Trace analysis method and device for three phenolic endocrine disrupters in surface water

Abstract

The invention discloses a trace analysis method and device for three phenolic endocrine disruptors in surface water. The method comprises the following steps: filtering collected surface water by adopting a glass fiber filter membrane to obtain an initial sample; activating, loading, leaching, drying and eluting the initial sample through a solid phase extraction (SPE) process to obtain a to-be-detected sample solution; detecting the three phenolic endocrine disrupters EDCs in the sample solution to be detected by using an ultra-high performance liquid chromatography tandem mass spectrometer UHPLC-MS / MS and a gas chromatography mass spectrometer GC-MS, and quantifying by using an external standard method. The technical problem that various phenol EDCs cannot be analyzed at the same time in the prior art is solved.

Description

Technical Field

[0001] This application relates to the field of environmental detection. Specifically, it relates to a trace analysis method and device for three types of phenolic endocrine disruptors in surface water. Background Art

[0002] This section aims to provide background or context for the content stated in the claims or the specification. The content described here is not admitted to be prior art merely because it is included in this section.

[0003] Endocrine disrupting chemicals (EDCs) are a class of exogenous chemical substances that can interfere with the hormone systems in organisms. There are numerous types of EDCs. Among them, the main ones are parabens (PBs) used as antibacterial preservatives, bisphenols (BPs) which are key raw materials for polycarbonates and epoxy resins, and synthetic phenolic antioxidants (SPAs) used to prevent product oxidation and degradation. Due to their extensive use, they are commonly detected in various water bodies, soils, sediments, indoor dust, food packaging, and organisms, thus attracting widespread attention. Research shows that exposure to these substances is closely related to health problems such as metabolic disorders, infertility, obesity, breast cancer, and reproductive disorders. With the deepening of the understanding of the hazards of EDCs, regulatory agencies in various countries have continuously updated monitoring standards, such as the "List of Chemical Pollutants" in the United States, the "Registration, Evaluation, Authorization and Restriction of Chemicals" in the European Union, and the "List of Key Controlled New Pollutants" in China, to match the needs of technological development and health risk assessment.

[0004] Although phenolic EDCs all contain the common phenolic hydroxyl group structure, different substituents result in significant differences in their physical and chemical properties. This diversity poses challenges to the simultaneous and accurate analysis of multiple phenolic EDCs. Especially in mass spectrometry detection, signal suppression or enhancement effects may occur, thus affecting the analysis accuracy and sensitivity. Existing methods mostly focus on the detection of single categories or limited ranges of EDCs. However, these pollutants often coexist in environmental samples in the form of mixtures. Research shows that SPAs, PBs, and BPs are commonly detected in surface water, with concentration ranges from ng / L to μg / L. Therefore, developing a trace analysis method that can simultaneously analyze multiple phenolic EDCs is crucial for comprehensively analyzing their environmental behaviors, interaction mechanisms, and toxic effects, etc. Such a method not only helps to evaluate the health risks of their combined exposure but also provides a scientific basis for formulating effective environmental management strategies.

[0005] No effective solution has been proposed for the above problems. Summary of the Invention

[0006] An embodiment of the present application provides a trace analysis method and device for three types of phenolic endocrine disruptors in surface water, so as to at least solve the technical problem in the prior art that multiple phenolic EDCs cannot be analyzed simultaneously.

[0007] According to one aspect of the embodiments of the present application, a trace analysis of three types of phenolic endocrine disruptors in surface water is provided, including: filtering the collected surface water with a glass fiber filter membrane to obtain an initial sample; activating, loading, rinsing, drying, and eluting the initial sample through a solid-phase extraction (SPE) process to obtain a sample solution to be measured; detecting three types of phenolic endocrine disruptors (EDCs) in the sample solution to be measured by using an ultra-high performance liquid chromatography-tandem mass spectrometer (UHPLC-MS / MS) and a gas chromatography-mass spectrometer (GC-MS), and quantifying by an external standard method, wherein the three types of phenolic endocrine disruptors (EDCs) include 9 parabens (PBs), 8 bisphenols (BPs), and 7 synthetic phenolic antioxidants (SPAs), the 9 parabens (PBs) include: methyl paraben, ethyl paraben, propyl paraben, isopropyl paraben, butyl paraben, isobutyl paraben, benzyl paraben, heptyl paraben, and paraben, the 8 bisphenols (BPs) include: bisphenol A, bisphenol S, bisphenol F, bisphenol AF, bisphenol AP, bisphenol P, bisphenol B, and bisphenol Z, and the 7 synthetic phenolic antioxidants (SPAs) include: 2,6-di-tert-butyl-p-cresol, 4-hydroxy-3-tert-butyl-anisole, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, 3,5-di-tert-butyl-4-hydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzyl alcohol, 2,6-di-tert-butyl-4-hydroxy-4-methyl-2,5-cyclohexadien-1-one, and 2,6-di-tert-butylbenzoquinone.

