Rapid detection and analysis method for nine endocrine disruptors in water

Abstract

The invention discloses a rapid detection and analysis method for nine endocrine disruptors in water, belongs to the technical field of environment detection, and aims to solve the technical problems that in the prior art, the dosage of an organic solvent for pretreatment of the endocrine disruptors in water is large, the treatment time is long, and the detection limit of the endocrine disruptors needs to be further improved. The method comprises the following steps: adding a water sample and an internal standard substance into a centrifuge tube, and separating and extracting the water sample and the internal standard substance by using an extract consisting of sodium chloride and acetonitrile to obtain a test sample. According to the method disclosed by the invention, by optimizing factors, such as an extraction solvent, an extraction volume, extraction time, a mobile phase, mass spectrum parameters and the like, which influence the selectivity and the quantitative accuracy of the method, the dosage of an extraction solution is effectively reduced, the pretreatment time is saved, and the ionization efficiency, the sensitivity and the detection limit are also improved.

Description

Technical Field

[0001] The present invention relates to the field of environmental detection technology, and in particular to a method for rapid detection and analysis of nine endocrine disruptors in water. Background Art

[0002] Endocrine disrupting chemicals (EDCs) refer to exogenous chemical substances that intervene in the synthesis, secretion, transport, combination, reaction and metabolism of hormones in humans or animals, disrupting the endocrine system in a manner similar to estrogen, and causing abnormal effects on organisms. The impact of endocrine disruptors on environmental safety and the harm to life and health have attracted widespread attention, among which alkylphenols and bisphenol A are the most common.

[0003] At present, the main analytical detection methods for alkylphenols and bisphenol A in the environment are gas chromatography-mass spectrometry, high performance liquid chromatography, and liquid chromatography-mass spectrometry. The pretreatment methods often use derivatization or solid phase extraction. However, liquid extraction or solid phase extraction methods consume a large amount of organic solvent (usually ≥50mL) and a large volume of water sample (≥500mL), resulting in time-consuming pretreatment (>2 hours), high cost, and cumbersome operation.

[0004] Most existing methods are developed for a single or a few compounds, and the physicochemical properties of the nine EDCs vary significantly (such as a large span of logKow values). It is difficult for traditional extraction systems to achieve simultaneous high recoveries of multiple targets. In addition, the concentration of EDCs in water samples is often at the ng / L level. However, existing HPLC-MS / MS methods rely on complex purification steps due to low ionization efficiency (such as APCI source) or significant matrix effects, which not only introduces operational errors but also prolongs the analysis cycle.

[0005] This study invented a method using small volume liquid-liquid extraction to extract alkylphenols and bisphenol A in water. Only 10 mL of sample is needed, the amount of organic solvent used is small, the operation is simple and convenient, and the pre-treatment time is greatly saved. At the same time, the liquid chromatography-triple quadrupole mass spectrometry uses an ESI source with high ionization efficiency and good sensitivity. The detection limit can also meet or exceed the requirements of existing analytical methods.

[0006] In view of the research in this area, a detection and analysis scheme is proposed. Summary of the invention

[0007] The purpose of the present invention is to provide a rapid detection and analysis method for 9 endocrine disruptors in water, which is used to solve the technical problems in the prior art that the pretreatment of endocrine disruptors in water requires a large amount of organic solvent, the treatment time is long, and the detection limit of endocrine disruptors needs to be further improved.

[0008] The object of the present invention can be achieved by the following technical solutions: A rapid detection and analysis method for 9 endocrine disruptors in water, comprising the following steps:

[0009] S1. Take a water sample and an internal standard and add them into a centrifuge tube, and use an extractant to separate and extract it to obtain a test sample. Among them, the extractant is composed of sodium chloride and acetonitrile;

[0010] S2. Adjust the chromatographic conditions and mass spectrometry conditions of a high performance liquid chromatography-tandem triple quadrupole mass spectrometer according to the detection conditions;

[0011] S3. The test sample in step S1 is measured by the high performance liquid chromatography-tandem triple quadrupole mass spectrometer in step S2 to obtain the content of endocrine disruptors in the test solution.

