Method for monitoring polybrominated diphenyl ether in environmental water and application

Abstract

The invention provides a method for monitoring polybrominated diphenyl ether in environmental water and application, and relates to the technical field of environmental water pollution monitoring. The invention discloses a method for monitoring polybrominated diphenyl ether in environmental water. The method comprises the following steps: S1, collecting an environmental water sample by adopting an extraction bottle; s2, performing solid-phase microextraction pretreatment on the environmental water sample to obtain a sample to be detected; and S3, determining and analyzing the polybrominated diphenyl ether in the sample to be detected by adopting a gas chromatography tandem mass spectrometer. According to the present invention, the silicone rubber film solid phase extraction bottle is adopted, the environmental water sample collection process and the environmental water sample extraction process are integrated, the polybrominated diphenyl ether in the water sample is specifically adsorbed and concentrated, and the triple quadrupole gas chromatography-tandem mass spectrometry detection technology is combined so as to substantially reduce or eliminate the matrix effect and improve the enrichment efficiency; the method realizes simple, convenient and sensitive detection of polybrominated diphenyl ether in environmental water, has the characteristics of low cost and small environmental pollution, and has a good application prospect in the field of monitoring of polybrominated diphenyl ether multi-residues in environmental water.

Description

Technical Field

[0001] The present invention relates to the technical field of environmental water pollution monitoring, and in particular to a monitoring method and application of polybrominated diphenyl ethers in environmental water. Background Art

[0002] Polybrominated diphenyl ethers are a typical class of persistent organic pollutants, widely used as flame retardants in building materials, automobiles, textiles, electronics, plastics and other fields. Domestic and foreign studies have shown that long-term exposure to polybrominated diphenyl ethers may cause liver toxicity, neurotoxicity, reproductive development toxicity and endocrine disruption toxicity. Products containing polybrominated diphenyl ethers will release them into the environment to varying degrees during the production, use and waste disposal stages, posing a potential threat to the ecosystem and human health. Tetrabromodiphenyl ether, pentabromodiphenyl ether, hexabromodiphenyl ether, heptabromodiphenyl ether and decabromodiphenyl ether among polybrominated diphenyl ethers have been included in the Class A elimination list of the Stockholm Convention and are banned from production and use in many countries and regions.

[0003] However, due to their stable chemical structure and strong lipid solubility, these substances are difficult to degrade in the environment. They then migrate and accumulate over long distances through diffusion, desorption, dry and wet deposition, and volatilization in the atmosphere, soil, and water, and eventually enter the human body through the food chain. So far, polybrominated diphenyl ethers have been detected in water environments and biological samples to varying degrees, and their presence in the environment has become a major focus of current environmental science.

[0004] Traditional pretreatment techniques for polybrominated diphenyl ethers in environmental water samples include liquid-liquid extraction and solid phase extraction. Although these methods were frequently used as routine methods in early studies, they still have defects such as long operation time, large amount of organic solvents, and low enrichment multiples. With the increasing complexity of the monitoring environment, the increasing amount of monitoring samples, and the low concentration of polybrominated diphenyl ethers in environmental samples, these pretreatment methods usually cannot meet the detection requirements in terms of convenience, specificity and sensitivity. Therefore, it is necessary to develop a detection method with low consumption, weak matrix effect and high enrichment efficiency to realize the monitoring of polybrominated diphenyl ether residues in environmental water. Summary of the invention

[0005] Based on the technical problems existing in the background technology, the present invention proposes a monitoring method and application of polybrominated diphenyl ethers in environmental water.

[0006] The present invention provides a method for monitoring polybrominated diphenyl ethers in environmental water, comprising the following steps:

[0007] S1. Collect environmental water samples using extraction bottles;

[0008] S2, subjecting the environmental water sample to solid phase microextraction pretreatment to obtain a sample to be tested;

[0009] S3. Use gas chromatography-tandem mass spectrometry to determine and analyze polybrominated diphenyl ethers in the sample.

[0010] Preferably, the polybrominated diphenyl ethers include 2,4,4'-tribromodiphenyl ether (BDE-28), 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',6-pentabromodiphenyl ether (BDE-100), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), 2,2',4,4',5,6'-hexabromodiphenyl ether (BDE-154), 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153), and 2,2',3,4,4',5',6-heptabromodiphenyl ether (PBDE-183).