[0008] According to another aspect of the embodiments of the present application, there is also provided a trace analysis device for three types of phenolic endocrine disruptors in surface water, including: a filtration module for filtering the collected surface water with a glass fiber filter membrane to obtain an initial sample; a processing module for activating, loading, rinsing, drying, and eluting the initial sample through a solid-phase extraction (SPE) process to obtain a sample solution to be detected; a detection module for detecting three types of phenolic endocrine disruptors (EDCs) in the sample solution to be detected by using an ultra-high performance liquid chromatography tandem mass spectrometer (UHPLC-MS / MS) and a gas chromatography mass spectrometer (GC-MS), and quantifying by the external standard method. Among them, the three types of phenolic endocrine disruptors (EDCs) include 9 parabens (PBs), 8 bisphenols (BPs), and 7 synthetic phenolic antioxidants (SPAs). The 9 parabens (PBs) include methyl paraben, ethyl paraben, propyl paraben, isopropyl paraben, butyl paraben, isobutyl paraben, benzyl paraben, heptyl paraben, and p-hydroxybenzoic acid. The 8 bisphenols (BPs) include bisphenol A, bisphenol S, bisphenol F, bisphenol AF, bisphenol AP, bisphenol P, bisphenol B, and bisphenol Z. The 7 synthetic phenolic antioxidants (SPAs) include 2,6-di-tert-butyl-p-cresol, 4-hydroxy-3-tert-butyl-anisole, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, 3,5-di-tert-butyl-4-hydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzyl alcohol, 2,6-di-tert-butyl-4-hydroxy-4-methyl-2,5-cyclohexadien-1-one, and 2,6-di-tert-butylbenzoquinone.

[0009] According to another aspect of the embodiments of the present application, there is also provided a computer-readable storage medium, which includes a stored program, and when the program runs, it executes the above method.

[0010] According to another aspect of the embodiments of the present application, there is also provided an electronic device, including a memory, a processor, and a computer program stored on the memory and executable on the processor. The processor executes the above method through the computer program.

[0011] According to one aspect of the present application, there is provided a computer program product or a computer program, which includes computer instructions stored in a computer-readable storage medium. The processor of the computer device reads the computer instructions from the computer-readable storage medium, and the processor executes the computer instructions, so that the computer device executes the steps of any one of the above methods.

[0012] In the embodiments of the present application, glass fiber filter membranes are used to filter the collected surface water to obtain an initial sample; the initial sample is activated, loaded, eluted, dried, and eluted through a solid-phase extraction (SPE) process to obtain a sample solution to be tested; an ultra-high performance liquid chromatography tandem mass spectrometer (UHPLC-MS / MS) and a gas chromatography mass spectrometer (GC-MS) are used to detect three types of phenolic endocrine disruptors (EDCs) in the sample solution to be tested, and external standard method is used for quantification, thereby solving the technical problem in the prior art that multiple phenolic EDCs cannot be analyzed simultaneously. This solution establishes a trace analysis method that is simple to operate and highly sensitive and can be used for the simultaneous detection of 3 types of phenolic EDCs in surface water. This method uses solid-phase extraction (SPE) pretreatment, has good extraction effect, is simple to operate, has fewer steps, reduces the experimental difficulty, shortens the experimental time, greatly improves the work efficiency, and has high method sensitivity and good repeatability. Description of the Drawings

[0013] The drawings described herein are used to provide a further understanding of the present application and constitute a part of the present application. The schematic embodiments of the present application and their descriptions are used to explain the present application and do not constitute an improper limitation to the present application. In the drawings:

[0014] Figure 1 is a flowchart of an optional trace analysis method for three types of phenolic endocrine disruptors in surface water according to an embodiment of the present application;

[0015] Figure 2-1 is the peak spectrum of a 4-HB standard sample according to an embodiment of the present application;

[0016] Figure 2-2 is the peak spectrum of a MeP standard sample according to an embodiment of the present application;

[0017] Figure 2-3 is the peak spectrum of an EtP standard sample according to an embodiment of the present application;

[0018] Figure 2-4 is the peak spectrum of a PrP standard sample according to an embodiment of the present application;

[0019] Figure 2-5 is the peak spectrum of an iso-PrP standard sample according to an embodiment of the present application;

[0020] Figure 2-6 is the peak spectrum of a BuP standard sample according to an embodiment of the present application;

[0021] Figure 2-7 is the peak spectrum of an iso-BuP standard sample according to an embodiment of the present application;

[0022] Figure 2-8 is the peak spectrum of a BzP standard sample according to an embodiment of the present application;

[0023] Figure 2-9 is the peak spectrum of the HeP standard sample according to the embodiment of the present application;

[0024] Figure 2-10 is the peak spectrum of the BPA standard sample according to the embodiment of the present application;

[0025] Figure 2-11 is the peak spectrum of the BPS standard sample according to the embodiment of the present application;

[0026] Figure 2-12 is the peak spectrum of the BPF standard sample according to the embodiment of the present application;

[0027] Figure 2-13 is the peak spectrum of the BPAF standard sample according to the embodiment of the present application;

[0028] Figure 2-14 is the peak spectrum of the BPAP standard sample according to the embodiment of the present application;

[0029] Figure 2-15 is the peak spectrum of the BPB standard sample according to the embodiment of the present application;

[0030] Figure 2-16 is the peak spectrum of the BPP standard sample according to the embodiment of the present application;

[0031] Figure 2-17 is the peak spectrum of the BPZ standard sample according to the embodiment of the present application;

[0032] Figure 2-18 is the peak spectrum of the BHA standard sample according to the embodiment of the present application;

[0033] Figure 2-19 is the peak spectrum of the BHT-OH standard sample according to the embodiment of the present application;

[0034] Figure 2-20 is the peak spectrum of the BHT-COOH standard sample according to the embodiment of the present application;

[0035] Figure 2-21 is the peak spectrum of the BHT-CHO standard sample according to the embodiment of the present application;

[0036] Figure 2-22 is the peak spectrum of the BHT-quinol standard sample according to the embodiment of the present application;

[0037] Figure 2-23 is the peak spectrum of the BHT standard sample according to the embodiment of the present application;

[0038] Figure 2-24 is the peak spectrum of the BHT-Q standard sample according to the embodiment of the present application;

[0039] Figure 3 It is a schematic diagram of a trace analysis device for three types of phenolic endocrine disruptors in surface water according to an embodiment of the present application;

[0040] Figure 4 It is a structural block diagram of a terminal according to an embodiment of the present application. Specific embodiments

[0041] In order to enable those skilled in the art to better understand the solution of the present application, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present application.

