to 6.0 with 1% dilute hydrochloric acid, without adding sodium chloride solution or solid, so that the salinity of the sample solution is 0.

(2) Take 15 mL of sample solution and put it in a brown sample bottle, put it into a stirring magnet, draw 10 μL of ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate with a liquid phase sampling needle, and pass through the sealing cap , with Teflon tubing on the needle cover to allow the droplet to hang more stably. Then dip the sampling needle into the solution in the sample bottle, tighten the bottle cap, place the sample bottle on the magnetic stirrer, and fix the sample injector at a specific position with a bracket.

(3) After fixing, push the push rod of the injector to push out all the ionic liquid in the injection needle, so that the ionic liquid forms droplets on the needle of the injector, and at the same time start the magnetic stirrer at a stirring speed of 600 rpm.

(4) After 20 minutes of extraction, turn off the magnetic stirrer. Since the ionic liquid will dissolve to a certain extent during the extraction process, the remaining liquid droplets can be sucked back into the injector. Take out the injector and suck the extractant for two times to mix evenly.

(5) Then, the samples were manually injected into liquid chromatography for analysis and detection, and the liquid chromatography detection results are shown in Table 1. The conditions of liquid chromatography are: chromatographic column, TC-C18, inner diameter 5μm, 4.6×150mm; mobile phase ratio, acetonitrile/water=20/80; column oven temperature, 25°C; flow rate set to 1ml/min; UV-visible Detector, the detection wavelength is set to 265nm.

Table 1 liquid chromatography detection detection result

substance Sulfadiazine Sulfamethazine Sulfamethazine Sulfamethoxine Sulfachloropyridazine Enrichment factor 2.6 3.3 3.7 6.0 10.1

Example 2

A single drop liquid phase microextraction device was used.

The ionic liquid [C ₈ MIM]PF ₆ (1-octyl-3-methylimidazolium hexafluorophosphate) was used as the extractant.

The sample solution is a mixed solution of 6 kinds of sulfonamides, sulfadiazine, sulfamethazine, sulfamethoxazole, sulfachloropyridazine, sulfamethoxypyridazine and sulfaquinoxaline, prepared in the laboratory, with a concentration of 1 ppm respectively.

(1) The pH of the sample solution was adjusted to 3.0 with concentrated hydrochloric acid and 1% dilute hydrochloric acid, and the concentration of salt in the sample solution was adjusted to 18 g/L with NaCl solid.

(2) Take 15 mL of sample solution and put it in a brown sample bottle, put it into a stirring magnet, draw 10 μL of ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate with a liquid phase sampling needle, and pass through the sealing cap , a Teflon tube is placed on the needle cover to allow the droplet to hang more stably. Then dip the sampling needle into the solution in the sample bottle, tighten the bottle cap, place the sample bottle on the magnetic stirrer, and fix the sample injector at a specific position with a bracket.

(3) After fixing, push the push rod of the injector to push out all the ionic liquid in the injection needle, so that the ionic liquid forms droplets on the needle of the injector, and at the same time start the magnetic stirrer at a stirring speed of 600 rpm.

(4) After 15 minutes of extraction, turn off the magnetic stirrer. Since the ionic liquid will dissolve to a certain extent during the extraction process, the remaining liquid droplets can be sucked back into the injector. Take out the injector and suck the extractant twice. , to make the mixture even.

(5) Then, the samples were manually injected into liquid chromatography for analysis and detection, and the liquid chromatography detection results are shown in Table 1. The conditions of liquid chromatography are: chromatographic column, TC-C18, inner diameter 5μm, 4.6×150mm; mobile phase ratio, acetonitrile/water=20/80; column oven temperature, 25°C; flow rate set to 1ml/min; UV-visible Detector, the detection wavelength is set to 265nm.

Table 2 liquid chromatography detection detection results

substance Sulfadiazine Sulfamethazine Sulfamethoxypyridazine Sulfachloropyridazine Sulfamethoxazole Sulfaquinoxaline Enrichment factor 5.0 5.2 11.7 21.8 28.5 40.7

Example 3

A single drop liquid phase microextraction device was used.

The ionic liquid [C ₈ MIM]PF ₆ (1-octyl-3-methylimidazolium hexafluorophosphate) was used as the extractant.

The pH was adjusted to 4.5 with 1% dilute hydrochloric acid, and the concentration of salt in the sample solution was adjusted to 36 g/L with KCl solid. Other steps and conditions were the same as in Example 2, and liquid phase microextraction was carried out.