[0012] Further, the preparation method of the test sample is as follows: Measure 10 mL of the water sample into a 25 mL centrifuge tube, add 4 g of dry sodium chloride and an internal standard solution to the centrifuge tube, vortex for 1 min to mix evenly, add 5 mL of acetonitrile to the centrifuge tube, vortex for 1 min, let stand for 5 min, and then use a pipette to take 1 mL of the supernatant into a 1.5 mL brown injection vial to obtain the test sample.

[0013] Further, the preparation method of the dry sodium chloride is: Place the sodium chloride in an atmosphere furnace at 400 °C and burn it for 4 - 6 h; The internal standard solution is composed of an internal standard and acetonitrile, with a concentration of 1 mg / L, and the internal standards are bisphenol A-D4 and nonylphenol-D4.

[0014] Further, the chromatographic conditions of the high performance liquid chromatography-tandem triple quadrupole mass spectrometer are as follows:

[0015] Chromatographic column: phenomenex LC Trapping column: (100 mm × 3.0 mm × 2.6 μm);

[0016] Waters BEH C18 liquid chromatography column (100 mm × 2.1 mm × 1.7 μm);

[0017] Column temperature: 40 °C;

[0018] Injection volume: 10 μL;

[0019] Flow rate: 0.3 mL / min;

[0020] Mobile phase: 0.02% ammonia water solution (A) and acetonitrile (B);

[0021] Gradient elution program: 0 - 2.0 min, 20% - 95% B; 2.1 - 5.0 min, 95% B; 5.1 - 7.0 min 20% B.

[0022] Furthermore, the mass spectrometry conditions of the high performance liquid chromatography - triple quadrupole mass spectrometer are as follows:

[0023] Ion source: ESI source, negative ion mode;

[0024] Scanning mode: multiple reaction monitoring (MRM);

[0025] Curtain gas pressure: 30 Kpa;

[0026] Spray voltage: -4500 V;

[0027] Atomization temperature: 500 °C;

[0028] Atomizing gas pressure: 50 Kpa;

[0029] Auxiliary gas pressure: 55 Kpa.

[0030] Furthermore, the 9 endocrine disruptors in water are: bisphenol A, 4 - branched nonylphenol, 4 - nonylphenol, 4 - butylphenol, 4 - pentylphenol, 4 - hexylphenol, 4 - heptylphenol, 4 - octylphenol, 4 - tert - octylphenol.

[0031] Furthermore, the detection limits of the 9 endocrine disruptors in water by this detection method are 0.025 - 0.08 μg / L.

[0032] The present invention has the following beneficial effects:

[0033] 1. The present invention adopts the small - volume liquid - liquid extraction - high performance liquid chromatography - mass spectrometry coupling technology. Compared with the common detection methods of alkylphenols and bisphenol A reported in the literature, the biggest advantage is that on the basis of ensuring the detection sensitivity, it greatly saves the time and cost of sample pretreatment and maximally ensures the recovery rates of various target substances.

[0034] 2. The present invention also examines and optimizes the factors affecting the method selectivity and quantitative accuracy, such as extraction solvent, extraction volume, extraction time, mobile phase, mass spectrometry parameters, etc., and establishes a method for simultaneous analysis and determination of 8 alkylphenols and bisphenol A in surface water. The detection limits of the method are between 0.025 and 0.08, and the relative standard deviations RSD are respectively between 4.2% - 12%, 1.9% - 6.1%, 1.5% - 17%. During the analysis of alkylphenols and bisphenol A in surface water by this method, 3 endocrine disruptors are detected, namely bisphenol A, nonylphenol, and 4 - tert - octylphenol. The results show that this method is simple to operate, has high sensitivity and good accuracy, and can meet the determination of trace alkylphenols and bisphenol A in surface water samples. Description of the Drawings

[0035] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0036] Figure 1 Table of information on the instruments and equipment mainly used in the present invention;

[0037] Figure 2 Table of mass spectrometry analysis conditions and data for alkylphenols and bisphenol A in the present invention;

[0038] Figure 3 Extraction efficiency of alkylphenols and bisphenol A in the present invention under different acetonitrile dosages;

[0039] Figure 4 Extraction efficiency of alkylphenols and bisphenol A in the present invention under different NaCl dosages;

