A method for simultaneously detecting the content of 16 novel brominated flame retardants in human serum

Abstract

The application provides a method for simultaneously detecting the content of 16 new types of brominated flame retardants in human serum, and the specific steps are as follows: S1: preparing a mixed standard solution; S2: preparing an internal standard solution; S3: drawing a standard working curve; S4: sample pretreatment: taking dichloromethane in a glass test tube, adding the internal standard solution, and blowing with nitrogen in a 40 DEG C water bath until nearly dry, then adding fetal bovine serum and pure water, and vortexing to mix; the mixed solution of dichloromethane and acetonitrile is used to form an emulsion with the sample, and after sufficient extraction of the emulsion by using a dispersing agent and an extracting agent, centrifugation is carried out at room temperature; finally, the organic precipitate phase is taken and filtered through a filter membrane to be transferred to a sample injection vial with a glass lining tube, and is left for machine detection; S5: detection and result analysis: a gas chromatograph-tandem triple quadrupole mass spectrometer is used for detecting and analyzing the content of the new types of brominated flame retardants. The method has the advantages of simple pretreatment, high sensitivity and strong practicability, and can be used for routine biological monitoring of NBFRs in the human population.

Description

Technical Field

[0001] This invention belongs to the field of organic pollutant detection technology, specifically relating to a method for simultaneously detecting the content of 16 novel brominated flame retardants in human serum. Background Technology

[0002] Traditional brominated flame retardants (BFRs) are widely used in plastics, textiles, adhesives, polyurethane foams, and cable coatings due to their excellent flame-retardant properties. Because BFRs do not chemically bond with the polymer matrix, they can leach into various environmental matrices, including air, sediment, water, and dust, during manufacturing, use, and disposal. Numerous studies have confirmed that BFRs can accumulate in organisms and cause significant adverse health effects, including interference with the thyroid endocrine system, neurotoxicity, immunotoxicity, genotoxicity, and reproductive toxicity. Due to their persistence and high toxicity, the Stockholm Convention in 2009 listed pentabromodiphenyl ethers (BDEs) and octabromodiphenyl ether (Octa-BRE) as persistent organic pollutants (POPs), followed by hexabromocyclododecane (HBCD) and decabromodiphenyl ether (BDE209) in 2013. As BFRs are gradually phased out, a series of new BFRs (NBFRs) have begun to enter the market and be used.

[0003] Although NBFRs are described as a substitute for BFRs, they were first detected in the environment in the 1970s, and their use is expected to continue to increase. It is estimated that annual NBFR production will exceed 1.3 million tons in 2020, with China and the United States being the main producers. Global production and consumption patterns are gradually shifting from BFRs to NBFRs. With the widespread use of NBFRs, they are increasingly detected in various environmental media. On the other hand, NBFRs have the same semi-volatility and lipophilicity as polybrominated diphenyl ethers (PBDEs), allowing them to be transported globally to different environmental media (dust, water, soil, sediment) via long-range atmospheric transport (LRAT) and accumulate in wildlife. Multiple studies have shown that NBFRs affect neurodevelopment, leading to impaired cognitive and motor function, exacerbating anxiety behaviors, attention problems, and intellectual disabilities, and also affecting brain development by influencing thyroid hormone (TH) levels. Therefore, research is needed on the environmental and population exposure characteristics of NBFRs, making the development of corresponding internal and external exposure detection methods essential.