[0011] Preferably, in S1, the extraction bottle is a silicone rubber film solid phase extraction bottle.

[0012] More preferably, the thickness of the silicone rubber film is 300-500 μm, and the silicone rubber film is attached to the wall of the extraction bottle in a ring shape.

[0013] More preferably, the silicone rubber film is made of polydimethylsiloxane, silane derivatives, and a catalyst cross-linked into a network structure.

[0014] Preferably, in S2, the solid phase microextraction pre-treatment includes: vortex extraction, ultrasonic elution, concentration, and constant volume.

[0015] More preferably, the solid phase microextraction pretreatment specifically includes: vortex extraction of the extraction bottle containing the environmental water sample, after removing the solution, adding an elution solvent to the extraction bottle for ultrasonic elution to obtain an eluent, and concentrating and fixing the eluent to obtain.

[0016] More preferably, the rotation speed of the vortex extraction is 2000-4000 r / min, and the time of the vortex extraction is 5-20 min.

[0017] More preferably, the elution solvent of the ultrasonic elution is selected from one or more of n-hexane and ethyl acetate.

[0018] More preferably, the volume ratio of n-hexane to ethyl acetate is (1-2):(1-2).

[0019] More preferably, the ultrasonic elution time is 5-20 min.

[0020] More preferably, the power of the ultrasonic elution is 500W.

[0021] More preferably, the concentrating comprises blowing to near dryness using a nitrogen blowing concentrator.

[0022] More preferably, the constant volume solvent is n-hexane.

[0023] Preferably, in the S3, the chromatographic detection conditions in the gas chromatography tandem mass spectrometer include: the chromatographic column is a DB-5MS capillary chromatographic column (30m×250μm, 0.25μm); the use conditions of the chromatographic column include: injection mode: non-split injection; injection volume: 1.0μL; carrier gas: high-purity helium; constant flow mode 1.0mL / min; column temperature program: initial temperature 90-120℃, maintained for 1-2min, increased to 210-220℃ at 10-20℃ / min, and finally increased to 280-300℃ at 20-30℃ / min, maintained for 10-15min; injection port temperature 250-270℃.

[0024] Preferably, in the S3, the mass spectrometry detection conditions in the gas chromatography tandem mass spectrometer include: ion source temperature: 290-310°C; quadrupole temperature: 150-160°C; auxiliary heating zone temperature: 270-280°C; ionization mode: EI ionization source; electron energy: 70eV; collision gas: Ar; transmission line temperature: 280-300°C; acquisition mode: Timed mode; solvent delay 2-4min; the full scan range is mass-to-charge ratio 50-800.

[0025] Preferably, in said S3, the analysis includes qualitative analysis and quantitative analysis.

[0026] More preferably, the qualitative analysis includes that the difference between the retention time of the target substance in the test sample and the retention time of the polybrominated diphenyl ether standard sample is within 20s, and the relative abundance of the qualitative ion to the quantitative ion is compared with the relative abundance of the polybrominated diphenyl ether standard sample, and the relative deviation should be <20%, so that the corresponding polybrominated diphenyl ether can be determined to exist in the test sample.

[0027] More preferably, the quantitative analysis comprises taking a series of concentrations of polybrominated diphenyl ether standard samples, drawing a standard curve with polybrominated diphenyl ether concentration as the horizontal axis and polybrominated diphenyl ether peak area as the vertical axis to obtain a linear regression equation, and calculating the concentration of polybrominated diphenyl ether in the sample to be tested by the linear equation.

[0028] More preferably, the polybrominated diphenyl ether standard sample includes polybrominated diphenyl ether standard substance and n-hexane.

[0029] More preferably, the concentration series includes 0.1 μg / L, 0.2 μg / L, 0.5 μg / L, 1.0 μg / L, 2.0 μg / L, 5.0 μg / L, and 10.0 μg / L.

[0030] Preferably, in the monitoring method, the average recovery rate of polybrominated diphenyl ethers is 80-113%, the relative standard deviation is 0.3-9.0%, and the detection limit of polybrominated diphenyl ethers is 0.001-0.068 μg / L.