Through manual injection into liquid chromatography analysis and detection, the liquid chromatography detection results are shown in Table 1. The conditions of liquid chromatography are: chromatographic column, TC-C18, inner diameter 5μm, 4.6×150mm; mobile phase ratio, acetonitrile/water=20/80; column oven temperature, 25°C; flow rate set to 1ml/min; UV-visible Detector, the detection wavelength is set to 265nm.

Table 3 liquid chromatography detection detection results

substance Sulfadiazine Sulfamethazine Sulfamethoxypyridazine Sulfachloropyridazine Sulfamethoxazole Sulfaquinoxaline Enrichment factor 3.1 3.4 7.6 15.3 18.6 25.8

Example 4

A single drop liquid phase microextraction device was used.

The ionic liquid [C ₈ MIM]PF ₆ (1-octyl-3-methylimidazolium hexafluorophosphate) was used as the extractant.

Use 1% dilute hydrochloric acid to adjust the pH to 4.5. Other steps and conditions are the same as in Example 2. The volume of the ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate is changed to 3 μL. The volume ratio is 1:5000.

Through manual injection into liquid chromatography analysis and detection, the liquid chromatography detection results are shown in Table 1. The conditions of liquid chromatography are: chromatographic column, TC-C18, inner diameter 5μm, 4.6×150mm; mobile phase ratio, acetonitrile/water=20/80; column oven temperature, 25°C; flow rate set to 1ml/min; UV-visible Detector, the detection wavelength is set to 265nm.

Table 4 liquid chromatography detection detection result

substance Sulfadiazine Sulfamethazine Sulfamethoxypyridazine Sulfachloropyridazine Sulfamethoxazole Sulfaquinoxaline Enrichment factor 1.1 1.2 2.3 4.0 5.1 6.9

Example 5

A single drop liquid phase microextraction device was used.

The ionic liquid [C ₈ MIM]PF ₆ (1-octyl-3-methylimidazolium hexafluorophosphate) was used as the extractant.

Other steps and conditions were the same as in Example 4, changing the volume of the ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate to 15 μL, so that the volume ratio of the ionic liquid to the sample solution was 1:1000.

Through manual injection into liquid chromatography analysis and detection, the liquid chromatography detection results are shown in Table 1. The conditions of liquid chromatography are: chromatographic column, TC-C18, inner diameter 5μm, 4.6×150mm; mobile phase ratio, acetonitrile/water=20/80; column oven temperature, 25°C; flow rate set to 1ml/min; UV-visible Detector, the detection wavelength is set to 265nm.

Table 4 liquid chromatography detection detection result

substance Sulfadiazine Sulfamethazine Sulfamethoxypyridazine Sulfachloropyridazine Sulfamethoxazole Sulfaquinoxaline Enrichment factor 4.8 4.8 9.5 18.8 21.8 27.5

Example 6

A single drop liquid phase microextraction device was used.

The ionic liquid [C ₈ MIM]PF ₆ (1-octyl-3-methylimidazolium hexafluorophosphate) was used as the extractant.

The pH was adjusted to 4.5 with 1% dilute hydrochloric acid, and the concentration of salt in the sample solution was adjusted to 36g/L with NaCl solid. Other steps and conditions were the same as in Example 2, and liquid phase microextraction was carried out for 5 minutes.

Through manual injection into liquid chromatography analysis and detection, the liquid chromatography detection results are shown in Table 1. The conditions of liquid chromatography are: chromatographic column, TC-C18, inner diameter 5μm, 4.6×150mm; mobile phase ratio, acetonitrile/water=20/80; column oven temperature, 25°C; flow rate set to 1ml/min; UV-visible Detector, the detection wavelength is set to 265nm.

Table 4 liquid chromatography detection detection result

substance Sulfadiazine Sulfamethazine Sulfamethoxypyridazine Sulfachloropyridazine Sulfamethoxazole Sulfaquinoxaline Enrichment factor 2.4 2.7 6.7 7.6 8.6 9.6

Example 7

A single drop liquid phase microextraction device was used.

The ionic liquid [C ₈ MIM]PF ₆ (1-octyl-3-methylimidazolium hexafluorophosphate) was used as the extractant.

The pH was adjusted to 6.0 with 1% dilute hydrochloric acid, and the other steps and conditions were the same as in Example 2, and the liquid phase microextraction was carried out, and the extraction time was 60 min.

