CN115097024A - PPCPS detection method based on UPLC-MS/MS method - Google Patents
PPCPS detection method based on UPLC-MS/MS method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000010811 Ultra-Performance Liquid Chromatography-Tandem Mass Spectrometry Methods 0.000 title claims abstract description 22
- 238000001514 detection method Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000004458 analytical method Methods 0.000 claims abstract description 12
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims abstract description 12
- 238000012544 monitoring process Methods 0.000 claims abstract description 6
- 238000004451 qualitative analysis Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- 239000012071 phase Substances 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 9
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 9
- 239000003814 drug Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 238000005070 sampling Methods 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 6
- 229940079593 drug Drugs 0.000 claims description 6
- 238000012417 linear regression Methods 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 4
- 239000003643 water by type Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 238000010813 internal standard method Methods 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 238000001819 mass spectrum Methods 0.000 claims description 3
- 239000006199 nebulizer Substances 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 3
- 238000004445 quantitative analysis Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 239000008399 tap water Substances 0.000 claims description 3
- 235000020679 tap water Nutrition 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000003755 preservative agent Substances 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000004704 ultra performance liquid chromatography Methods 0.000 description 1
- 238000005303 weighing Methods 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
-
- 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
-
- 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
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/30—Control of physical parameters of the fluid carrier of temperature
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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
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/32—Control of physical parameters of the fluid carrier of pressure or speed
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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
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- 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
- G01N30/7233—Mass spectrometers interfaced to liquid or supercritical fluid chromatograph
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- 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
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- G01N30/86—Signal analysis
- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N2030/062—Preparation extracting sample from raw material
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N2030/342—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient fluid composition fixed during analysis
Abstract
The invention discloses a method for detecting ppcps based on a UPLC-MS/MS method, belonging to the technical field of water quality detection and analysis; the method can solve the problem that a multi-component high-throughput analysis method which comprehensively covers common Ppcps is lacked, once the simultaneous determination of multiple Ppcps is related, the relatively complex pretreatment technologies such as solid phase extraction are required to separate and enrich the Ppcps in a sample, not only time is consumed, but also a large amount of organic solvent is consumed, UPLC-MS/MS can rapidly separate 126 Ppcps within 14.1min, and the MRM monitoring mode of UPLC-MS/MS is utilized to perform qualitative analysis and quantitative determination on 126 Ppcps, so that the method is convenient to use, and reduces the consumption of organic solution.
Description
Technical Field
The invention discloses a method for detecting ppcps based on a UPLC-MS/MS method, belonging to the technical field of water quality detection and analysis.
Background
The PPCPs (pharmaceutical and personal care products) cover various different types of chemicals, including chemicals added in clinical medicines and personal care products, the PPCPs have higher biological activity, slow biodegradability and false persistence, the PPCPs are exposed to the environment for a long time, not only can damage an ecological system, but also can generate huge threat to human health, because the physical and chemical properties of the PPCPs of different types are different greatly, a mobile phase system suitable for chromatographic separation of the PPCPs also has large difference, a liquid chromatography-tandem mass spectrometry (LC-MS/MS) has the advantages of high analysis sensitivity, strong qualitative capability and capability of analyzing multi-component PPCPs simultaneously, and the existing detection method of the PPCPs can only be well suitable for detecting the PPCPs of single type or several types with similar physical and chemical properties, and a multi-component high-flux analysis method for comprehensively covering common PPCPs types is lacked, once the simultaneous determination of multiple PPCPs is involved, the separation and enrichment of PPCPs in a sample need to be carried out by adopting a relatively complex pretreatment technology such as solid phase extraction, which is time-consuming and needs to consume a large amount of organic solvents.
Disclosure of Invention
The method for detecting the PPCPs based on the UPLC-MS/MS method can solve the problems that a multi-component high-throughput analysis method which comprehensively covers common PPCPs is lacked, once the detection method relates to the simultaneous determination of multiple PPCPs, the PPCPs in a sample need to be separated and enriched by adopting a complex pretreatment technology such as solid phase extraction, the time is consumed, and a large amount of organic solvent is consumed.