[0040] Figure 5 Extraction efficiency of alkylphenols and bisphenol A in the present invention under different vortex times;

[0041] Figure 6 MRM spectra of the target compounds of alkylphenols and bisphenol A in the present invention;

[0042] Figure 7 MRM spectra of each target compound of alkylphenols and bisphenol A in the present invention;

[0043] Figure 8 Table of linear equations, correlation coefficients, detection limits, and lower limits of determination of each target compound of alkylphenols and bisphenol A in the present invention;

[0044] Figure 9 Table of recovery rates and precision determination data for the rapid detection and analysis method of 9 endocrine disruptors in the present invention. Detailed implementation manners

[0045] The following will clearly and completely describe the technical solutions of the present invention in combination with the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0046] The information on the instruments and equipment mainly used in this application is shown in Table 1.

[0047] Example 1

[0048] This embodiment provides the analysis conditions of a high performance liquid chromatography - triple quadrupole mass spectrometer for the rapid detection and analysis of 9 endocrine disruptors in water:

[0049] The chromatographic conditions of the high performance liquid chromatography - triple quadrupole mass spectrometer are as follows:

[0050] Chromatographic column: phenomenex LC trapping column: (100 mm × 3.0 mm × 2.6 μm);

[0051] Waters BEH C18 liquid chromatography column (100 mm × 2.1 mm × 1.7 μm);

[0052] Column temperature: 40 °C;

[0053] Injection volume: 10 μL;

[0054] Flow rate: 0.3 mL / min;

[0055] Mobile phase: 0.02% ammonia aqueous solution (A) and acetonitrile (B);

[0056] Gradient elution program: 0 - 2.0 min, 20% - 95% B; 2.1 - 5.0 min, 95% B; 5.1 - 7.0 min 20% B.

[0057] The mass spectrometry conditions of the high performance liquid chromatography - triple quadrupole mass spectrometer are as follows:

[0058] Ion source: ESI source, negative ion mode;

[0059] Scanning mode: multiple reaction monitoring (MRM);

[0060] Curtain gas pressure: 30 Kpa;

[0061] Spray voltage: -4500 V;

[0062] Atomization temperature: 500 °C;

[0063] Atomization gas pressure: 50 Kpa;

[0064] Auxiliary gas pressure: 55 Kpa.

[0065] Example 2

[0066] This embodiment provides a rapid detection and analysis method for 9 endocrine disruptors in water, including the following steps:

[0067] S1. Startup preparation

[0068] According to the chromatographic conditions of Example 1, start up and set the analysis conditions of the high performance liquid chromatography - triple quadrupole mass spectrometer. After the system is balanced, enter the detection preparation.

[0069] S2. Prepare the test sample

[0070] Measure 10 mL of the water sample into a 25 mL centrifuge tube. Add 4 g of dry sodium chloride and the internal standard solution to the centrifuge tube, vortex for 1 min to mix evenly. Add 5 mL of acetonitrile to the centrifuge tube, vortex for 1 min, let it stand for 5 min, and then use a pipette to take 1 mL of the supernatant into a 1.5 mL brown injection vial to obtain the test sample.

[0071] S3. Determine the sample

[0072] Transport the test sample to the high performance liquid chromatography - triple quadrupole mass spectrometer that has entered the detection preparation in step S1 for detection and analysis;

[0073] The mass spectrometry analysis conditions and data of alkylphenols and bisphenol A are shown in Table 2.

[0074] Example 3

[0075] This example provides an exploration of the volume dosage of the extraction solvent for the rapid detection and analysis of 9 endocrine disruptors in water, including the following steps:

[0076] A1. Add the alkylphenol and bisphenol A standard solutions to the water sample to make the concentration of the target substances in the water sample 0.1 μg / L to obtain the test solution;

[0077] A2. Prepare 4 25 mL centrifuge tubes. Add 10 mL of the test solution to each of the 4 centrifuge tubes, then add 4 g of sodium chloride to each of the four centrifuge tubes, vortex for 1 min to mix evenly. Add 2.5 mL, 5 mL, 8 mL, and 10 mL of acetonitrile to the 4 centrifuge tubes respectively, vortex for 1 min, let it stand for 5 min, and take the upper layer of acetonitrile as the extraction solution;

[0078] A3. Determine the concentrations of alkylphenols and bisphenol A in the extraction solution, and calculate the extraction rate according to the formula Determine the extraction rates of alkylphenols and bisphenol A.