Through manual injection into liquid chromatography analysis and detection, the liquid chromatography detection results are shown in Table 1. The conditions of liquid chromatography are: chromatographic column, TC-C18, inner diameter 5μm, 4.6×150mm; mobile phase ratio, acetonitrile/water=20/80; column oven temperature, 25°C; flow rate set to 1ml/min; UV-visible Detector, the detection wavelength is set to 265nm.

Table 4 liquid chromatography detection detection result

substance Sulfadiazine Sulfamethazine Sulfamethoxypyridazine Sulfachloropyridazine Sulfamethoxazole Sulfaquinoxaline Enrichment factor 2.6 3.8 9.3 13.4 21.1 51.1

Example 8

A single drop liquid phase microextraction device was used.

The ionic liquid [C ₈ MIM]PF ₆ (1-octyl-3-methylimidazolium hexafluorophosphate) was used as the extractant.

The pH was adjusted to 7.0 with sodium hydroxide, and the extraction time was 15 minutes. Other steps and conditions were the same as in Example 2, and liquid phase microextraction was carried out.

Through manual injection into liquid chromatography analysis and detection, the liquid chromatography detection results are shown in Table 1. The conditions of liquid chromatography are: chromatographic column, TC-C18, inner diameter 5μm, 4.6×150mm; mobile phase ratio, acetonitrile/water=20/80; column oven temperature, 25°C; flow rate set to 1ml/min; UV-visible Detector, the detection wavelength is set to 265nm.

Table 4 liquid chromatography detection detection result

substance Sulfadiazine Sulfamethazine Sulfamethoxypyridazine Sulfachloropyridazine Sulfamethoxazole Sulfaquinoxaline Enrichment factor 1.8 2.0 4.5 2.9 5.1 12.4

Example 9

A single drop liquid phase microextraction device was used.

The ionic liquid [C ₈ MIM]PF ₆ (1-octyl-3-methylimidazolium hexafluorophosphate) was used as the extractant.

The pH was adjusted to 7.0 with potassium hydroxide, and the extraction time was 15 minutes. Other steps and conditions were the same as in Example 2, and liquid phase microextraction was carried out.

Through manual injection into liquid chromatography analysis and detection, the liquid chromatography detection results are shown in Table 1. The conditions of liquid chromatography are: chromatographic column, TC-C18, inner diameter 5μm, 4.6×150mm; mobile phase ratio, acetonitrile/water=20/80; column oven temperature, 25°C; flow rate set to 1ml/min; UV-visible Detector, the detection wavelength is set to 265nm.

Table 4 liquid chromatography detection detection result

substance Sulfadiazine Sulfamethazine Sulfamethoxypyridazine Sulfachloropyridazine Sulfamethoxazole Sulfaquinoxaline Enrichment factor 2.0 1.9 4.2 2.8 4.6 11.2

Example 10

A single drop liquid phase microextraction device was used.

The ionic liquid [C ₈ MIM]PF ₆ (1-octyl-3-methylimidazolium hexafluorophosphate) was used as the extractant.

The pH was adjusted to 2.0 with 1% dilute sulfuric acid, and the other steps and conditions were the same as in Example 2, and liquid-phase microextraction was carried out.

Through manual injection into liquid chromatography analysis and detection, the liquid chromatography detection results are shown in Table 1. The conditions of liquid chromatography are: chromatographic column, TC-C18, inner diameter 5μm, 4.6×150mm; mobile phase ratio, acetonitrile/water=20/80; column oven temperature, 25°C; flow rate set to 1ml/min; UV-visible Detector, the detection wavelength is set to 265nm.

Table 3 liquid chromatography detection detection results

substance Sulfadiazine Sulfamethazine Sulfamethoxypyridazine Sulfachloropyridazine Sulfamethoxazole Sulfaquinoxaline Enrichment factor 2.5 2.0 5.1 14.1 20.2 35.1

Example 11

A single drop liquid phase microextraction device was used.

The ionic liquid [C ₈ MIM]PF ₆ (1-octyl-3-methylimidazolium hexafluorophosphate) was used as the extractant.

The pH was adjusted to 6.0 with phosphate buffer, and other steps and conditions were the same as in Example 2, and liquid phase microextraction was carried out.

