CN111595958A - Method for determining multi-class medicines and personal care products in landfill leachate - Google Patents
Method for determining multi-class medicines and personal care products in landfill leachate Download PDFInfo
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- CN111595958A CN111595958A CN202010327307.8A CN202010327307A CN111595958A CN 111595958 A CN111595958 A CN 111595958A CN 202010327307 A CN202010327307 A CN 202010327307A CN 111595958 A CN111595958 A CN 111595958A
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- personal care
- care products
- water
- leachate
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Abstract
The invention belongs to the technical field of environmental monitoring, and provides a method for detecting various types of medicines and personal care products in landfill leachate. The test method comprises pretreatment, enrichment, elution and UPLC-MS/MS detection. The invention can simultaneously detect various types of medicines and personal care products in the percolate by one-time sample introduction, and has short detection time. Because the matrix of the leachate is complex and the number of interfering substances is large, the method can effectively remove interfering components by optimizing the water sample pretreatment and solid phase extraction enrichment conditions, is successfully applied to the detection of 46 medicaments and personal care products in the landfill leachate, has accurate result and has good practicability.
Description
Technical Field
The invention belongs to the technical field of environmental monitoring, and particularly relates to a method for measuring various types of medicines and personal care products in landfill leachate.
Background
In recent years, Pharmaceuticals and Personal Care Products (PPCPs) have received much attention as an important emerging class of pollutants. Due to the enormous consumption and continuous input of PPCPs, which gradually accumulate in water environments, exhibit pseudo-persistence and potential toxicity to aquatic organisms, PPCPs have become a research hotspot in the field of water environments.
Research shows that PPCPs are mainly discharged into water environment through domestic sewage, effluent of sewage treatment plants, pharmaceutical industry wastewater, hospital wastewater, livestock and poultry breeding wastewater, landfill leachate and the like. However, research on PPCPs in landfill leachate is relatively limited compared to other discharge sources, and one important factor is that the quality of leachate is complex, which makes the PPCP difficult to quantify in the leachate, thus hindering the development of research.
The landfill has the advantages of simple operation, low cost and the like, and is widely applied to the treatment of urban solid wastes. In addition to general household waste, landfill sites are also the final disposal sites for various overdue or useless household drugs and other personal care product residues. The PPCPs are partially degraded by microorganisms or adsorbed by solid wastes, but most of the PPCPs are dissolved or separated by leaching of organic matter decomposition water, free water, rainwater, runoff and the like in the solid wastes, so that landfill leachate with complex components and high concentration is formed. These PPCPs may also penetrate into groundwater through the soil at the bottom of the landfill, and threaten the safety of the surrounding groundwater.
Medicines and personal care products are generally detected in environmental water, wherein CN201510148387.X discloses a method for measuring tetracycline and sulfonamide antibiotics in underground water, river water and pig raising wastewater, and CN201310247043.5 discloses a method for measuring tetracycline antibiotics in surface water, but most of the existing researches aim at detecting antibiotics, and no report is provided for a related method for simultaneously detecting various types of medicines and personal care products in percolate, so that the method has certain limitations.
In summary, the existing analysis methods for PPCPs in landfill leachate have the disadvantages of single detection type, small number and the like. In view of the reasons that the PPCPs in the leachate are various and the potential harm to the surrounding ecological environment and the human health is not negligible, the establishment of the method for detecting the PPCPs in the leachate has important practical significance.
Disclosure of Invention
The invention aims to provide a method for determining various types of medicines and personal care products in leachate. The method can separate and enrich multi-component medicines and personal care products in the leachate matrix, and overcomes the defect of analysis only aiming at certain medicines and personal care products.
The technical concept of the invention is as follows:
the method provided by the invention adopts the combination of solid-phase extraction pretreatment and high performance liquid chromatography tandem mass spectrometry technology, and finally can realize accurate, stable, small-interference, rapid and efficient enrichment and quantitative determination of 46 typical medicines and personal care products in landfill leachate samples through optimization of the pretreatment process.