[0031] The present invention also proposes an application of the monitoring method in environmental water pollution control.

[0032] The beneficial effects of the present invention are:

[0033] The present invention provides a monitoring method and application of polybrominated diphenyl ethers in environmental water, which overcomes the problems of long pre-treatment cycle, large amount of organic solvent, obvious interference of impurities in the prior art, and realizes simple and sensitive detection of polybrominated diphenyl ethers in environmental water. The present invention collects environmental water samples through a solid phase extraction bottle, and quickly adsorbs polybrominated diphenyl ethers in water based on a silicone rubber film, so as to realize the in-situ collection and extraction and elution process of environmental water samples in one; a triple quadrupole gas chromatography tandem mass spectrometer is used as a detection means to eliminate the matrix effect, improve the enrichment efficiency, and improve the analysis sensitivity, thereby establishing a monitoring technology and application research of 7 polybrominated diphenyl ethers in environmental water; the technology simplifies the sampling and analysis steps, has high detection efficiency, and uses extraction materials with low pollution and low cost, which meets the detection needs of common polybrominated diphenyl ethers in environmental water, and can be promoted and applied to daily routine monitoring work of environmental water pollution control. The technology provided by the present invention is convenient for sampling and has strong environmental applicability, and can realize the monitoring of polybrominated diphenyl ethers in environmental water. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 The figure is a flow chart of a monitoring method for polybrominated diphenyl ethers in environmental water.

[0035] Figure 2 This is the total ion current chromatogram of 7 polybrominated diphenyl ether standard samples (100μg / L).

[0036] Figure 3 Extracted ion chromatograms of 7 PBDE standard samples (100 μg / L).

[0037] Figure 4 This is the total ion current chromatogram of Chaohu Lake environmental water sample with polybrominated diphenyl ethers added (0.1 μg / L).

[0038] Figure 5 This is the total ion current chromatogram of Chaohu Lake environmental water sample with polybrominated diphenyl ethers added (1 μg / L).

[0039] Figure 6 This is the total ion current chromatogram of Chaohu Lake environmental water sample with polybrominated diphenyl ethers added (10 μg / L).

[0040] Figure 7 This is the chromatogram of the test results of Chaohu water sample 1.

[0041] Figure 8 This is the chromatogram of the test results of Chaohu water sample 2.

[0042] Fig. 9 This is the chromatogram of the test results of Chaohu water sample 3. DETAILED DESCRIPTION

[0043] The technical solution of the present invention is described in detail through specific embodiments.

[0044] Unless otherwise specified, the instruments, materials, reagents, etc. used in the following examples can be obtained from commercial sources.

[0045] Instruments: TSQ Quantum XLS triple quadrupole gas chromatograph tandem mass spectrometer (Thermo Corporation, USA); VXMTAL multi-tube vortex mixer (OHRUS Corporation, USA); KQ600-B ultrasonic cleaner (Kunshan Ultrasonic Instrument Co., Ltd.); nitrogen blow concentrator (Organization Inc, USA).

[0046] Reagents and Materials n-hexane was chromatographically pure (Dima Technology Co., Ltd.); ethyl acetate was analytically pure (Xilong Chemical Co., Ltd.); silicone rubber film, thickness 400 μm (Hefei Baierdi Chemical Technology Co., Ltd.). The solid phase extraction bottle had a diameter of 2.6 cm, a height of 7.6 cm, and a volume of 40 mL; the silicone rubber film had a specification of 7.6 cm × 0.6 cm, a thickness of 400 μm, and was completely attached to the wall of the extraction bottle in a ring shape.

[0047] Standards: 2,4,4'-tribromodiphenyl ether (BDE-28), 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',6-pentabromodiphenyl ether (BDE-100), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), 2,2',4,4',5,6'-hexabromodiphenyl ether (BDE-154), 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153), 2,2',3,4,4',5',6-heptabromodiphenyl ether (PBDE-183) mixed standards (Shanghai Anpu Laboratory Technology Co., Ltd.). The basic information of the seven polybrominated diphenyl ethers is shown in Table 1.