[0004] Several studies have investigated methods for detecting NBFRs in human blood. However, these methods generally suffer from limitations such as large serum volume requirements, high experimental costs (due to solid-phase extraction columns and the consumption of large amounts of organic solvents), cumbersome and time-consuming pretreatment procedures, and a focus on only a few NBFRs. Therefore, based on dispersive liquid-liquid extraction, we have established a method for detecting NBFRs in human blood using gas chromatography-tandem mass spectrometry (GC-MS / MS) with low blood volume (200 μL serum), coverage of a wide range of 16 NBFRs, relatively simple operation (3-hour pretreatment time), and high sensitivity (0.020-0.750 ng / mL). This method can be effectively applied to large-scale epidemiological studies and provides fundamental data for improving population-based NBFR exposure assessment. Summary of the Invention

[0005] This invention provides a method for simultaneously detecting the content of 16 novel brominated flame retardants in human serum. The spiked recovery test results show that the recovery rate of the target NBFRs ranges from 76.1% to 120.5%, the relative standard deviation is between 0.60% and 21.05%, and the method detection limit is between 0.020 ng / mL and 0.750 ng / mL. The method of this invention has simple pretreatment, high sensitivity, and strong practicality, and can be used for routine biomonitoring of NBFRs in the human population.

[0006] Description of the reagents involved in this invention:

[0007] In this invention, TBP is 2,4,6-tribromophenol, ATE is tribromophenylallyl ether, TBX is 2,3,5,6-tetrabromo-p-xylene, PBT is pentabromotoluene, PBEB is pentabromophenylethane, DPTE is 2,3-dibromopropyl-2,4,6-tribromophenyl ether, HBB is hexabromobenzene, 2IPPDPP is 2-isopropylphenyl diphenyl phosphate, 4tBPDPP is p-tert-butylbenzene phosphate, and PBBA is propylene. Pentabromobenzyl ester, HCDBCO is hexachlorodibromooctane, TBB is 2-ethylhexyl-2,3,4,5-tetrabromobenzoate, TBBPA-BME is tetrabromobisphenol A dimethyl ether, DBPP is phenyl (di-tert-butylphenyl) phosphate, BTBPE is 1,2-bis(2,4,6-tribromophenoxy)ethane, TBPH is 3,4,5,6-tetrabromo-1,2-benzenediacarboxylic acid bis(2-ethylhexyl) ester, HBB-C 13 The internal standard is hexabromobenzene.

[0008] In this invention, the concentrations of the following standards are specified: TBP standard (100 μg / mL), ATE standard (99.5% purity), TBX standard (100 μg / mL), PBT standard (1000 μg / mL), PBEB standard (100 μg / mL), DPTE standard (99.5% purity), HBB standard (1000 μg / mL), 2IPPDPP standard (100 μg / mL), 4tBPDPP standard (98.6% purity), PBBA standard (98.7% purity), HCDBCO standard (100 μg / mL), TBB standard (98.2% purity), TBBPA-BME standard (98.5% purity), DBPP standard (100 μg / mL), BTBPE standard (100 μg / mL), and TBPH standard (98.2% purity); the isotope HBB-C... 13 The concentration was 10 μg / mL, and all the above reagents were purchased from Tianjin Alta Company.

[0009] In this invention, fetal bovine serum was purchased from Phygene, acetone, toluene, dichloromethane, n-hexane, acetonitrile, and methanol were all chromatographically pure and purchased from Merck, Germany, deionized water was prepared using a Milli-Q Academic ultrapure water system, and sulfuric acid (analytical grade) was purchased from Shanghai Lingfeng Reagent Co., Ltd.

[0010] The technical solution adopted by the present invention to achieve the above-mentioned objective is: a method for simultaneously detecting the content of 16 novel brominated flame retardants in human serum, characterized by the following specific steps:

[0011] S1: Preparation of mixed standard working solution: Accurately weigh appropriate amounts of TBP, ATE, TBX, PBT, PBEB, DPTE, HBB, 2IPPDPP, 4tBPDPP, PBBA, HCDBCO, TBB, TBBPA-BME, DBPP, BTBPE, and TBPH standards respectively, and prepare single standard solutions with a concentration of 100 μg / mL using n-hexane; pipette 100 μL of each single standard solution into a 100 mL volumetric flask; dilute to the mark with n-hexane to prepare a mixed standard working solution with a concentration of 100 ng / mL;

[0012] S2: Preparation of internal standard solution: Take 10 μg / mL of isotope internal standard HBB-C. 13 Prepare an internal standard solution with a concentration of 100 ng / mL;