[0042] It should be noted that the terms "first", "second", etc. in the specification and claims of the present application and the above-mentioned drawings are used to distinguish similar objects, and do not necessarily need to describe a specific order or sequence. It should be understood that such data can be interchanged under appropriate circumstances so that the embodiments of the present application described herein can be implemented in an order other than those illustrated or described herein. In addition, the terms "including" and "having" and any variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, system, product, or device that includes a series of steps or units does not necessarily have to be limited to those steps or units clearly listed, but may include other steps or units not clearly listed or inherent to these processes, methods, products, or devices.

[0043] According to one aspect of the embodiments of the present application, a method embodiment of a trace analysis method for three types of phenolic endocrine disruptors in surface water is provided.

[0044] Figure 1 It is a flowchart of an optional trace analysis method for three types of phenolic endocrine disruptors in surface water according to an embodiment of the present application. As Figure 1 shown, the method may include the following steps:

[0045] Step S102, filtering the collected surface water with a glass fiber filter membrane to obtain an initial sample.

[0046] Optionally, filtering the collected surface water with a glass fiber filter membrane to obtain an initial sample includes: sampling the surface water in the area to be measured to obtain 500 mL of sample surface water; filtering the 500 mL of sample surface water with a glass fiber filter membrane with a pore size of 0.45 μm to obtain an initial sample.

[0047] Step S104, activate, load, wash, dry, and elute the initial sample through a solid-phase extraction (SPE) process to obtain a sample solution to be measured.

[0048] Optionally, 6 mL of methanol and 6 mL of ultrapure water can be used as activation liquids successively to activate the initial sample; pass the activated initial sample through a solid-phase extraction column at a flow rate of 5 mL / min for loading, where the solid-phase extraction column used is a Waters solid-phase extraction column Oasis MCX 500 mg / 6 cc (the extraction effects of Oasis MCX and Oasis HLB cartridges as extraction columns were experimentally investigated. When using the HLB extraction column, the recovery rates of 4-HB, BHT, BHT-Q, and BHT-quinol were between 14.6% and 58.3%; when using the MCX extraction column, the recovery rates of these substances were significantly improved (42% - 61.5%); the recovery rates of other substances did not vary much between the two extraction columns. Finally, the Oasis MCX cartridge was selected as the extraction column); use 12 mL of 20% methanol-water solution as the washing liquid to wash the initial sample after loading (the washing effects of 9 mL, 12 mL, and 15 mL of aqueous solutions containing 20% methanol were experimentally investigated. For most substances, as the volume of the washing liquid increased, the recovery rate of the substances increased. However, for 4-HB, the recovery rate reached a peak when the volume of the eluent was 12 mL, indicating that the retention of 4-HB on the extraction column was relatively weak, and it was eluted with impurities as the volume of the washing liquid increased. Based on the above considerations, 12 mL of aqueous solution containing 20% methanol was finally selected as the washing liquid); set the drying time to 30 min to dry the initial sample after washing; use 3 mL of methanol and 3 mL of ethyl acetate as the eluent (the elution effects of 6 mL of methanol, 6 mL of ethyl acetate, and 3 mL of methanol + 3 mL of ethyl acetate were experimentally investigated. The elution efficiency of the mixed solvent was the highest, and the recovery rates of the target substances were 64.0% - 116%. Moreover, compared with single solvents, the extraction effects of the mixed solvent on 4-HB and BHT-quinol were significantly improved. Finally, 3 mL of methanol + 3 mL of ethyl acetate was selected as the eluent), elute the initial sample after drying to obtain a sample solution to be measured. Specifically, 3 mL of methanol and 3 mL of ethyl acetate can be used as the eluent to elute the analyte, and the collected eluate is concentrated and fixed to 1 mL under a gentle nitrogen stream to obtain a sample solution to be measured.

[0049] Step S106, use an ultra-high performance liquid chromatography tandem mass spectrometer UHPLC-MS / MS and a gas chromatography mass spectrometer GC-MS to detect three types of phenolic endocrine disruptors EDCs in the sample solution to be tested, and quantify them by the external standard method. The external standard method quantifies the concentration of the target substance in the sample to be tested. Specifically: first, establish a standard curve (concentration-signal response relationship) with a standard product of known concentration, then measure the signal of the unknown sample, and substitute it into the standard curve to calculate the concentration.

[0050] The three types of phenolic endocrine disruptors EDCs include 9 parabens PBs, 8 bisphenols BPs, and 7 synthetic phenolic antioxidants SPAs. The 9 parabens PBs include: methyl paraben, ethyl paraben, propyl paraben, isopropyl paraben, butyl paraben, isobutyl paraben, benzyl paraben, heptyl paraben, and p-hydroxybenzoic acid. The 8 bisphenols BPs include: bisphenol A, bisphenol S, bisphenol F, bisphenol AF, bisphenol AP, bisphenol P, bisphenol B, and bisphenol Z. The 7 synthetic phenolic antioxidants SPAs include: 2,6-di-tert-butyl-p-cresol, 4-hydroxy-3-tert-butyl-anisole, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, 3,5-di-tert-butyl-4-hydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzyl alcohol, 2,6-di-tert-butyl-4-hydroxy-4-methyl-2,5-cyclohexadien-1-one, and 2,6-di-tert-butylbenzoquinone.