The technical scheme of the invention is as follows:
the invention provides a method for determining various types of medicines and personal care products in leachate, which comprises the following steps:
(1) pretreatment of water samples (pretreatment)
Taking a certain amount of landfill leachate, diluting a water sample by ultrapure water, filtering the water sample by a filter membrane to remove suspended matters, and adding Na2Adding an internal standard substance indicating the recovery rate into the EDTA aqueous solution, and adjusting the pH value of the water sample to 6.5 +/-0.2 by using 1-2 mol/L dilute sulfuric acid;
(2) solid phase extraction for enriching target medicine and personal care product
Activating and activating a solid-phase extraction column (HLB (hydrophile-lipophile balance) column) by using methanol and high-purity water in sequence, enabling the sample treated in the step (1) to pass through the column, and controlling the flow rate of the sample passing through the column; after the enrichment is finished, leaching the solid phase extraction column by using leacheate, and drying the solid phase extraction column in vacuum; finally, eluting the solid phase extraction column by using a certain volume of elution solvent, collecting eluent and concentrating to obtain a concentrated sample; (blowing with nitrogen blower under mild nitrogen flow to obtain residue, dissolving the residue with organic solvent of certain concentration, diluting to desired volume, filtering, transferring to small bottle, and diluting with mixed solution of methanol and water at a ratio of 1: 4)
(3) Determining the content of 46 medicines and personal care products in the leachate by using a high performance liquid chromatography-tandem mass spectrometry method; an internal standard method is adopted, and a high performance liquid chromatography tandem mass spectrometer is used for quantitatively detecting 46 medicines and personal care products in the percolate; the 46 drugs and personal care products include anti-inflammatory drugs (paracetamol, naproxen, diclofenac), hypotensive drugs (diltiazem, metoprolol), hypoglycemic drugs (gliclazide, hypoglycemic drugs), hypolipidemic drugs (bezafibrate, gemfibrozil), antagonists (cimetidine), anticoagulants (warfarin), antipruritic agents (crotamiton), antibacterial agents (triclosan), anthelmintics (fenbendazole, febantel), anthelmintics (deet), anticonvulsants (carbamazepine), amidol antibiotics (chloramphenicol), sulfa antibiotics (trimethoprim, sulfachloropyridazine, sulfadiazine, sulfaquinoxaline, sulfamethoxazole, sulfamonomethoxazole, sulfamethazine, sulfamethoxazole, sulfamethoxydiazine, tetracyclines antibiotics (milbemycin, tetramycin, tetramethrin, metoclopramide, trimethoprim, sulfamethoxazole, etc.) Demeclocycline, terramycin, tetracycline, chlortetracycline), quinolone antibiotics (flumequine, sparfloxacin, ciprofloxacin, difloxacin, enrofloxacin, lomefloxacin, marbofloxacin, norfloxacin, ofloxacin, pefloxacin), macrolide antibiotics (leucomycin, tylosin, erythromycin dehydrate) and various pollutants.
The further technical scheme is as follows:
in the step (1), Na is contained in the sample2The mass-volume concentration of EDTA was 0.10g/100mL (0.10 g increase per 100mL water sample).
In the step (1), 100 μ L of phenacetin-one with the concentration of 1000 μ g/L is respectively added before the solid phase extraction of the sample13C. Gemfibrozil-6D. Atrazine-5D. 2-methyl-4-chloropropionic acid-3D. Sulfamethazine-13C. Deet and mosquito repellent7D. Tetracycline-6D. Fenbendazole-3D. Roxithromycin-7D、13C3 15N-ciprofloxacin and ofloxacin-3D eleven internal standards indicate recovery.
In the step (1), Na is added firstly after a water sample is filtered by a glass fiber filter membrane to remove granular suspended matters2Adding an internal standard substance indicating the recovery rate into the EDTA aqueous solution, and adjusting the pH value to be 6.5 by using dilute sulfuric acid, wherein the approximate range of the pH value is about a target value +/-0.2.
In the step (2), an HLB column is adopted as an extraction column of the solid-phase extraction, and the column filling amount of the HLB column is 500 mg.
In the step (2), in the activation step of the solid-phase extraction, methanol and water are respectively adopted to activate the extraction column of the solid-phase extraction; the activation time can be 5-10 min, such as 10 min; the flow rate of the activated solid phase extraction column can be 1-3 mL/min, such as 3 mL/min.
In the step (2), the flow rate of the sample flowing through the solid phase extraction column can be 5-10mL/min, such as 5 mL/min.