In order to solve the problems, the invention provides the following technical scheme: a method for detecting ppcps based on a UPLC-MS/MS method comprises the following specific steps:
step 1: collecting a water sample: measuring 500mL of water sample by using a 1L brown screw bottle, repeatedly washing the screw bottle by using tap water before sampling, then washing the screw bottle by using methanol for 2 times, and finally washing the screw bottle by using ultrapure water for 3 times, wherein the collected water sample is refrigerated and stored in a dark place, and the refrigerating temperature is 0-4 ℃;
step 2: acidic substance adjusting the PH of the sample: the acidic substance is a mixture of monopotassium phosphate and phosphoric acid, wherein the monopotassium phosphate is 2.824-3.024g, the phosphoric acid is 1.8-2.0mL, and the sample is 500mL, so that the pH value is 1.8-2.2;
and step 3: solid-phase extraction by using a full-automatic solid-phase extractor: the method comprises the steps of enriching and purifying PPCPs in a water sample by using a solid phase extraction column, loading the sample with HLB/PSD (6cc, 500mg), loading the sample at the flow rate of 10mL/min, pushing the sample with nitrogen at the flow rate of 40mL/min for 10min, blowing the column with nitrogen at negative pressure (40min, the nitrogen pressure is 20psi), cleaning an injection pump with 10mL of methanol, eluting with 3mL of methanol at the flow rate of 1mL/min, then eluting with 5mL of methanol at the flow rate of 1mL/min, pushing the sample with nitrogen at the flow rate of 2mL/min at a slow speed, then rapidly pushing with nitrogen at the flow rate of 60mL/min, and blowing the collected eluent to be nearly dry by using nitrogen under the condition of 40 ℃ water bath. Carrying out constant volume to 1mL by using an initial mobile phase, then carrying out vortex mixing, centrifuging for 5min at the rotating speed of 13000rpm, and taking supernatant for UPLC-MS/MS analysis and determination;
and 4, step 4: adjusting mass spectrum detection conditions: the type of ion source: ESI, ion monitoring mode: MRM, nebulizer flow rate: 3mL/min, heating air flow: 10mL/min, interface temperature: 300 ℃, DL tube (desolventizing tube) temperature: 250 ℃, heating block temperature: 400 ℃, dry gas flow: 10 mL/min;
and 5: drawing a standard spectrogram and a standard curve: acquiring by using an MRM mode to obtain spectrograms of standard substances of 126 medicines and personal care products, performing linear regression by using an internal standard method, taking the peak area ratio of each PPCPs to the peak area ratio of the corresponding internal standard substance as a vertical coordinate, taking the concentration of the standard substance as a horizontal coordinate, and obtaining a corresponding PPCPs standard curve;
and 6: detecting a sample to be detected: performing UPLC-MS/MS analysis and determination on the water sample to be detected after pretreatment in the step 1 according to the detection conditions in the steps 2 and 3, comparing the obtained spectrogram of the sample to be detected with a standard spectrogram, determining signals to be detected with the same retention time and the same qualitative ion pair as the standard spectrogram, and performing quantitative and qualitative analysis on each PPCPs through a standard curve linear regression equation;
the chromatographic conditions used by the LC-MS/MS are chromatographic column: waters BEHC18 column, 1.7 μm, 2..1 mm. times.100 mm, column temperature: 40 ℃, sample introduction: 5uL, mobile phase: mobile phase A: water (with 0.05% formic acid), mobile phase B: acetonitrile, flow rate 0.4mL/min, mobile phase A and mobile phase B over time as follows:
| time (min) | Flow rate (mL/min) | A(％) | B(％) |
| 1 | 0.4 | 90 | 10 |
| 3 | 0.4 | 80 | 20 |
| 8 | 0.4 | 30 | 70 |
| 9 | 0.4 | 0 | 100 |
| 11 | 0.4 | 0 | 100 |
| 11.1 | 0.4 | 90 | 10 |
| 14.1 | 0.4 | 90 | 10 |
Further, before the step 3, respectively activating an equilibrium solid phase extraction column by using methanol (1mL/min) and ultrapure water (the pH is adjusted to be about 2 by using potassium dihydrogen phosphate and phosphoric acid, and the pH is adjusted to be 1 mL/min);
further, step 3 was paused for 3 minutes between two loads.
The invention has the beneficial effects that:
firstly, the UPLC-MS/MS can rapidly separate 126 PPCPs within 14.1 min;
secondly, performing qualitative analysis and quantitative determination on the 126 PPCPs by using an MRM monitoring mode of UPLC-MS/MS;
thirdly, the use is convenient, and the consumption of organic solution is reduced.
Drawings
FIG. 1 is a flow chart of a method for detecting ppcps based on the UPLC-MS/MS method.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
Example 1
According to the illustration of FIG. 1: the invention provides a method for detecting ppcps based on a UPLC-MS/MS method, which comprises the following steps:
1 Instrument and sample
1.1 Instrument:
ultra performance liquid chromatography tandem triple quadrupole mass spectrometer (Shimadzu LCMS-8060, Shimadzu), full automatic solid phase extractor (ASPEultra, Rui Ke) Waters BEHC18 column, (2.1mm 100mm, 1.7 μm, Watt).