[0013] S3: Plotting the Standard Working Curve: Accurately pipette 1, 2, 4, 10, 20, 40, and 100 μL of the mixed standard solution into glass test tubes containing 200 μL of dichloromethane. Simultaneously, add 20 μL of internal standard solution to each tube. Blow under nitrogen until nearly dry, then add 200 μL of fetal bovine serum and 4 mL of purified water. Vortex for 30 seconds to mix. Accurately pipette 200 μL of a mixture of dichloromethane and 1 mL of acetonitrile and quickly inject it into 200 μL of the sample to form an emulsion. Use a dispersant and extractant to adjust the emulsion... After thorough extraction by vortexing the turbid liquid for 10 s, centrifuge at 4700 r / min for 5 min at room temperature. Finally, use a 1 mL syringe to aspirate the organic precipitate from the bottom, filter it through a 0.22 μm nylon needle filter membrane, and transfer it to a vial with a glass-lined tube for instrumental analysis. A series of working curves with concentrations of 0.5, 1, 2, 5, 10, 20, and 50 ng / mL were obtained. Finally, a standard working curve was plotted using the mass concentration ratio x of the compound to the internal standard versus the peak area ratio y of their quantitative ion pairs.

[0014] S4: Sample pretreatment: Take 200 μL of dichloromethane into a glass test tube, add 20 μL of internal standard solution, place the glass test tube in a nitrogen blower at 40℃ water bath, blow with nitrogen until nearly dry, add 200 μL of fetal bovine serum and 4 mL of pure water, vortex for 30 s to mix; accurately pipette 200 μL of the mixture of dichloromethane and 1 mL of acetonitrile and quickly add it to 200 μL of sample to form an emulsion, use a dispersant and extractant to vortex the emulsion for 10 s to fully extract, and centrifuge at 4700 r / min for 5 min at room temperature; finally, use a 1 mL syringe to aspirate the organic precipitate at the bottom, filter it through a 0.22 μm nylon needle filter membrane and transfer it to a vial with a glass liner tube for instrumental analysis;

[0015] S5: Detection and Result Analysis: Gas chromatography-tandem triple quadrupole mass spectrometry was used to detect and analyze the content of the novel brominated flame retardant.

[0016] Furthermore, the novel brominated flame retardants include TBP, ATE, TBX, PBT, PBEB, DPTE, HBB, 2IPPDPP, 4tBPDPP, PBBA, HCDBCO, TBB, TBBPA-BME, DBPP, BTBPE, and TBPH.

[0017] Furthermore, the internal standard concentration in the working curve in S3 is 10 ng / mL.

[0018] Furthermore, in S3 and S4, the dispersant is acetonitrile, the extractant is dichloromethane, and the volume ratio of the dispersant, extractant, and emulsion is 25:1.

[0019] Furthermore, the volume ratio of the dispersant to the extractant is 5:1.

[0020] Furthermore, the gas chromatograph-tandem triple quadrupole mass spectrometer in S5 is an Agilent 8890-7000D gas chromatograph-tandem triple quadrupole mass spectrometer.

[0021] Furthermore, the gas chromatographic conditions for the gas chromatography-tandem triple quadrupole mass spectrometer are as follows:

[0022] The chromatographic column was an HP-5MS capillary column with an injection port temperature of 300℃. Splitless injection was used with a column flow rate of 1.5 mL / min and an injection volume of 1.0 μL. The optimized temperature program conditions were as follows: initial temperature 100℃ held for 3 min, temperature increased at 20℃ / min to 200℃ held for 1.5 min, temperature increased at 5℃ / min to 250℃ / min, and then temperature increased at 15℃ / min to 280℃ held for 4 min.

[0023] The method as described in claim 5 is characterized in that the HP-5MS capillary column has dimensions of 15m × 250um × 0.25um.