In the step (2), in the step of leaching the solid-phase extraction, a methanol-water solution with the volume concentration of 5% is adopted, so that impurities are removed, and noise interference is reduced. The flow rate of the leaching solution can be 1-5 mL/min, such as 5 mL/min.
In the step (2), the organic solvent used for eluting the solid-phase extraction column is methanol. The elution step flow rate may be 1 mL/min.
In the step (2), the organic solvent used for dissolving the residual substances after nitrogen blowing is methanol: water 1:4 methanol-water solution.
In the step (3), LCMS8050 high performance liquid chromatography tandem mass spectrometry of Shimadzu corporation is selected for detection; the column was Shimadzu Shim-pack GIST C18 (100X 2.1mm, 2 μm).
In the step (3), the liquid chromatography separation parameters are as follows: the flow rate of the mobile phase is 0.4 mL/min; the sample injection amount is 2.0 mu L; the column temperature is 40 ℃; mobile phase a was a formic acid (0.1%) -ammonium acetate (2mmol/L) -aqueous solution (where the water was Milli-Q ultrapure water) in volume concentration; the mobile phase B is chromatographic grade methanol; the gradient elution procedure was: 0-0.5min, 10% B; 0.5-5min, 10% B-100% B; 5-7min, 100% B; 7-7.1min, 100% B-10% B; 7.1-10min, 10% B.
In the step (3), the mass spectrum detection conditions are as follows: ionization mode: ESI; the detection mode is as follows: monitoring multiple reactions; ion spray voltage: 4.0 KV; atomizing: nitrogen gas is 3L/min; drying gas: nitrogen gas is 10L/min; heating gas: nitrogen gas is 10L/min; collision gas: argon gas; DL temperature: 250 ℃; heating module temperature: 400 ℃; ion source temperature: at 300 ℃.
The invention has the difficulties of complex water quality, various types, optimized experimental process and optimized instrument test.
The invention has the beneficial effects that:
the detection method can realize high-efficiency, sensitive and accurate detection of 46 medicaments and personal care products in the landfill leachate by a solid-phase extraction-high performance liquid chromatography tandem mass spectrometry detection technology, and has stable detection result and small interference.
Compared with the prior art, the invention has the following advantages:
1. the Oasis HLB solid-phase extraction column selected by the invention is used for enriching and purifying 46 medicines and personal care products, has high and stable recovery rate (the recovery rate meets the requirement of 60-140 percent, and the relative standard deviation of a parallel water sample is less than 20 percent), has strong selectivity and large adsorption capacity, and achieves the aim of effectively separating and enriching target substances.
2. The pretreatment method disclosed by the invention is simple to operate, strong in repeatability, small in organic solvent usage amount, small in relative standard deviation of the same batch of samples, and capable of meeting the detection requirements of medicines and personal care products under the condition of analyzing complex leachate matrixes.
3. The detection method can simultaneously detect 46 medicaments and personal care products in the percolate by one-time machine feeding and sample feeding, and has the advantages of short detection process (consuming 10min) and good practicability.
4. Because the matrix of the leachate is complex and the number of interfering substances is large, the method can effectively eliminate interfering components and enrich target drugs and personal care products by optimizing the water sample pretreatment and solid phase extraction enrichment conditions, so that the subsequent detection sensitivity is high and the result is accurate.
Drawings
FIG. 1 shows the difference in Na in example 12And measuring the adding standard recovery rate of 46 medicaments and personal care products in the leachate under the condition of adding EDTA.
Figure 2 is a graph of the normalized recovery of 46 drugs and personal care products in leachate measured at different eluent volumes in example 1.
FIG. 3 shows a reaction condition in Na2MRM spectrum of representative substance under the condition of EDTA addition amount of 0.10g/100mL, pH 6.5, eluent of methanol and eluent volume of 10mL
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the content of the present invention is not limited to the following examples.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1: optimization of solid phase extraction conditions
(1)Na2Optimization of EDTA
Adding a heavy metal complexing agent Na into a water sample2EDTA solution capable of masking Ca2+，Mg2+And (3) metal ions are used for inhibiting the chelation of fluoroquinolone antibiotics and tetracycline antibiotics in the leachate with the metal ions, so that the target object is kept in a stable state.