[0051] The liquid chromatography conditions are as follows: chromatographic column: Acquity BEH-C18, 2.1 mm×100 mm×1.7 μm (indicating a particle size of 1.7 μm, column inner diameter×length is 2.1 mm×100 mm); mobile phase: methanol, pure water; column temperature: 40°C; injection volume: 5 μL; flow rate: 0.3 mL / min; gradient elution: initially 10% organic phase is maintained for 1 min, increased to 55% within 1 min, then increased to 100% within 1 min, maintained for 4 min, then decreased to 10% within 1 min, and maintained for 1 min. 10% organic phase means the volume ratio of methanol (organic phase) to pure water (aqueous phase) in the mobile phase is 10:90. The gradient is: from 0 to 1 minute, maintain 10%; from 1 to 2 minutes, increase to 55%; from 2 to 3 minutes, increase to 100%; from 3 to 7 minutes, maintain 100%; from 7 to 8 minutes, decrease to 10%; from 8 to 9 minutes, maintain 10%.

[0052] In this application, the chromatographic separation effects of methanol and acetonitrile as the organic phase of the mobile phase were investigated in experiments. When methanol was used as the organic phase, the chromatographic peak shape was improved and the peak response was higher. For some compounds, such as EtP, BHA, BPA, and BPF, the response values in methanol were 5 to 10 times higher than those in acetonitrile. In addition, when acetonitrile was used as the mobile phase, the elution time of 4-HB advanced and obvious tailing occurred. Methanol was finally selected as the organic phase. The experiments also investigated three combinations of mobile phases: methanol and pure water, methanol and pure water containing 2 mM ammonium acetate, and methanol and pure water containing 0.1% formic acid. Only a few substances, such as HeP, BPZ, BHT-OH, and BHT-CHO, showed higher responses in the buffer salt solution or organic acid. Most substances, especially parabens and BPs, showed the highest response values in the pure water phase. For example, the response values of BPS, BPF, and EtP in pure water were 1.75 to 6.05 times higher than those in pure water containing additives; the response values of BPA, BPAF, BzP, iso-BuP, BHA, and BHT-COOH in pure water were 1.78 to 3.43 times higher than those in 0.1% aqueous formic acid solution. Methanol and pure water were finally selected as the mobile phase composition.

[0053] The gas chromatography conditions were as follows: Chromatographic column: DB-5HT, 30 m × 0.25 mm × 0.10 μm, where 0.10 μm was the film thickness, 30 m was the length, and 0.25 mm was the inner diameter; Column temperature: 50 °C; Injection port temperature: 280 °C; Carrier gas: helium, injection was carried out in splitless mode with an injection volume of 1 μL; Constant flow mode: Column flow rate 1.0 mL / min; Programmed temperature rise: Initial temperature 50 °C was maintained for 3 min, then increased to 280 °C at a rate of 20 °C per minute and maintained for 0.5 min (i.e., maintained at 280 °C for 0.5 min after reaching 280 °C). That is, from the 0th to the 3rd minute, 50 °C was maintained; from the 3rd to the 14.5th minute, it increased to 280 °C; from the 14.5th to the 15th minute, 280 °C was maintained.

[0054] The liquid chromatography - mass spectrometry conditions were as follows: Scanning mode: Negative electrospray ionization ESI and dynamic multiple reaction monitoring dMRM mode; Gas temperature: 300 °C; Gas flow rate: 8 L / min; Nebulizer gas: 45 psi; Capillary voltage: 3500 V; Sheath gas temperature: 400 °C; Sheath gas flow rate: 11 L / min; Nozzle voltage: 1000 V.

[0055] The gas chromatography - mass spectrometry conditions were as follows: Scanning mode: Single ion monitoring SIM mode; Ion source temperature: 280 °C; Interface temperature: 280 °C; Solvent delay time: 6 min; The mass spectrometry parameters of the three types of phenolic endocrine disruptors EDCs met the parameter requirements in the preset table.

[0056] Through the above steps, the collected surface water is filtered using a glass fiber filter membrane to obtain an initial sample; the initial sample is activated, loaded, rinsed, dried, and eluted through a solid-phase extraction (SPE) process to obtain a sample solution to be measured; an ultra-high performance liquid chromatography tandem mass spectrometer (UHPLC-MS / MS) and a gas chromatography mass spectrometer (GC-MS) are used to detect three types of phenolic endocrine disruptors (EDCs) in the sample solution to be measured, and external standard method is used for quantification, which can solve the technical problem in the prior art that multiple phenolic EDCs cannot be analyzed simultaneously.

[0057] As an alternative embodiment, referring to Figures 2-1 to 2-24 (The chromatographic method of the present application can effectively separate 24 target compounds and avoid co-elution), the technical solution of the present application will be further described in detail below in conjunction with specific embodiments:

[0058] Specific determination method:

[0059] 1) Measure 500 mL of water sample, filter it through a 0.45 μm glass fiber filter membrane, and add 50 ng of deuterated standard.

[0060] 2) Add 6 mL of methanol and 6 mL of ultrapure water to the Oasis MCX column in sequence, pre-treat the water sample, and pass it through the extraction column at a flow rate of 5 mL / min. After the sample is loaded, rinse the column with 12 mL of aqueous solution containing 20% methanol, dry it under vacuum for 30 min, and then elute the analyte with 3 mL of methanol and 3 mL of ethyl acetate.

[0061] 3) Concentrate the collected eluate to 0.5 mL under a gentle nitrogen stream, and make the volume up to 1 mL for measurement.

[0062] UHPLC-MS / MS analysis conditions:

[0063] Chromatographic conditions: Chromatographic column: Acquity BEH-C18 (2.1 mm × 100 mm × 1.7 μm); Mobile phase: methanol, pure water; Column temperature: 40 °C; Injection volume: 5 μL; Flow rate: 0.3 mL / min; Gradient elution: Initially, 10% organic phase is maintained for 1 min, increased to 55% within 1 min, then increased to 100% within 1 min, maintained for 4 min, and then decreased to 10% within 1 min and maintained for 1 min.