[0079] The measurement data of the extraction rates of alkylphenols and bisphenol A extracted by extraction solutions with different volumes are shown in the appendix Figure 3 .

[0080] Example 4

[0081] This example provides an exploration of the amount of sodium chloride added for the preparation of the test sample for the rapid detection and analysis of 9 endocrine disruptors in water, including the following steps:

[0082] Adding salts to water to form a strong ionic atmosphere in the solution can effectively promote the extraction of organic matter from water into the organic phase and facilitate the effective stratification of the organic phase and the aqueous phase. Since sodium chloride has a low cost, this study investigated the effects of different amounts of sodium chloride (1.0 g, 2.0 g, 4.0 g, 6.0 g) on the extraction efficiency of each target substance. As shown in the appendix Figure 4 As shown, the results indicate that when 1.0 g of sodium chloride was added, the solvent stratification was not obvious, and the recovery rates of 4-butylphenol and 4-pentylphenol were only 55.0% and 57.0%, respectively; when 2.0 g of sodium chloride was added, the solvent stratification was also not obvious, and the recovery rate of 4-pentylphenol was only 61.5%; when 4.0 g of sodium chloride was added, the solvent stratification was obvious, the recovery rate of bisphenol A was 91.5%, and the recovery rates of the other 8 alkylphenols were 78.5% - 129%; when 4.0 g of sodium chloride was added, the solvent stratification was obvious, the recovery rate of bisphenol A was 80.5%, and the recovery rates of the other 8 alkylphenols were 80.5% - 128%. Considering that the saturated solubility of sodium chloride in water is approximately 36.2 g of sodium chloride per 100 g of water at room temperature (25°C), 4.0 g of sodium chloride was selected as the addition amount for this experiment.

[0083] Example 5

[0084] This example provides an exploration of the vortex time for the preparation of test samples for the rapid detection and analysis of 9 endocrine disruptors in water, including the following steps:

[0085] Prepare 5 blank water samples, add alkylphenol and bisphenol A standard solutions to the water samples so that the concentration of the target substances in the water samples is 0.1 μg / L, and vortex for 1, 2, 4, and 8 min respectively. As shown Figure 5 As shown, at different vortex times, the recovery rates of bisphenol A and alkylphenols were maintained between 76% - 126%, and the difference in the recovery efficiency of each target substance was not obvious. When vortexed for 1 min, the recovery rate of bisphenol A was 115%, and the recovery rates of the other 8 alkylphenols ranged from 76% - 118%. Therefore, the vortex time was finally determined to be 1 min.

[0086] Example 5

[0087] This example provides an exploration of the optimization of chromatographic column conditions for the rapid detection and analysis of 9 endocrine disruptors in water, including the following steps:

[0088] A trapping column, Phenomenex LC column (100 mm × 3.0 mm × 2.6 μm), was installed between the infusion pump and the injection valve. This trapping column effectively solved the problem of blank interference caused by alkylphenols and bisphenol A in the liquid chromatography system. According to the properties of the target compounds, a reverse-phase chromatography column available in the laboratory was selected for this experiment. It was found that the Waters BEH C18 liquid chromatography column (100 mm × 2.1 mm × 1.7 μm) could separate the target compounds with appropriate elution times and good peak shapes. Based on the Waters BEH C18 (100 mm × 2.1 mm × 1.7 μm) ultra-high performance liquid chromatography column, the effects of using acetonitrile or methanol as the organic phase of the mobile phase on the separation of alkylphenols and bisphenol A were investigated. It was found that when methanol-water was used as the mobile phase, the peak width was slightly narrower, the baseline was more stable, and the response was better. Finally, methanol was selected as the organic phase of the mobile phase. To fully investigate the effect of the aqueous phase on the ionization of the target compounds and obtain better peak shapes and sensitivities, the response intensities, chromatographic peak shapes, and separation effects of alkylphenols and bisphenol A were compared under three different mobile phase systems: methanol-water, methanol-0.02% ammonia water, and methanol-0.1% formic acid water under the same conditions. The response signals of the target compound ions were stronger under the methanol-0.02% ammonia water mobile phase system, and the baseline was stable and the peak shape was good. It was speculated that the reason was that alkylphenols and bisphenol A were more easily dissociated under alkaline conditions, and the hydroxyl groups in their structures could ionize hydrogen ions and exhibit certain weak acidity. Adding a certain amount of alkaline ionization reagent to the mobile phase system could promote the ionization of the target compounds and improve their ionization efficiency.