[0048] Table 1 Basic information of polybrominated diphenyl ethers

[0049] Serial number Chinese name Abbreviation CAS Number Molecular formula Molecular weight 1 2,4,4'-Tribromodiphenyl ether BDE-28 41348-75-6 <h2 style=";text-align:left;direction:ltr"><![CDATA[C <h2 style=";text-align:left;direction:ltr"> 12 <h2 style=";text-align:left;direction:ltr"> H7Br3O]]><h2 style=";text-align:left;direction:ltr"> 406.9 2 2,2',4,4'-Tetrabromodiphenyl ether BDE-47 5436-43-1 <![CDATA[C 12 H6Br4O]]> 485.79 3 2,2',4,4',6-Pentabromodiphenyl ether BDE-100 189084-64-8 <![CDATA[C 12 H5Br5O]]> 564.69 4 2,2',4,4',5-Pentabromodiphenyl ether BDE-99 60348-60-9 <![CDATA[C 12 H5Br5O]]> 564.69 5 2,2',4,4',5,6'-Hexabromodiphenyl ether BDE-154 207122-15-4 <![CDATA[C 12 H4Br6O]]> 643.58 6 2,2',4,4',5,5'-Hexabromodiphenyl ether BDE-153 68631-49-2 <![CDATA[C 12 H4Br6O4]]> 643.58 7 2,2',3,4,4',5',6-Heptabromodiphenyl ether BDE-183 207122-16-5 <h2 style=";text-align:left;direction:ltr"><![CDATA[C <h2 style=";text-align:left;direction:ltr"> 12 <h2 style=";text-align:left;direction:ltr"> H3Br7O]]><h2 style=";text-align:left;direction:ltr"> 722.48

[0050] Standard working solution: Pipette an appropriate amount of mixed standard solution, dilute with n-hexane to make a mixed standard working solution, and store at 0-4°C.

[0051] Example 1

[0052] (1) Selection of extraction method

[0053] 0.08 mL of 7 kinds of polybrominated diphenyl ethers with a concentration of 5 mg / L were added to the 40 mL water sample collected in the extraction bottle. The vortex and ultrasonic extraction were performed for 5, 10, and 20 min, respectively. Then the water sample was discarded, and 5 mL of a mixed solvent of n-hexane and ethyl acetate (volume ratio of 1 / 1) was added to the silicone rubber film for ultrasonic elution for 10 min. The elution was repeated 3 times and the eluents were combined. After nitrogen blowing to near dryness, 1 ml of n-hexane was added to the volume, and the target was finally detected. Three repetitions were used for each method, and the relative standard deviation was less than 10%. The average recovery results are shown in Table 2.

[0054] The results show that the adsorption rate of the 7 polybrominated diphenyl ethers on the silicone rubber film by vortexing is generally higher than that by ultrasound. The extraction rate of vortexing for 10 minutes is better than that of vortexing for 5 minutes, while vortexing for 20 minutes has no significant improvement compared with 10 minutes. Therefore, vortexing for 10 minutes can meet the requirements of analytical recovery rate and can be used as an extraction method.

[0055] Table 2 Effect of extraction method on recovery rate

[0056]

[0057] (2) Selection of elution solvent

[0058] 0.08 mL of 7 kinds of polybrominated diphenyl ethers were added to the 40 mL water sample collected in the extraction bottle. The concentration of each PBDE was 5 mg / L. After vortex extraction for 10 minutes, the water sample was discarded, and 5 mL of n-hexane, ethyl acetate, and n-hexane / ethyl acetate (volume ratio 1 / 1) were added to the silicone rubber film for ultrasonic elution for 10 minutes. The elution was repeated 3 times and the eluents were combined. After nitrogen blowing to near dryness, 1 ml of n-hexane was added to the volume, and the target was finally detected. Three replicates were used for each elution solvent, and the relative standard deviation was less than 10%. The average recovery results are shown in Table 3.

[0059] The results showed that when n-hexane / ethyl acetate (volume ratio 1 / 1) was used as the eluent, the elution recovery rate of the seven polybrominated diphenyl ethers was significantly better than that of n-hexane or ethyl acetate. Therefore, n-hexane / ethyl acetate (volume ratio 1 / 1) was selected as the elution solvent.