[0064] Mass spectrometry conditions: Scanning mode: negative electrospray ionization (ESI) and dynamic multiple reaction monitoring (dMRM) mode; Gas temperature: 300 °C; Gas flow rate: 8 L / min; Nebulizer gas: 45 psi; Capillary voltage: 3500 V; Sheath gas temperature: 400 °C; Sheath gas flow rate: 11 L / min; Nozzle voltage: 1000 V.

[0065] GC-MS analysis conditions:

[0066] Chromatographic conditions: Chromatographic column: DB-5HT (30 m × 0.25 mm × 0.10 μm); Column temperature: 50 °C; Injection port temperature: 280 °C; Carrier gas: Helium, injection in splitless mode, injection volume 1 μL; Constant flow mode, column flow rate 1.0 mL / min; Programmed temperature rise: Initial temperature 50 °C held for 3 min, then raised to 280 °C at a rate of 20 °C / min and held for 0.5 min.

[0067] Mass spectrometry conditions: Scanning mode: Single ion monitoring (SIM) mode; Ion source temperature: 280 °C; Interface temperature: 280 °C; Solvent delay time: 6 min. Additionally, other mass spectrometry parameters for 3 types of EDCs are shown in Table 1.

[0068] Table 1

[0069]

[0070]

[0071] 4) Linear range and method detection limit.

[0072] Using methanol as the solvent, a mixed standard solution of 3 types of EDCs at 1 mg / L was serially diluted into a series of mixed standard solutions at 0.1, 0.5, 1, 5, 10, 25, 50, and 100 μg / L. After detection by UHPLC-MS / MS and GC-MS, with the analyte concentration as the abscissa (x, μg / L) and the peak area as the ordinate (y), a standard curve was plotted. The results showed that the correlation coefficients (R 2 ) of all EDCs' standard curves were greater than 0.993 (see Table 2). The detection limit and quantification limit were determined through 6 spiking experiments, with the concentration 10 times higher than the lowest point on the calibration curve. The method detection limit (LOD) and quantification limit (LOQ) were calculated based on 3 times and 10 times the relative standard deviation (RSD) respectively. The method LODs and LOQs for 3 types of EDCs were 0.228 - 0.940 ng / L and 0.758 - 3.13 ng / L respectively.

[0073] Table 2

[0074]

[0075]

[0076] 5) Method recovery rate, detection limit, and quantification limit.

[0077] Measure 500 mL of water samples, add EDCs standards, and adjust the spiked mass concentrations to 1, 20, and 50 μg / L respectively. Set 3 parallel groups for each concentration level. The results are shown in Table 3. When the spiked concentrations of the 3 types of EDCs in water are 1, 20, and 50 μg / L, the spiked recovery ranges are 64.7 - 114%, 68.2 - 118%, and 65.3 - 123% respectively, and the RSDs are 2.05 - 17.1%, 1.04 - 14.5%, and 0.830 - 14.8% respectively.

[0078] Table 3

[0079]

[0080]

[0081] 6) Determination of actual surface water samples.

[0082] Use this method to analyze the 3 types of EDCs in 8 actual surface water samples. The specific results are shown in Table 4 (nd means less than the detection limit).

[0083] Table 4

[0084]

[0085]

[0086] It should be noted that for the foregoing method embodiments, for the sake of simple description, they are all expressed as a series of action combinations. However, those skilled in the art should know that this application is not limited by the described action sequence, because according to this application, certain steps can be performed in other sequences or simultaneously. Secondly, those skilled in the art should also know that the embodiments described in the specification are all preferred embodiments, and the actions and modules involved are not necessarily essential to this application.

[0087] Through the description of the above embodiments, those skilled in the art can clearly understand that the method according to the above embodiments can be implemented by means of software plus a necessary general hardware platform. Of course, it can also be implemented by hardware, but in many cases the former is a better implementation method. Based on such an understanding, the technical solution of this application, in essence, or the part that contributes to the prior art, can be embodied in the form of a software product. This computer software product is stored in a storage medium (such as ROM / RAM, magnetic disk, optical disc), and includes several instructions to enable a terminal device (which can be a mobile phone, computer, server, or network device, etc.) to execute the methods described in various embodiments of this application.

[0088] According to another aspect of the embodiments of the present application, there is also provided a trace analysis device for three types of phenolic endocrine disruptors in surface water for implementing the trace analysis method of the three types of phenolic endocrine disruptors in surface water described above. Figure 3 FIG. is a schematic diagram of an optional trace analysis device for three types of phenolic endocrine disruptors in surface water according to an embodiment of the present application. As Figure 3 shown, the device may include:

[0089] A filtration module 31 for filtering the collected surface water with a glass fiber filter membrane to obtain an initial sample;

[0090] A processing module 32 for activating, loading, eluting, drying and eluting the initial sample through a solid phase extraction (SPE) process to obtain a sample solution to be detected;

[0091] A detection module 33 for detecting three types of phenolic endocrine disruptors (EDCs) in the sample solution to be detected by using an ultra-high performance liquid chromatography tandem mass spectrometer (UHPLC-MS / MS) and a gas chromatography mass spectrometer (GC-MS), and quantifying by an external standard method. Among them, the three types of phenolic endocrine disruptors (EDCs) include 9 parabens (PBs), 8 bisphenols (BPs) and 7 synthetic phenolic antioxidants (SPAs). The 9 parabens (PBs) include: methyl paraben, ethyl paraben, propyl paraben, isopropyl paraben, butyl paraben, isobutyl paraben, benzyl paraben, heptyl paraben and paraben. The 8 bisphenols (BPs) include: bisphenol A, bisphenol S, bisphenol F, bisphenol AF, bisphenol AP, bisphenol P, bisphenol B and bisphenol Z. The 7 synthetic phenolic antioxidants (SPAs) include: 2,6-di-tert-butyl-p-cresol, 4-hydroxy-3-tert-butyl-anisole, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, 3,5-di-tert-butyl-4-hydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzyl alcohol, 2,6-di-tert-butyl-4-hydroxy-4-methyl-2,5-cyclohexadiene-1-one and 2,6-di-tert-butylbenzoquinone.