Fixing other extraction conditions, respectively adopting Na of 0, 0.05g/100mL, 0.10g/100mL and 0.15g/100mL2The EDTA solution was tested for the following quinolone and tetracycline antibiotics.
The results are shown in FIG. 1, and it was found that 0.10g/100mL of Na2The EDTA solution can obviously improve the recovery rate of quinolone and tetracycline medicaments and personal care products. The recovery rate of fluoroquinolone antibiotics and tetracycline antibiotics is between 60% and 140%, and the requirement of an analysis method is met.
(2) pH optimization and eluent optimization of water samples
Due to the wide variety of target PPCPs, the structures and properties are different. The pH value of a water sample has great influence on solid phase extraction; meanwhile, in solid phase extraction, solvents such as methanol and acetonitrile are often adopted to elute the target from the solid phase extraction column. Thus the examples measure the extraction effect on water samples at different pH conditions using different eluents. Four replicates were set up for each experiment.
And (3) fixing eluent, adjusting the pH value of a water sample by respectively adopting pH values of 2.5, 4.0 and 6.5, performing experiments on all targets, and determining the recovery rate.
Fixing pH, respectively adopting methanol and acetonitrile, eluting the extraction column, and determining the recovery rate.
The results are shown in table 1, and the following conclusions can be drawn: the pH value of the water sample is 6.5, the recovery rate of most medicines and personal care products is good under the condition that the eluent is methanol, the recovery rate is 60-140%, and the analysis method has certain reliability in general. In addition, the results of parallel experiments show that the Relative Standard Deviation (RSD) of the recovery rate of each drug and personal care product is less than 20 percent, and the analysis requirements of common environmental samples are met.
Table 1 standard recovery (RSD,%) (n ═ 4) of drug and personal care products from water samples at different pH and different eluents
(3) Eluent volume optimization
Elution volume also has some influence on the enrichment process of the drug, and elution is performed with methanol under the condition that the pH of a water sample is 6.5, and the elution volume is set to be 6mL and 10 mL.
As shown in FIG. 2, 10mL of eluent can elute more substances, and most substances have recovery rates of 60% -140%, resulting in good recovery rates.
Example 2 comparison of the present invention with the detection techniques in existing percolate
The existing analysis method for medicines and personal care products in landfill leachate in the prior art has the defects of single detection type and small number, for example, Sui et al, 2017 discloses that 18 medicines and personal care products can be detected (but detected by two methods), only 9 substances can be detected under the conditions that the pH is 6.5 and the eluent is methanol ((bezafibrate, carbamazepine, gemfibrozil, caffeine, chloramphenicol, sulpiride, trimethoprim, diclofenac and metoprolol)), Wu et al, 2015 discloses that 20 antibiotics including sulfonamides, tetracyclines, macrolides and quinolones can be detected, but the method is only limited to the antibiotic type.
The landfill leachate is measured by the existing method, compared with the test scheme of the invention, and the condition of the recovery rate of the added standard is inspected. The results show that: the invention has good standard recovery rate (falling in the range of 68-106 percent) and stable test result (RSD falling in the range of 2-15 percent). In the prior art, the recovery rate is occasionally lower than 60% or higher than 140%, which is not very satisfactory for the analysis method.
TABLE 2 comparison of the recovery rates of the invention with the spiked recovery of the prior art
Example 3: drug and personal Care assay in actual percolate samples
In order to further verify the feasibility of the method, the experiment carries out 2 sampling activities on the percolate of a certain refuse landfill, two groups of parallel samples are set in each experiment, and the operation is carried out according to the following steps:
(1) diluting and filtering the collected water sample: taking 4mL of water sample, diluting 50 times to 200mL, setting 100mL of parallel samples (the water samples are divided into two groups), and filtering through a glass fiber filter membrane with the aperture of 0.7 mu m.
(2) Na was added at a concentration of 0.10g/100mL2The aqueous EDTA solution was thoroughly shaken to homogenize the mixture. The pH was adjusted to 6.5 (6.5. + -. 0.2) with 1mol/L sulfuric acid and 100. mu.L of recovery internal standard indicator was added at a concentration of 1000. mu.g/L.