[0024] Furthermore, the mass spectrometry conditions are as follows:

[0025] The electron impact ion source mode was used, with an ionization energy of 70 eV and an ion source temperature of 280℃; the transfer line temperature was 300℃; the temperatures of the first and second stage quadrupoles were both 150℃; the collision cell gases were nitrogen and helium, with a nitrogen flow rate of 1.5 mL / min and a helium flow rate of 2.25 mL / min; the solvent delay time was 4.00 min; and the scanning mode was multiple reaction monitoring.

[0026] Compared with the prior art, the beneficial effects that at least one technical solution adopted in the embodiments of this specification can achieve include at least:

[0027] (1) This invention uses dichloromethane-acetonitrile dispersion liquid-liquid extraction to extract 16 NBFRs in serum and analyzes them by gas chromatography-tandem quadrupole mass spectrometry. A large number of optimization experiments were carried out on the chromatographic and mass spectrometry conditions and sample pretreatment methods in terms of linearity, accuracy, precision, detection limit and quantitation limit, so as to realize the simultaneous detection and analysis of 16 NBFRs in serum.

[0028] (2) The spiked recovery test results of fetal bovine serum of the present invention showed that the recovery rate of the target NBFRs ranged from 76.1% to 120.5%, the relative standard deviation was between 0.60% and 21.05%, and the method detection limit was between 0.020 ng / mL and 0.750 ng / mL. The method has simple pretreatment, high sensitivity and strong practicality, and can be used for routine biomonitoring of NBFRs in the human population. Attached Figure Description

[0029] To more clearly illustrate the technical solutions of the embodiments of this application, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on the drawings without creative effort.

[0030] Figure 1 The total ion chromatogram is shown for a mixed standard solution of 16 NBFRs, where 1 is 2,4,6-tribromophenol, 2 is tribromophenyl allyl ether, 3 is 2,3,5,6-tetrabromo-p-xylene, 4 is pentabromotoluene, 5 is pentabromophenylethane, 6 is 2,3-dibromopropyl-2,4,6-tribromophenyl ether, 7 is hexabromobenzene and C 13 8 is hexabromobenzene, 9 is 2-isopropylphenyl diphenyl phosphate, 10 is p-tert-butylbenzene phosphate, 11 is pentabromobenzyl acrylate, 12 is hexachlorodibromooctane, 13 is 2-ethylhexyl-2,3,4,5-tetrabromobenzoate, 14 is tetrabromobisphenol A dimethyl ether, 15 is phenyl (di-tert-butylphenyl) phosphate, 16 is 1,2-bis(2,4,6-tribromophenoxy)ethane, and 17 is 3,4,5,6-tetrabromo-1,2-benzenediacarboxylic acid bis(2-ethylhexyl) ester.

[0031] Figure 2 Recovery rates for different combinations of extraction solvents;

[0032] Figure 3 Extraction efficiency for different dispersant volumes;

[0033] Figure 4 Extraction efficiency at different vortex times. Detailed Implementation

[0034] The embodiments of this application will now be described in detail with reference to the accompanying drawings.

[0035] The following specific examples illustrate the implementation of this application. Those skilled in the art can easily understand other advantages and effects of this application from the content disclosed in this specification. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of them. This application can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of this application. It should be noted that, in the absence of conflict, the following embodiments and features in the embodiments can be combined with each other. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0036] Example 1: Gas Chromatography and Mass Spectrometry Conditions

[0037] 1. Gas chromatography conditions

[0038] The chromatographic column was an HP-5MS capillary column (15m×250um×0.25um, Agilent Technologies, USA). The injection port temperature was 300℃, splitless injection was used, the column flow rate was 1.5mL / min, and the injection volume was 1.0μL. The optimized temperature program conditions were: initial temperature 100℃ held for 3 min, temperature increased to 200℃ at 20℃ / min held for 1.5 min, temperature increased to 250℃ / min at 5℃ / min, and then temperature increased to 280℃ at 15℃ / min held for 4 min.