[0089] In summary, based on the investigation of the organic phase and aqueous phase of the mobile phase, methanol-0.02% ammonia water was finally selected as the mobile phase system for this experiment. The chromatogram of the standard sample is shown in the appendix Figure 6 。

[0090] Example 6

[0091] This example provides an exploration of the optimization of chromatographic column conditions for the rapid detection and analysis of 9 endocrine disruptors in water, including the following steps:

[0092] The phenolic ion functional group in the structure of phenolic compounds carries a negative charge and is prone to generating a high response in the negative ion mode of the electrospray ionization source. Therefore, the establishment and optimization of mass spectrometry conditions were carried out in the ESI negative mode in this experiment.

[0093] First, the primary parent ion scan was performed in the SCAN mode to determine the parent ions of alkylphenols, bisphenol A, and the internal standard. Subsequently, the Product Ion Scan mode was used to scan and analyze their daughter ions, and two ion fragments with higher abundances and better response intensities were respectively selected as the quantitative ion and auxiliary qualitative ion for the target substance (appendix Figure 2) Finally, under the MRM mode, by adjusting and optimizing the mass spectrometry acquisition parameters such as capillary voltage, fragmentation voltage, collision energy, nebulizer pressure, drying gas (N2) temperature and flow rate, sheath gas temperature and flow rate, etc., the response intensities of the parent ions and characteristic fragment daughter ion pairs of bisphenol A, alkylphenols, bisphenol A-D4, and nonylphenol-D4 are maximized.

[0094] Finally, the optimized mass spectrometry acquisition parameters of this method are shown in the appendix Figure 2 , and the MRM spectra of each target compound after optimization are shown in the appendix Figure 7 .

[0095] Example 7

[0096] This example provides an exploration of the standard curve and detection limit of a rapid detection and analysis method for 9 endocrine disruptors in water, including the following steps:

[0097] Prepare standard curves with concentrations of alkylphenols and bisphenol A of 0.2, 0.5, 1.0, 2.0, and 5.0 μg / L, analyze according to the optimized method, and use the internal standard method for quantification. Taking the ratio of the peak areas of the quantitative ions of the target compounds to the quantitative ions of the internal standard as the ordinate and the concentration ratio as the abscissa, draw the standard curve. The detection limit is determined according to the general determination method of the method detection limit in the "Technical Guidelines for the Revision of Environmental Monitoring Analytical Method Standards" (HJ168-2020). According to the formula MDL = t(n-1)×Sd (the t value is 3.143), by repeating the blank spike experiment 7 times, calculate the detection limit, and take 4 times the detection limit as the determination limit. The linear equations, correlation coefficients (r), detection limits, and determination limit results of each target compound are shown in the appendix Figure 8 .

[0098] Example 9

[0099] This example provides an exploration of the spike recovery rate and precision of a rapid detection and analysis method for 9 endocrine disruptors in water, including the following steps:

[0100] Perform spike recovery tests for alkylphenols and bisphenol A at 3 levels using the actual blank sample. The spike levels are 0.1, 0.5, and 2.0 μg / L respectively. After the water sample is extracted by liquid-liquid extraction with acetonitrile, it is ready for liquid chromatography-mass spectrometry analysis. Each level is determined in parallel 6 times, calculate the recovery rate and its relative standard deviation (RSD), and the results are shown in the appendix Figure 9 . The recovery rates at the low, medium, and high 3 addition levels are between 75.0%-117%, 69.3%-123%, and 73.5%-128% respectively, and the relative standard deviations RSD are between 4.2%-12%, 1.9%-6.1%, and 1.5%-17% respectively. It shows that this method has a good recovery rate and high precision, and is suitable for the detection and analysis of actual samples.