(3) The method comprises the following specific implementation steps of performing solid-phase extraction on a water sample: respectively activating the HLB extraction column by 6mL of methanol and 6mL of high-purity water multiplied by 3 for 10min, enabling the water sample in the step (2) to flow through the column at the flow rate of 5mL/min, leaching the extraction column by 6mL of methanol/water solution (1/19, v/v), vacuumizing the extraction column for one hour, and leaching the extraction column by 10mL of methanol to obtain eluent.
(4) After collecting the eluate, the eluate was purged with nitrogen at 40 ℃ in a water bath to 0.3mL by a nitrogen purge apparatus, and the volume of the eluate was adjusted to 1mL by a methanol/water (1/4, v/v) solution.
(5) 46 drugs and personal care products were analyzed using a SHIMADZU UPLC-MS/MS combination.
The results of the two sampling measurements are shown in the table.
The data in the table show that the method can be used for the detection of drugs and personal care products in landfill leachate. Of the 46 drugs and personal care products tested, over 30 contaminants were detected in two sampling runs and the RSD of the replicates was less than 20%, demonstrating that the method is robust. The concentration level of pollutants in the leachate is high (ND-49790 ng/L), which indicates that the residues of medicines and personal care products in the landfill leachate are not negligible.
TABLE 3 detection results of contaminants such as drugs and personal Care products present in leachate from a certain landfill
Note: ND means not detected
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the concept of the present invention, and these modifications and decorations should also be regarded as being within the protection scope of the present invention.
Claims (10)
1. A method for determining multi-class drugs and personal care products in landfill leachate is characterized by comprising the following steps:
(1) pretreatment: taking a certain amount of landfill leachate, diluting and filtering a water sample, adding ethylene diamine tetraacetic acid, adding an internal standard substance indicating the recovery rate, and adjusting the pH value of the water sample to 6.5 +/-0.2 by using 1-2 mol/L dilute sulfuric acid;
(2) enrichment: sequentially activating the HLB small column by using methanol and high-purity water, introducing a pretreated water sample, leaching by using a methanol water solution with the volume ratio of 5% after finishing enrichment, and drying the solid-phase extraction column under a vacuum condition;
(3) and (3) elution: eluting the enriched small column with eluent, collecting the eluent and concentrating to obtain a concentrated sample;
(4) UPLC-MS/MS detection: and (3) carrying out constant volume on the concentrated solution by using a mixed solution of methanol and water, and detecting by using a high performance liquid chromatography-tandem mass spectrometry instrument.
2. The method of claim 1, wherein the pharmaceutical and personal care products comprise 46 pharmaceutical and personal care products.
3. The method of claim 1, wherein the amount of disodium edetate added in step (1) is 0.10g per 100mL of water sample.
4. The method for detecting multiple types of drugs and personal care products in leachate according to claim 1, wherein in step (2), the flow rate of the water sample through the column is controlled to be 5-10 mL/min.
5. The method for detecting the multi-class drugs and the personal care products in the leachate according to claim 1, wherein the flow rate of the leaching in the step (2) is controlled to be 1-5 mL/min.
6. The method of claim 1, wherein the eluent in step (3) is 10mL of methanol and the eluent flow rate for eluting the HLB column is not more than 1 mL/min.
7. The method for the determination of multi-class drugs and personal care products in leachate according to claim 1, wherein the concentrated sample obtained in step (3) is dried by mild nitrogen flow through nitrogen blower to obtain residue; dissolving the residue with organic solvent, diluting to desired volume, filtering, transferring to small bottle, and testing.
8. The method of claim 1, wherein the HPLC-MS/MS detection conditions in step (4) are as follows: a chromatographic column: Shimadzum-packGISTC 18 (100X 2.1mm, 2 μm); mobile phase: phase A is a formic acid (0.1%) -ammonium acetate (2mmol/L) -aqueous solution (where the water is Milli-Q ultrapure water) in volume concentration; phase B is chromatographic grade methanol; flow rate: 0.4mL/min, sample size: 2 mu L of the solution; the column temperature is 40 ℃; the mobile phase gradient elution procedure was: 0-0.5min, 10% B; 0.5-5min, 10% B-100% B; 5-7min, 100% B; 7-7.1min, 100% B-10% B; 7.1-10min, 10% B.