[0039] 2. Mass spectrometry conditions

[0040] The electron impact ionization source mode was used, with an ionization energy of 70 eV, an ion source temperature of 280 °C, a transfer line temperature of 300 °C, and temperatures of both the first and second stage quadrupoles of 150 °C. The collision cell gases were nitrogen (flow rate 1.5 mL / min) and helium (flow rate 2.25 mL / min), and the solvent delay time was 4.00 min. The scanning mode was multiple reaction monitoring (MRM), and the residence time was adjusted to 30 ms-100 ms based on the number of characteristic ion pairs in each time window to achieve 3-5 scan cycles / second (Hz). Other mass spectrometry parameters are shown in Table 1.

[0041] Table 1. Retention times, ion-pair parameters, collision energies, and electron multiplier gain parameters for 16 NBFRs and isotopic internal standards.

[0042]

[0043] Note: * indicates quantitative ion pairs.

[0044] Under the above conditions, the mixed standard solution of the above 16 NBFRs was analyzed and determined, and the results are as follows: Figure 1 As shown, the 16 NBFRs mixed standard solutions showed good separation within 25.5 min, with symmetrical peak shapes.

[0045] Example 2: Optimization of Sample Pretreatment Procedure

[0046] 1. Optimization of the types of dispersants and extractants

[0047] In this invention, a standard solution (10 ng / mL) was added to fetal bovine serum, and five different combinations of dispersants and extractants, namely n-hexane-acetone, toluene-methanol, toluene-acetone, dichloromethane-acetonitrile, and dichloromethane-methanol, were used for dispersion-liquid extraction. After extraction, the effects of different combinations on the recovery rate of NBFRs were compared (with the response of dichloromethane-acetonitrile being 100%).

[0048] See results Figure 2 , Figure 2 The results show that the hexane-acetone and toluene-methanol combinations have low recovery rates for most NBFRs, and the dichloromethane-methanol combination has poor recovery rates for TBP and ATE. Toluene-acetone and dichloromethane-acetonitrile have good recovery rates for all NBFRs. Considering that dichloromethane and acetonitrile have low toxicity and that toluene and acetone are controlled explosive solvents, dichloromethane-acetonitrile was chosen as the dispersant and extractant.

[0049] 2. Optimization of dispersant and extractant volumes

[0050] The volume of the extractant directly affects the enrichment factor of the method. Increasing the volume leads to a larger volume of the organic phase after centrifugation, resulting in a lower analyte concentration, a decreased enrichment factor, and consequently, a lower sensitivity. Therefore, to ensure a high enrichment factor while also having sufficient organic phase for analysis, the extractant volume selected in this invention is 200 μL.

[0051] The volume of the dispersant directly affects the formation of the "water / dispersant / extractant / emulsion system," thus influencing the extraction efficiency. This invention investigated the extraction efficiency of the target compound using 0.6, 0.8, 1.0, 1.2, and 1.4 mL of acetonitrile as the dispersant. The results are shown in [Figure number missing]. Figure 3 When the dispersant volume was increased to 1.0 mL, the extraction efficiency of most NBFRs reached its maximum; further increasing the volume did not significantly change the extraction efficiency. Furthermore, with a larger dispersant volume, the analyte's solubility in water increased, making it harder to extract and reducing the extraction efficiency. Considering both reagent dosage and extraction efficiency, 1.0 mL was chosen as the dispersant volume.

[0052] 3. Optimization of extraction time

[0053] Extraction time refers to the time from when the extractant / dispersant system is injected into the sample solution to centrifugation. After the extraction solvent system enters the sample solution, vortexing allows the extractant to quickly form a large number of tiny droplets in the aqueous phase, increasing the specific surface area and thus enabling the target analyte to migrate rapidly into the extraction solvent. The recoveries of 16 NBFRs were investigated with vortexing times set to 5, 10, 30, 60, and 120 s, and the results are shown below. Figure 4The results showed that when the vortex oscillation time was between 10s and 30s, the extraction efficiency no longer showed a significant increasing trend with the extraction time. When the vortex oscillation time was 60s, there was more protein precipitation in the sample, which was not conducive to subsequent liquid aspiration. Therefore, centrifugation could be performed directly after vortex oscillation for 10s.