[0092] According to another aspect of the embodiments of the present application, there is also provided a server or a terminal for implementing the trace analysis method of the three types of phenolic endocrine disruptors in surface water described above.

[0093] Figure 4 FIG. is a structural block diagram of a terminal according to an embodiment of the present application. As Figure 4 shown, the terminal may include: one or more (only one is shown in the figure) processors 401, a memory 403, and a transmission device 405. As Figure 4 shown, the terminal may further include an input / output device 407.

[0094] Among them, the memory 403 can be used to store software programs and modules, such as the program instructions / modules corresponding to the trace analysis method and device for three types of phenolic endocrine disruptors in surface water in the embodiments of the present application. The processor 401 executes various functional applications and data processing by running the software programs and modules stored in the memory 403, that is, realizes the above-mentioned trace analysis method for three types of phenolic endocrine disruptors in surface water. The memory 403 may include a high-speed random access memory, and may also include a non-volatile memory, such as one or more magnetic storage devices, flash memory, or other non-volatile solid-state memories. In some instances, the memory 403 may further include a memory remotely disposed relative to the processor 401, and these remote memories can be connected to the terminal through a network. Examples of the above network include but are not limited to the Internet, enterprise intranet, local area network, mobile communication network, and combinations thereof.

[0095] The above-mentioned transmission device 405 is used to receive or send data via a network, and can also be used for data transmission between the processor and the memory. Specific examples of the above network may include a wired network and a wireless network. In one instance, the transmission device 405 includes a network adapter (Network Interface Controller, NIC), which can be connected to other network devices and routers through a network cable, so as to communicate with the Internet or local area network. In one instance, the transmission device 405 is a radio frequency (Radio Frequency, RF) module, which is used to communicate with the Internet wirelessly.

[0096] Among them, specifically, the memory 403 is used to store application programs.

[0097] The processor 401 can call the application programs stored in the memory 403 through the transmission device 405 to execute the following steps:

[0098] Filter the collected surface water with a glass fiber filter membrane to obtain an initial sample;

[0099] Activate, load, wash, dry, and elute the initial sample through the solid-phase extraction SPE process to obtain a sample solution to be measured;

[0100] The three types of phenolic endocrine disruptors (EDCs) in the sample solution to be measured are detected by an ultra-high performance liquid chromatography tandem mass spectrometer (UHPLC-MS / MS) and a gas chromatography mass spectrometer (GC-MS), and quantified by the external standard method. Among them, the three types of phenolic endocrine disruptors (EDCs) include 9 parabens (PBs), 8 bisphenols (BPs), and 7 synthetic phenolic antioxidants (SPAs). The 9 parabens (PBs) include: methyl paraben, ethyl paraben, propyl paraben, isopropyl paraben, butyl paraben, isobutyl paraben, benzyl paraben, heptyl paraben, and paraben. The 8 bisphenols (BPs) include: bisphenol A, bisphenol S, bisphenol F, bisphenol AF, bisphenol AP, bisphenol P, bisphenol B, and bisphenol Z. The 7 synthetic phenolic antioxidants (SPAs) include: 2,6-di-tert-butyl-p-cresol, 4-hydroxy-3-tert-butyl-anisole, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, 3,5-di-tert-butyl-4-hydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzyl alcohol, 2,6-di-tert-butyl-4-hydroxy-4-methyl-2,5-cyclohexadien-1-one, and 2,6-di-tert-butylbenzoquinone.

[0101] Optionally, the specific examples in this embodiment may refer to the examples described in the above embodiment, and will not be elaborated here.

[0102] Those of ordinary skill in the art can understand that Figure 4 The structure shown is only schematic. The terminal can be a smart phone (such as an Android phone, an iOS phone, etc.), a tablet computer, a palm computer, and a mobile Internet device (MID), a PAD and other terminal devices. Figure 4 It does not limit the structure of the above electronic device. For example, the terminal may further include more or fewer components (such as a network interface, a display device, etc.) than those shown Figure 4 in the figure, or have a different configuration from that shown Figure 4 in the figure.

[0103] Those of ordinary skill in the art can understand that all or part of the steps in the various methods of the above embodiments can be completed by a program instructing the relevant hardware of the terminal device. The program can be stored in a computer-readable storage medium, and the storage medium can include: a flash drive, a read-only memory (ROM), a random access memory (RAM), a magnetic disk, or an optical disc, etc.

[0104] Embodiments of the present application also provide a storage medium. Optionally, in this embodiment, the above storage medium can be used to execute the program code of the trace analysis method for three types of phenolic endocrine disruptors in surface water.

[0105] Optionally, in this embodiment, the above storage medium can be located on at least one of multiple network devices in the network shown in the above embodiment.