9. The method for detecting multi-class drugs and personal care products in leachate according to claim 1, wherein in step (4), the liquid quality detection condition is: ionization mode: ESI; the detection mode is as follows: monitoring multiple reactions; ion spray voltage: 4.0 KV; atomizing: nitrogen gas is 3L/min; drying gas: nitrogen gas is 10L/min; heating gas: nitrogen gas is 10L/min; collision gas: argon gas; DL temperature: 250 ℃; heating module temperature: 400 ℃; ion source temperature: at 300 ℃.
10. The method for detecting multiple types of drugs and personal care products in leachate according to any of claims 1 to 9, which has been successfully applied to the detection of target pollutants in leachate samples of actual landfill sites, the relative standard deviation of parallel samples is less than 20%, the results are stable and accurate, and the method has good practicability.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114942289A (en) * | 2022-06-02 | 2022-08-26 | 贵州大学 | Method for determining anticoccidial drugs in water in surrounding environment of farm by liquid chromatography-mass spectrometry |
| CN115097024A (en) * | 2022-05-31 | 2022-09-23 | 重庆市疾病预防控制中心(重庆市救灾防病应急处理中心) | PPCPS detection method based on UPLC-MS/MS method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105699537A (en) * | 2016-04-07 | 2016-06-22 | 大连理工大学 | Synchronous detection method for plurality of types of drug residues in water body |
| MY161081A (en) * | 2012-06-15 | 2017-04-14 | Univ Putra Malaysia | Method for the quantification of pharmaceuticals and personal care products |
| CN107024548A (en) * | 2016-07-10 | 2017-08-08 | 华中农业大学 | The method for detecting 92 kinds of antibacterial medicine residues in water environment simultaneously |
| CN108254481A (en) * | 2016-12-29 | 2018-07-06 | 深圳先进技术研究院 | A kind of method of multi-class drug and personal care articles and pesticide in quick detection water |
| CN109342588A (en) * | 2018-10-19 | 2019-02-15 | 重庆大学 | Optimization method for PFOA Solid Phase Extraction in landfill leachate |
-
2020
- 2020-04-23 CN CN202010327307.8A patent/CN111595958A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MY161081A (en) * | 2012-06-15 | 2017-04-14 | Univ Putra Malaysia | Method for the quantification of pharmaceuticals and personal care products |
| CN105699537A (en) * | 2016-04-07 | 2016-06-22 | 大连理工大学 | Synchronous detection method for plurality of types of drug residues in water body |
| CN107024548A (en) * | 2016-07-10 | 2017-08-08 | 华中农业大学 | The method for detecting 92 kinds of antibacterial medicine residues in water environment simultaneously |
| CN108254481A (en) * | 2016-12-29 | 2018-07-06 | 深圳先进技术研究院 | A kind of method of multi-class drug and personal care articles and pesticide in quick detection water |
| CN109342588A (en) * | 2018-10-19 | 2019-02-15 | 重庆大学 | Optimization method for PFOA Solid Phase Extraction in landfill leachate |
Non-Patent Citations (6)
| Title |
|---|
| MYRSINI PAPAGEORGIOU 等: "Seasonal occurrence, removal, mass loading and environmental risk assessment of 55 pharmaceuticals and personal care products in a municipal wastewater treatment plant in Central Greece", 《SCIENCE OF THE TOTAL ENVIRONMENT》 * |
| 柯润辉 等: "上海某城市污水处理厂污水中药物类个人护理用品(PPCPs)的调查研究" * |
| 王鑫 等: "再生水及地下水EDCs和PPCPs污染特征分析与生态风险评估" * |
| 陈永艳 等: "超高效液相色谱串联质谱测定饮用水中PPCPs残留", 《中国给水排水》 * |
| 陈溪 等: "基于超高效液相色谱-高分辨质谱技术的水中112种药品和个人护理用品的高通量筛查和定量方法" * |
| 陈溪 等: "基于超高效液相色谱-高分辨质谱技术的水中112种药品和个人护理用品的高通量筛查和定量方法", 《色谱》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115097024A (en) * | 2022-05-31 | 2022-09-23 | 重庆市疾病预防控制中心(重庆市救灾防病应急处理中心) | PPCPS detection method based on UPLC-MS/MS method |
| CN114942289A (en) * | 2022-06-02 | 2022-08-26 | 贵州大学 | Method for determining anticoccidial drugs in water in surrounding environment of farm by liquid chromatography-mass spectrometry |
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