1.2 sample: drinking water for life;
2 step (c)
Step 1: collecting a water sample: collecting water sample with 1L brown screw bottle, repeatedly washing with tap water before sampling, washing with methanol for 2 times, washing with ultrapure water for 3 times, and air drying for use (without washing, heating and brushing). When sampling, the sampling personnel wear the disposable gloves, thereby avoiding smearing the medicine on the skin. If the water sample is sampled from a faucet, the faucet is opened to drain water for a plurality of minutes, then the water sample is collected, and the bottle is filled for sampling. Besides water source water, ascorbic acid (30mg/L) and sodium thiosulfate (80mg/L) are added into the factory water and the peripheral water sample according to the sampling volume to serve as preservatives, and the preservatives are slightly shaken to dissolve the preservatives after the preservatives are added. The collected water sample needs to be refrigerated (0-4 ℃) and stored in dark place;
and 2, step: sample pretreatment: measuring 500mL of water sample, adding an internal standard solution, fully and uniformly mixing, adding 2.824g of monopotassium phosphate and 1.8mL of phosphoric acid to adjust the pH value to 1.8, then adding 0.25g of disodium ethylenediamine tetraacetic acid as a metal chelating agent, fully and uniformly mixing, enriching and purifying PPCPs in the water sample by using a solid phase extraction column filled with HLB/PSD (6cc, 500mg) mixed filler, and completing a solid phase extraction step by using a full-automatic solid phase extractor, wherein the procedure is as follows: before loading, activating an equilibrium solid phase extraction column by using methanol (1mL/min) and ultrapure water (adjusting the pH to be about 2 by using potassium dihydrogen phosphate and phosphoric acid, wherein the pH value is 1mL/min) respectively, and loading at the flow rate of 10 mL/min; pushing with nitrogen gas at a flow rate of 40mL/min for 10min, blowing the column with nitrogen gas at a negative pressure (40min, the nitrogen pressure is 20psi), cleaning an injection pump with 10mL methanol, eluting with 3mL methanol at a flow rate of 1mL/min, pausing for 3 min, eluting with 5mL methanol at a flow rate of 1mL/min, pushing with nitrogen gas at a flow rate of 2mL/min, rapidly pushing with nitrogen gas at a flow rate of 60mL/min, blowing the collected eluent to near dryness with nitrogen gas under a water bath condition of 40 ℃, carrying out vortex mixing after the initial mobile phase is fixed to 1mL, centrifuging at a rotation speed of 13000rpm for 5min, and taking the supernatant for UPLC-MS/MS analysis and determination;
and step 3: adjusting mass spectrum detection conditions: the type of ion source: ESI, ion monitoring mode: MRM, nebulizer flow rate: 3mL/min, heating air flow: 10mL/min, interface temperature: 300 ℃, DL tube (desolventizing tube) temperature: 250 ℃, heating block temperature: 400 ℃, dry gas flow: 10 mL/min;
and 4, step 4: drawing a standard spectrogram and a standard curve: acquiring spectrograms of 126 standard substances of medicines and personal care products by using an MRM mode, performing linear regression by using an internal standard method, taking the peak area of each PPCPs and the peak area ratio of the corresponding internal standard substance as vertical coordinates, and taking the concentration of the standard substance as horizontal coordinates to obtain a corresponding PPCPs standard curve;
and 5: detecting a sample to be detected: performing UPLC-MS/MS analysis and determination on the water sample to be detected after pretreatment in the step 1 according to the detection conditions in the steps 2 and 3, comparing the obtained spectrogram of the sample to be detected with a standard spectrogram, determining signals to be detected with the same retention time and the same qualitative ion pair as the standard spectrogram, and performing quantitative and qualitative analysis on each PPCPs through a standard curve linear regression equation;
further, the chromatographic conditions used for the LC-MS/MS are column: waters BEHC18 column, 1.7 μm, 2..1 mm. times.100 mm, column temperature: 40 ℃, sample introduction: 5uL, mobile phase: a mobile phase A: water (with 0.05% formic acid), mobile phase B: acetonitrile, flow rate 0.4mL/min, mobile phase a and mobile phase B as follows over time:
| time (min) | Flow rate (mL/min) | A(％) | B(％) |
| 1 | 0.4 | 90 | 10 |
| 3 | 0.4 | 80 | 20 |
| 8 | 0.4 | 30 | 70 |
| 9 | 0.4 | 0 | 100 |
| 11 | 0.4 | 0 | 100 |
| 11.1 | 0.4 | 90 | 10 |
| 14.1 | 0.4 | 90 | 10 |
The purposes that the UPLC-MS/MS can rapidly separate 126 medicines and personal care products within 14.1min, and the MRM monitoring mode of the UPLC-MS/MS is utilized to perform qualitative analysis and quantitative determination on the 126 medicines and the personal care products are achieved;
example 2
Example 2 compared to example 1, step 2: sample pretreatment: weighing 500mL of water sample, adding the internal standard solution, fully and uniformly mixing, adding 3.024g of monopotassium phosphate and 2.0mL of phosphoric acid, and adjusting the pH value to 2.2.