[0106] Optionally, in this embodiment, the storage medium is set to store program code for performing the following steps:

[0107] Filter the collected surface water with a glass fiber filter membrane to obtain an initial sample;

[0108] Activate, load, wash, dry, and elute the initial sample through the solid-phase extraction (SPE) process to obtain a sample solution to be measured;

[0109] Detect three types of phenolic endocrine disruptors (EDCs) in the sample solution to be measured using an ultra-high performance liquid chromatography tandem mass spectrometer (UHPLC-MS / MS) and a gas chromatography mass spectrometer (GC-MS), and quantify by the external standard method. Among them, the three types of phenolic endocrine disruptors (EDCs) include 9 parabens (PBs), 8 bisphenols (BPs), and 7 synthetic phenolic antioxidants (SPAs). The 9 parabens (PBs) include: methyl paraben, ethyl paraben, propyl paraben, isopropyl paraben, butyl paraben, isobutyl paraben, benzyl paraben, heptyl paraben, and paraben. The 8 bisphenols (BPs) include: bisphenol A, bisphenol S, bisphenol F, bisphenol AF, bisphenol AP, bisphenol P, bisphenol B, and bisphenol Z. The 7 synthetic phenolic antioxidants (SPAs) include: 2,6-di-tert-butyl-p-cresol, 4-hydroxy-3-tert-butyl-anisole, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, 3,5-di-tert-butyl-4-hydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzyl alcohol, 2,6-di-tert-butyl-4-hydroxy-4-methyl-2,5-cyclohexadien-1-one, and 2,6-di-tert-butylbenzoquinone.

[0110] Optionally, specific examples in this embodiment can refer to the examples described in the above embodiment, and will not be repeated here.

[0111] Optionally, in this embodiment, the above storage medium can include but is not limited to: USB flash drives, read-only memories (ROMs), random access memories (RAMs), mobile hard disks, magnetic disks, or optical discs, etc., various media that can store program code.

[0112] The serial numbers of the embodiments of the present application above are only for description and do not represent the superiority or inferiority of the embodiments.

[0113] If the integrated units in the above embodiments are implemented in the form of software function units and sold or used as independent products, they can be stored in the above computer-readable storage media. Based on such an understanding, the technical solution of the present application, in essence, or the part that contributes to the prior art, or all or part of the technical solution, can be embodied in the form of a software product. This computer software product is stored in a storage medium and includes several instructions for causing one or more computer devices (which can be personal computers, servers, or network devices, etc.) to execute all or part of the steps of the methods described in the various embodiments of the present application.

[0114] In the above embodiments of the present application, the descriptions of the various embodiments each have their own focuses. For the parts not detailed in a certain embodiment, reference can be made to the relevant descriptions of other embodiments.

[0115] In the several embodiments provided by the present application, it should be understood that the disclosed client can be implemented in other ways. Among them, the device embodiments described above are only illustrative. For example, the division of the units is only a logical function division. In actual implementation, there can be other division methods. For example, multiple units or components can be combined or integrated into another system, or some features can be ignored or not executed. Another point is that the displayed or discussed couplings or direct couplings or communication connections to each other can be through some interfaces. The indirect couplings or communication connections of the units or modules can be in electrical or other forms.

[0116] The units described as separate components may or may not be physically separated. The components displayed as units may or may not be physical units, that is, they can be located in one place or distributed to multiple network units. Some or all of the units can be selected according to actual needs to achieve the purpose of the solution of this embodiment.

[0117] In addition, the functional units in the various embodiments of the present application can be integrated in a processing unit, or each unit can exist physically alone, or two or more units can be integrated in one unit. The above integrated units can be implemented in the form of hardware or in the form of software function units.

[0118] The above is only the preferred embodiment of the present application. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present application, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present application.

Claims

1. A trace analysis method for three types of phenolic endocrine disruptors in surface water, characterized in that, Including: Filtering the collected surface water with a glass fiber filter membrane to obtain an initial sample; Activating, loading, eluting, drying, and eluting the initial sample through a solid-phase extraction (SPE) process to obtain a sample solution to be measured; Detecting three types of phenolic endocrine disruptors (EDCs) in the sample solution to be measured using an ultra-high performance liquid chromatography-tandem mass spectrometer (UHPLC-MS / MS) and a gas chromatography-mass spectrometer (GC-MS), and quantifying by the external standard method. Among them, the three types of phenolic endocrine disruptors (EDCs) include 9 parabens (PBs), 8 bisphenols (BPs), and 7 synthetic phenolic antioxidants (SPAs). The 9 parabens (PBs) include methyl paraben, ethyl paraben, propyl paraben, isopropyl paraben, butyl paraben, isobutyl paraben, benzyl paraben, heptyl paraben, and p-hydroxybenzoic acid. The 8 bisphenols (BPs) include bisphenol A, bisphenol S, bisphenol F, bisphenol AF, bisphenol AP, bisphenol P, bisphenol B, and bisphenol Z. The 7 synthetic phenolic antioxidants (SPAs) include 2,6-di-tert-butyl-p-cresol, 4-hydroxy-3-tert-butyl-anisole, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, 3,5-di-tert-butyl-4-hydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzyl alcohol, 2,6-di-tert-butyl-4-hydroxy-4-methyl-2,5-cyclohexadien-1-one, and 2,6-di-tert-butylbenzoquinone.

2. The method according to claim 1, wherein Filtering the collected surface water with a glass fiber filter membrane to obtain an initial sample, including: Sampling the surface water in the area to be measured to obtain 500 mL of sample surface water; Filtering the 500 mL of sample surface water with a glass fiber filter membrane with a pore size of 0.45 μm to obtain an initial sample.