[0054] Example 3 Method Verification

[0055] 1. Linear range of the working curve, regression equation, limit of detection, and limit of quantitation.

[0056] Within the linear range of 0.5-50 ng / mL, the regression equations for all NBFRs showed good linearity, with R0... 2 The concentration was between 0.9974 and 0.9998. The blank sample preparation solution was spiked at a concentration of 1.0 ng / mL. The limit of detection (LOD) was set at a signal-to-noise ratio (SNR) of 3 and a SNR of 10. The method's LOD ranged from 0.020 to 0.750 ng / mL. See Table 2.

[0057] Table 2. Working curves, limits of detection, and limits of quantitation for gas chromatography-tandem mass spectrometry (GC-MS / MS) of 16 NBFRs in serum.

[0058]

[0059] 2. Precision and accuracy of the method

[0060] Using blank serum as a background, spiking recovery experiments were conducted by adding low (1.0 ng / mL), medium (10 ng / mL), and high (20 ng / mL) concentrations of a mixed standard solution of 16 NBFRs. Six parallel determinations were performed, and the results are shown in Table 3. The average recovery rate of this method ranged from 76.1% to 120.5%, with RSDs of 0.60%–21.05%.

[0061] Table 3. Results of spiked recovery experiments of 16 NBFRs in serum by gas chromatography-tandem mass spectrometry (n=6)

[0062]

[0063] Note: "Low", "Medium", and "High" correspond to concentrations of 2 ng / mL, 10 ng / mL, and 30 ng / mL, respectively; Internal standard C 13 -HBB retention time is 13.24 min.

[0064] Example 4: Determination of actual samples

[0065] The analytical methods established in this study were used to analyze serum samples from 89 Shanghai residents. The results are shown in Table 4. Twelve NBFRs were detected in the blood samples, with a detection rate of 2.27%-14.80%. The highest detection rates were for HBB (14.8%), TBB (10.2%), and TBBPA-BME (11.4%). The total NBFR concentration ranged from 0 to 2.569 ng / mL.

[0066] Table 4. NBFRs test results in blood samples from residents of a community in Shanghai (n = 89, ng / mL)

[0067]

[0068] As can be seen from the above, the method of the present invention has simple pretreatment, high sensitivity, and strong practicality, and can be used for routine biological monitoring of NBFRs in the human population.