The present invention and its embodiments have been described above, but the description is not limited thereto, and the structure shown in the drawings is only one embodiment of the present invention, and the actual structure is not limited thereto. In summary, those skilled in the art should be able to conceive of the invention that any similar structural modes and embodiments as those of the above technical solutions are not devised without departing from the spirit of the invention, and therefore, the invention shall fall within the scope of the invention.
Claims (4)
1. A method for detecting ppcps based on a UPLC-MS/MS method is characterized in that: the method comprises the following specific steps: step 1: collecting a water sample: measuring 500mL of water sample by using a 1L brown screw bottle, repeatedly washing the screw bottle with tap water before sampling, then washing the screw bottle with methanol for 2 times, finally washing the screw bottle with ultrapure water for 3 times, and refrigerating the collected water sample at 0-4 ℃ in a dark place;
step 2: acidic substance adjusting the PH of the sample: the acid substance is a mixture of monopotassium phosphate and phosphoric acid, wherein the monopotassium phosphate is 2.824-3.024g, the phosphoric acid is 1.8-2.0mL, and the sample is 500mL, so that the pH value is 1.8-2.2;
and step 3: solid-phase extraction by using a full-automatic solid-phase extractor: the method comprises the steps of enriching and purifying PPCPs in a water sample by using a solid phase extraction column, loading the sample with HLB/PSD (6cc, 500mg), loading the sample at the flow rate of 10mL/min, pushing the sample with nitrogen at the flow rate of 40mL/min for 10min, blowing the column with nitrogen at negative pressure (40min, the nitrogen pressure is 20psi), cleaning an injection pump with 10mL of methanol, eluting with 3mL of methanol at the flow rate of 1mL/min, then eluting with 5mL of methanol at the flow rate of 1mL/min, pushing the sample with nitrogen at the flow rate of 2mL/min at a slow speed, then rapidly pushing with nitrogen at the flow rate of 60mL/min, and blowing the collected eluent to be nearly dry by using nitrogen under the condition of 40 ℃ water bath. Carrying out constant volume to 1mL by using an initial mobile phase, then carrying out vortex mixing, centrifuging for 5min at the rotating speed of 13000rpm, and taking supernatant for UPLC-MS/MS analysis and determination;
and 4, step 4: adjusting mass spectrum detection conditions: the type of ion source: ESI, ion monitoring mode: MRM, nebulizer flow rate: 3mL/min, heating air flow: 10mL/min, interface temperature: 300 ℃, DL tube (desolventizing tube) temperature: 250 ℃, heating block temperature: 400 ℃, dry gas flow: 10 mL/min;
and 5: drawing a standard spectrogram and a standard curve: acquiring by using an MRM mode to obtain spectrograms of standard substances of 126 medicines and personal care products, performing linear regression by using an internal standard method, taking the peak area ratio of each PPCPs to the peak area ratio of the corresponding internal standard substance as a vertical coordinate, taking the concentration of the standard substance as a horizontal coordinate, and obtaining a corresponding PPCPs standard curve;
and 6: detecting a sample to be detected: and (3) carrying out UPLC-MS/MS analysis and determination on the water sample to be detected after pretreatment in the step (1) according to the detection conditions in the steps (2) and (3), comparing the obtained spectrogram of the sample to be detected with a standard spectrogram, determining signals to be detected with the same retention time and the same qualitative ion pair as the standard spectrogram, and carrying out quantitative and qualitative analysis on each PPCPs through a standard curve linear regression equation.
2. The method for detecting ppcps based on the UPLC-MS/MS method as claimed in claim 1, wherein: the chromatographic conditions used by the LC-MS/MS are chromatographic columns: waters BEHC18 column, 1.7 μm, 2..1 mm. times.100 mm, column temperature: 40 ℃, sample introduction: 5uL, mobile phase: mobile phase A: water (with 0.05% formic acid), mobile phase B: acetonitrile, flow rate 0.4mL/min, mobile phase A and mobile phase B over time as follows.
3. The method for detecting ppcps according to claim 1, wherein the method comprises the following steps: and 3, activating the equilibrium solid-phase extraction column by using methanol (1mL/min) and ultrapure water (the pH is adjusted to be about 2 by using potassium dihydrogen phosphate and phosphoric acid, and the pH is adjusted to be 1mL/min) respectively before loading in the step.
4. The method for detecting ppcps according to claim 1, wherein the method comprises the following steps: pause for 3 minutes between two loads in step 3.
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