[0060] Table 3 Effect of elution solvent on recovery rate

[0061]

[0062]

[0063] (3) Selection of elution method

[0064] 0.08 mL of a mixed standard of 7 polybrominated diphenyl ethers with a concentration of 5 mg / L was added to the 40 mL water sample collected in the extraction bottle. After vortex extraction for 10 min, the water sample was discarded, and 5 mL of n-hexane / ethyl acetate (volume ratio 1 / 1) was added. The silicone rubber film was vortexed and ultrasonically eluted for 10 min and 20 min, respectively. The elution was repeated 3 times and the eluents were combined. After nitrogen blowing to near dryness, 1 ml of n-hexane was used to make up the volume, and finally the target was detected. Three replicates were used for each elution solvent, and the relative standard deviation was less than 10%. The average recovery results are shown in Table 4.

[0065] The results show that the ultrasonic elution effect is better than the vortex method, and the recovery rate of ultrasound for 10 minutes has reached the requirements of analytical detection recovery rate. Therefore, ultrasound for 10 minutes was selected as the elution method. The final established in-situ sampling and pretreatment analysis process is shown in Figure 1 .

[0066] Table 4 Effect of elution mode on recovery rate

[0067]

[0068] Example 2

[0069] (1) Triple quadrupole gas chromatography tandem mass spectrometry detection conditions

[0070] The polybrominated diphenyl ethers in the environmental water extract were determined using a triple quadrupole gas chromatography tandem mass spectrometer. The chromatographic detection conditions were as follows: the chromatographic column was a DB-5MS capillary column (30m×250μm, 0.25μm); the conditions for using the chromatographic column included: injection mode: splitless injection; injection volume: 1.0μL; carrier gas: high-purity helium; constant flow mode 1.0mL / min; column temperature program: initial temperature 90°C, maintained for 1min, increased to 210°C at 20°C / min, and finally increased to 300°C at 30°C / min, maintained for 10min; injection port temperature 270°C.

[0071] The mass spectrometry conditions were as follows: ion source temperature: 300°C; quadrupole temperature: 150°C; auxiliary heating zone temperature: 270°C; ionization mode: EI ionization source; electron energy: 70 eV; collision gas: Ar; transfer line temperature: 290°C; acquisition mode: Timed mode; solvent delay 3 min; full scan range of mass-to-charge ratio 50-800. The characteristic ions, retention times and collision voltages of the seven polybrominated diphenyl ethers measured are shown in Table 5.

[0072] Table 5 Mass spectrometry parameters of polybrominated diphenyl ethers

[0073]

[0074] Note: * is the quantitative ion

[0075] (2) Qualitative and quantitative analysis

[0076] For each target, two characteristic ion pairs are selected for qualitative analysis, including one parent ion and one daughter ion for quantitative analysis. The result of the qualitative analysis is output as follows: the difference between the retention time of the target in the tested water sample and the retention time of the standard is within 20s, and the relative abundance of the qualitative ion relative to the quantitative ion is compared with the relative abundance of the most recently obtained standard sample. The relative deviation should be <20%, which can determine that the corresponding analyte exists in the sample.

[0077] The external standard method is used for quantitative determination. According to the above instrument conditions, each standard working solution and water sample extract are tested respectively. With the peak area of ​​the target substance measured in the standard working solution as the ordinate and the detection concentration as the abscissa, a standard curve is drawn to obtain a linear regression equation, and the concentration of the polybrominated diphenyl ether in the water sample extract to be tested is calculated by the linear equation. The calculation formula is as follows:

[0078]

[0079] Where:

[0080] X——Residual concentration of the substance being measured in the water sample, in micrograms per liter (μg / L);

[0081] Cin——the concentration of the analyte in the injected extract, in micrograms per liter (μg / L);

[0082] Vin——the final volume of the sample solution, in milliliters (mL);

[0083] Vs – volume of water sample, in milliliters (mL).

[0084] (3) Linear relationship and detection limit

[0085] Seven kinds of polybrominated diphenyl ether mixed standard working solutions with different concentrations were prepared with n-hexane, which were 0.1, 0.2, 0.5, 1.0, 2.0, 5.0, and 10.0 μg / L, respectively. The gas chromatography-mass spectrometry was performed, and the standard curve was drawn with the peak area of ​​the polybrominated diphenyl ethers in the standard solution as the ordinate and the concentration of the measured component as the abscissa, and the regression equation and correlation coefficient were obtained. The relevant results are shown in Table 6.