[0101] The above content is only an example and illustration of the structure of the present invention. Those skilled in the art of this technology can make various modifications, supplements, or use similar methods to replace the specific embodiments described, as long as they do not deviate from the structure of the invention or exceed the scope defined by this claim book, they should all fall within the protection scope of the present invention.

[0102] In the description of this specification, the description with reference to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0103] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not elaborate on all details and do not limit the invention to only the specific implementation manners. Obviously, according to the content of this specification, many modifications and changes can be made. This specification selects and specifically describes these embodiments to better explain the principle and practical application of the present invention, so that those skilled in the art of this technology can understand and utilize the present invention well. The present invention is only limited by the claim book and its full scope and equivalents.

Claims

1. A rapid detection and analysis method for 9 endocrine disruptors in water, characterized in that, It includes the following steps: S1. Take a water sample and an internal standard substance and add them into a centrifuge tube, and use an extractant to separate and extract it to obtain a test sample. The extractant is composed of sodium chloride and acetonitrile. S2. Adjust the chromatographic conditions and mass spectrometry conditions of the high performance liquid chromatography-tandem triple quadrupole mass spectrometer according to the detection conditions. S3. The test sample in step S1 is determined by using the high performance liquid chromatography-tandem triple quadrupole mass spectrometer in step S2 to obtain the content of endocrine disruptors in the test solution.

2. The rapid detection and analysis method for nine endocrine disruptors in water according to claim 1, characterized in that, The preparation method of the test sample is as follows: Measure 10 mL of the water sample into a 25 mL centrifuge tube, add 4 g of dry sodium chloride and an internal standard solution into the centrifuge tube, vortex for 1 min to mix evenly, add 5 mL of acetonitrile into the centrifuge tube, vortex for 1 min, let it stand for 5 min, and then use a pipette to take 1 mL of the supernatant into a 1.5 mL brown injection vial to obtain the test sample.

3. The rapid detection and analysis method for nine endocrine disruptors in water according to claim 2, characterized in that, The preparation method of the dry sodium chloride is as follows: Burn sodium chloride in an atmosphere furnace at 400 °C for 4 - 6 h; The internal standard solution is composed of an internal standard substance and acetonitrile, with a concentration of 1 mg / L, and the internal standard substances are bisphenol A-D4 and nonylphenol-D4.

4. The rapid detection and analysis method for nine endocrine disruptors in water according to claim 1, characterized in that The chromatographic conditions of the high performance liquid chromatography-tandem triple quadrupole mass spectrometer are as follows: Chromatographic column: phenomenex LC Trapping column: (100 mm × 3.0 mm × 2.6 μm); Waters BEH C18 liquid chromatography column (100 mm × 2.1 mm × 1.7 μm); Column temperature: 40 °C; Injection volume: 10 μL; Flow rate: 0.3 mL / min; Mobile phase: 0.02% ammonia water solution (A) and acetonitrile (B); Gradient elution program: 0 - 2.0 min, 20% - 95% B; 2.1 - 5.0 min, 95% B; 5.1 - 7.0 min 20% B.

5. The rapid detection and analysis method for nine endocrine disruptors in water according to claim 1, characterized in that, The mass spectrometry conditions of the high performance liquid chromatography-tandem triple quadrupole mass spectrometer are as follows: Ion source: ESI source, negative ion mode; Scanning mode: Multiple reaction monitoring (MRM); Curtain gas pressure: 30 Kpa; Spray voltage: -4500 V; Atomization temperature: 500 °C; Atomizing gas pressure: 50 Kpa; Auxiliary gas pressure: 55 Kpa.

6. The rapid detection and analysis method for nine endocrine disruptors in water according to claim 1, characterized in that, The 9 endocrine disruptors in the water are respectively: bisphenol A, 4-branched nonylphenol, 4-nonylphenol, 4-butylphenol, 4-pentylphenol, 4-hexylphenol, 4-heptylphenol, 4-octylphenol, 4-tert-octylphenol.

7. A rapid detection and analysis method for nine endocrine disruptors in water according to claim 1, characterized in that The detection limit of this detection method for 9 endocrine disruptors in water is 0.025 - 0.08 μg / L.

Images