3. The method according to claim 1, characterized in that, Activating, loading, eluting, drying, and eluting the initial sample through a solid-phase extraction (SPE) process to obtain a sample solution to be measured, including: Using 6 mL of methanol and 6 mL of ultrapure water as the activation solution to perform activation treatment on the initial sample; Passing the activated initial sample through a solid-phase extraction column at a flow rate of 5 mL / min for loading treatment. Among them, the used solid-phase extraction column is a Waters solid-phase extraction column Oasis MCX 500 mg / 6 cc; Using 12 mL of 20% methanol-water as the eluent to perform elution treatment on the initial sample after loading treatment; Setting the drying time to 30 min to perform drying treatment on the initial sample after elution treatment; Successively using 3 mL of methanol and 3 mL of ethyl acetate as the eluent to perform elution treatment on the initial sample after drying treatment to obtain the sample solution to be measured.

4. The method according to claim 3, characterized in that, Successively using 3 mL of methanol and 3 mL of ethyl acetate as the eluent to perform elution treatment on the initial sample after drying treatment to obtain the sample solution to be measured, including: Using 3 mL of methanol and 3 mL of ethyl acetate as the eluent to elute the analyte, and concentrating and fixing the volume of the collected eluent to 1 mL under a gentle nitrogen stream to obtain the sample solution to be measured.

5. The method according to claim 1, wherein During the detection of three types of phenolic endocrine disruptors (EDCs) in the sample solution to be tested using an ultra-high performance liquid chromatography tandem mass spectrometer (UHPLC-MS / MS) and a gas chromatography mass spectrometer (GC-MS), the liquid chromatography conditions are as follows: Chromatographic column: Acquity BEH-C18, 2.1 mm × 100 mm × 1.7 μm; Mobile phase: methanol, pure water; Column temperature: 40°C; injection volume: 5 μL; flow rate: 0.3 mL / min; gradient elution: initially 10% organic phase is maintained for 1 min, increased to 55% within 1 min, then increased to 100% within 1 min, maintained for 4 min, and then decreased to 10% within 1 min and maintained for 1 min.

6. The method according to claim 1, wherein During the detection of three types of phenolic endocrine disruptors (EDCs) in the sample solution to be tested using an ultra-high performance liquid chromatography tandem mass spectrometer (UHPLC-MS / MS) and a gas chromatography mass spectrometer (GC-MS), the gas chromatography conditions are as follows: Chromatographic column: DB-5HT, 30 m × 0.25 mm × 0.10 μm, where 0.10 μm is the film thickness, 30 m is the length, and 0.25 mm is the inner diameter; column temperature: 50°C; injection port temperature: 280°C; carrier gas: helium, injection is carried out in splitless mode, injection volume 1 μL; constant flow mode: column flow rate 1.0 mL / min; programmed temperature rise: initial temperature 50°C is maintained for 3 min, increased to 280°C at a rate of 20°C per minute, and maintained for 0.5 min.

7. The method according to claim 1, wherein During the detection of three types of phenolic endocrine disruptors (EDCs) in the sample solution to be tested using an ultra-high performance liquid chromatography tandem mass spectrometer (UHPLC-MS / MS) and a gas chromatography mass spectrometer (GC-MS), the liquid mass spectrometry conditions are as follows: Scanning mode: negative electrospray ionization (ESI) and dynamic multiple reaction monitoring (dMRM) mode; gas temperature: 300°C; gas flow rate: 8 L / min; nebulizer gas: 45 psi; capillary voltage: 3500 V; sheath gas temperature: 400°C; sheath gas flow rate: 11 L / min; nozzle voltage: 1000 V.

8. The method according to claim 1, characterized in that During the detection of three types of phenolic endocrine disruptors (EDCs) in the sample solution to be tested using an ultra-high performance liquid chromatography tandem mass spectrometer (UHPLC-MS / MS) and a gas chromatography mass spectrometer (GC-MS), the gas mass spectrometry conditions are as follows: Scanning mode: single ion monitoring (SIM) mode; ion source temperature: 280°C; interface temperature: 280°C; solvent delay time: 6 min; the mass spectrometry parameters of the three types of phenolic endocrine disruptors (EDCs) meet the parameter requirements in the preset table.

9. A trace analysis device for three types of phenolic endocrine disruptors in surface water, characterized in that, Including: A filtration module for filtering the collected surface water using a glass fiber filter membrane to obtain an initial sample; A processing module for activating, loading, rinsing, drying, and eluting the initial sample through a solid phase extraction (SPE) process to obtain a sample solution to be tested; The detection module is used to detect three types of phenolic endocrine disruptors (EDCs) in the sample liquid to be tested by using an ultra-high performance liquid chromatography-tandem mass spectrometer (UHPLC-MS / MS) and a gas chromatography-mass spectrometer (GC-MS), and quantify them by the external standard method. Among them, the three types of phenolic endocrine disruptors (EDCs) include 9 parabens (PBs), 8 bisphenols (BPs), and 7 synthetic phenolic antioxidants (SPAs). The 9 parabens (PBs) include: methyl paraben, ethyl paraben, propyl paraben, isopropyl paraben, butyl paraben, isobutyl paraben, benzyl paraben, heptyl paraben, and p-hydroxybenzoic acid. The 8 bisphenols (BPs) include: bisphenol A, bisphenol S, bisphenol F, bisphenol AF, bisphenol AP, bisphenol P, bisphenol B, and bisphenol Z. The 7 synthetic phenolic antioxidants (SPAs) include: 2,6-di-tert-butyl-p-cresol, 4-hydroxy-3-tert-butyl-anisole, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, 3,5-di-tert-butyl-4-hydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzyl alcohol, 2,6-di-tert-butyl-4-hydroxy-4-methyl-2,5-cyclohexadien-1-one, and 2,6-di-tert-butylbenzoquinone.

10. A computer-readable storage medium, characterized in that, The storage medium includes a stored program, wherein the program, when running, executes the method described in any one of claims 1 to 7 above.

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