[0069] The above embodiments are merely illustrative of the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent changes or modifications made based on the essence of the content of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A method for simultaneously detecting the content of 16 novel brominated flame retardants in human serum, characterized in that, The specific steps are as follows: S1: Preparation of mixed standard working solution: Accurately weigh appropriate amounts of TBP, ATE, TBX, PBT, PBEB, DPTE, HBB, 2IPPDPP, 4tBPDPP, PBBA, HCDBCO, TBB, TBBPA-BME, DBPP, BTBPE, and TBPH standards respectively, and prepare single standard solutions with a concentration of 100 μg / mL using n-hexane; pipette 100 μL of each single standard solution into a 100 mL volumetric flask; dilute to the mark with n-hexane to prepare a mixed standard working solution with a concentration of 100 ng / mL; S2: Preparation of internal standard solution: Take 10 μg / mL of isotope internal standard HBB-C. 13 Prepare an internal standard solution with a concentration of 100 ng / mL; S3: Plotting the Standard Working Curve: Accurately pipette 1, 2, 4, 10, 20, 40, and 100 μL of the mixed standard solution into glass test tubes containing 200 μL of dichloromethane. Simultaneously, add 20 μL of internal standard solution to each tube. Blow under nitrogen until nearly dry, then add 200 μL of fetal bovine serum and 4 mL of pure water. Vortex for 30 seconds to mix. Accurately pipette 200 μL of a mixture of dichloromethane and 1 mL of acetonitrile and quickly inject it into 200 μL of the sample to form an emulsion. Use a dispersant and extractant to adjust the emulsion... After thorough extraction by vortexing the turbid liquid for 10 s, centrifuge at 4700 r / min for 5 min at room temperature. Finally, use a 1 mL syringe to aspirate the organic precipitate from the bottom, filter it through a 0.22 μm nylon needle filter membrane, and transfer it to a vial with a glass-lined tube for instrumental analysis. A series of working curves with concentrations of 0.5, 1, 2, 5, 10, 20, and 50 ng / mL were obtained. Finally, a standard working curve was plotted using the mass concentration ratio x of the compound to the internal standard versus the peak area ratio y of their quantitative ion pairs. S4: Sample pretreatment: Take 200 μL of dichloromethane into a glass test tube, add 20 μL of internal standard solution, place the glass test tube in a nitrogen blower at 40℃ water bath, blow with nitrogen until nearly dry, add 200 μL of fetal bovine serum and 4 mL of pure water, vortex for 30 s to mix; accurately pipette 200 μL of the mixture of dichloromethane and 1 mL of acetonitrile and quickly add it to 200 μL of sample to form an emulsion, use a dispersant and extractant to vortex the emulsion for 10 s to fully extract, and centrifuge at 4700 r / min for 5 min at room temperature; finally, use a 1 mL syringe to aspirate the organic precipitate at the bottom, filter it through a 0.22 μm nylon needle filter membrane and transfer it to a vial with a glass liner tube for instrumental analysis; S5: Detection and Result Analysis: Gas chromatography-tandem triple quadrupole mass spectrometry was used to detect and analyze the content of the novel brominated flame retardant.

2. The method as described in claim 1, characterized in that, The novel brominated flame retardants include TBP, ATE, TBX, PBT, PBEB, DPTE, HBB, 2IPPDPP, 4tBPDPP, PBBA, HCDBCO, TBB, TBBPA-BME, DBPP, BTBPE, and TBPH.

3. The method as described in claim 1, characterized in that, In the working curve of S3, the concentration of the internal standard is 10 ng / mL.

4. The method as described in claim 1, characterized in that, In S3 and S4, the dispersant is acetonitrile, the extractant is dichloromethane, and the volume ratio of dispersant, extractant and emulsion is 25:

1.

5. The method as described in claim 4, characterized in that, The volume ratio of the dispersant to the extractant is 5:

1.

6. The method as described in claim 1, characterized in that, The gas chromatograph-tandem triple quadrupole mass spectrometer in S5 is an Agilent 8890-7000D gas chromatograph-tandem triple quadrupole mass spectrometer.

7. The method as described in claim 6, characterized in that, The gas chromatography conditions for the gas chromatography-tandem triple quadrupole mass spectrometer are as follows: The chromatographic column was an HP-5MS capillary column with an injection port temperature of 300℃. Splitless injection was used with a column flow rate of 1.5 mL / min and an injection volume of 1.0 μL. The optimized temperature program conditions were as follows: initial temperature 100℃ held for 3 min, temperature increased at 20℃ / min to 200℃ held for 1.5 min, temperature increased at 5℃ / min to 250℃ / min, and then temperature increased at 15℃ / min to 280℃ held for 4 min.

8. The method as described in claim 7, characterized in that, The HP-5MS capillary column has dimensions of 15m × 250um × 0.25um.

9. The method as described in claim 6, characterized in that, The mass spectrometry conditions are as follows: The electron impact ion source mode was used, with an ionization energy of 70 eV and an ion source temperature of 280℃; the transfer line temperature was 300℃; the temperatures of the first and second stage quadrupoles were both 150℃; the collision cell gases were nitrogen and helium, with a nitrogen flow rate of 1.5 mL / min and a helium flow rate of 2.25 mL / min; the solvent delay time was 4.00 min; and the scanning mode was multiple reaction monitoring.

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