Through manual injection into liquid chromatography analysis and detection, the liquid chromatography detection results are shown in Table 1. The conditions of liquid chromatography are: chromatographic column, TC-C18, inner diameter 5μm, 4.6×150mm; mobile phase ratio, acetonitrile/water=20/80; column oven temperature, 25°C; flow rate set to 1ml/min; UV-visible Detector, the detection wavelength is set to 265nm.

Table 3 liquid chromatography detection detection results

substance Sulfadiazine Sulfamethazine Sulfamethoxypyridazine Sulfachloropyridazine Sulfamethoxazole Sulfaquinoxaline Enrichment factor 3.1 3.9 8.3 7.8 11.9 21.3

The above description of the embodiments is for those of ordinary skill in the art to understand and apply the present invention. It is obvious that those skilled in the art can easily make various modifications to these embodiments, and apply the general principles described here to other embodiments without creative effort. Therefore, the present invention is not limited to the embodiments herein. Improvements and modifications made by those skilled in the art according to the disclosure of the present invention without departing from the scope of the present invention should fall within the protection scope of the present invention.

Claims (10)

1. A method for measuring PPCPs in liquid phase microextraction, comprising steps: (1) first use a pH regulator to adjust the pH value of the sample solution, and use an inorganic salt to adjust the concentration of the salt in the sample solution; (2) The sample solution is packed in the sample bottle, put into the stirring magnet, the liquid phase sampling needle absorbs the ionic liquid, passes through the sealing cap, and puts a small tube with a trumpet-shaped opening on the needle head, so that the droplet can be suspended; then Immerse the sampling needle into the solution in the sample bottle, tighten the bottle cap, place the sample bottle on the magnetic stirrer, and fix the sampler with a bracket; (3) After fixing, push the push rod of the injector to push out all the ionic liquid in the injection needle, so that the ionic liquid forms droplets on the needle of the injector, and start the magnetic stirrer at the same time; (4) After extracting for a certain period of time, turn off the magnetic stirrer, suck the remaining liquid droplets back into the injector, take out the injector, suck the extractant, and mix evenly; (5) Then directly enter the liquid chromatography analysis and detection. 2. the method for measuring PPCPs in liquid phase microextraction according to claim 1 is characterized in that: described salinity is 0～36g/L; Described inorganic salt is sodium-chlor, potassium chloride and inorganic salt. Sodium Sulphate of Water. 3. the method for PPCPs in liquid phase microextraction measurement water according to claim 1, is characterized in that: described pH value is the pH value that target analyte is in molecular form rather than ionic form to the greatest extent; For alkaline target For analytes, the pH needs to be adjusted to alkaline conditions; for analytes that are themselves acidic, the pH needs to be adjusted to acid; for neutral target analytes, the pH needs to be neutral. 4. the method for measuring PPCPs in water by liquid phase microextraction according to claim 1, is characterized in that: described small tube is polytetrafluoroethylene tube or polypropylene tube. 5. the method for measuring PPCPs in liquid phase microextraction according to claim 1, is characterized in that: described liquid phase chromatographic micro-injector is 10 μ L or 25 μ L, all cleans 5 times with methanol or acetonitrile before each extraction above. 6. the method for measuring PPCPs in water by liquid phase microextraction according to claim 1 is characterized in that: described pH adjuster is from hydrochloric acid, sulfuric acid, phosphoric acid, sodium hydroxide, potassium hydroxide or phosphate buffer solution. 7. the method for measuring PPCPs in liquid phase microextraction according to claim 1, is characterized in that: described stirring speed is regulated between zero and as large as possible rotating speed, and as possible large rotating speed is for not making sample introduction The maximum rotational speed at which the needle tip liquid falls off; the extraction time is 0 to 60 minutes. 8. The method for measuring PPCPs in water by liquid phase microextraction according to claim 1, is characterized in that: the detection condition of described high performance liquid chromatography is: chromatographic column, TC-C18, internal diameter 5 μ m, 4.6 * 150mm; Phase ratio, acetonitrile/water=20/80; column oven temperature, 25°C; flow rate set to 1.0ml/min; VWD ultraviolet detector and FLD fluorescence detector. 9. the method for measuring PPCPs in water by liquid phase microextraction according to claim 1, is characterized in that: described sample bottle is a brown sample bottle. 10. The method for measuring PPCPs in water by liquid phase microextraction according to claim 1, characterized in that: the volume ratio of the sample solution to the ionic liquid is 1:5000 to 1:1000.

Images