[0086] Table 6 Linear regression equation and detection limit of polybrominated diphenyl ethers

[0087]

[0088]

[0089] (4) Accuracy and precision

[0090] The target polybrominated diphenyl ethers were added to the environmental water samples to make the concentrations in the water 0.1, 1, and 10 μg / L, respectively. The environmental water samples were pretreated and tested using the above experimental method. The recoveries, relative standard deviations, and detection limits of the seven polybrominated diphenyl ethers in the samples are shown in Table 7.

[0091] The results showed that in the environmental water samples spiked with three levels of 0.1, 1, and 10 μg / L, the recovery rates of the seven polybrominated diphenyl ethers were 80-113%, the relative standard deviations were 0.3-9.2%, and the detection limits were 0.001-0.050 μg / L. This method has good accuracy, repeatability, and high sensitivity, and can fully meet the detection needs of the seven polybrominated diphenyl ethers in environmental water. The total ion current and extracted ion chromatograms of the standard working solutions of the seven polybrominated diphenyl ethers are shown in Figure 2 and Figure 3 The chromatograms of Chaohu water sample addition recovery at three levels are shown in Figure 4-Figure 6 .

[0092] Table 7 Average recovery and relative standard deviation of polybrominated diphenyl ethers in environmental water samples

[0093]

[0094]

[0095] Example 3

[0096] A method for monitoring polybrominated diphenyl ethers in environmental water comprises the following steps:

[0097] S1. Collect water samples from Chaohu Lake in March 2024, immerse three silicone rubber film solid phase extraction bottles to 1m below the water surface, take out the extraction bottles after they are full, and tighten the bottle caps; collect water once every week, randomly change a sampling point each time, and collect water 3 times in total;

[0098] S2. Pre-treatment of the environmental water sample with solid phase microextraction: vortex extraction of the extraction bottle containing the environmental water sample for 10 minutes, after removing the solution, add a mixed solvent of elution solvent n-hexane and ethyl acetate (volume ratio of 1 / 1) into the extraction bottle to ultrasonically elute the silicone rubber film for 10 minutes, repeat the elution 3 times and combine the eluents, blow nitrogen to dryness, and then make up to volume with 1 ml of n-hexane to obtain the sample to be tested;

[0099] S3. Use a gas chromatography-tandem mass spectrometer to determine and analyze polybrominated diphenyl ethers in the sample to be tested. Specifically: Use a triple quadrupole gas chromatography-tandem mass spectrometer to determine polybrominated diphenyl ethers in the environmental water extract. Among them, the chromatographic detection conditions are as follows: The chromatographic column is a DB-5MS capillary chromatographic column (30 m × 250 μm, 0.25 μm); The operating conditions of the chromatographic column include: Injection mode: splitless injection; Injection volume: 1.0 μL; Carrier gas: high-purity helium; Constant flow mode: 1.0 mL / min; Column temperature program: Initial temperature 90 °C, hold for 1 min, increase to 210 °C at 20 °C / min, and finally increase to 300 °C at 30 °C / min, hold for 10 min; Injection port temperature: 270 °C. The mass spectrometry conditions are as follows: Ion source temperature: 300 °C; Quadrupole temperature: 150 °C; Auxiliary heating zone temperature: 270 °C; Ionization mode: EI ionization source; Electron energy: 70 eV; Collision gas: Ar; Transfer line temperature: 290 °C; Acquisition mode: Timed mode; Solvent delay: 3 min; The full scan range is mass-to-charge ratio 50 - 800. Qualitative and quantitative analysis of polybrominated diphenyl ethers is carried out, and the detection results are shown in Table 8.

[0100] The results show that except for BDE-183, other polybrominated diphenyl ethers can be detected, but the detected concentrations are relatively low, ranging from 0.001 to 0.020 μg / L. The chromatogram of the actual water sample detection is shown in Figure 7-Figure 9 .

[0101] Table 8 Detection of 7 polybrominated diphenyl ethers in Chaohu Lake water (μg / L)

[0102]

[0103] Note: ND means not detected, <LOD means below the detection limit.

[0104] In summary, the monitoring method provided by the present invention meets the detection requirements of common polybrominated diphenyl ethers in environmental water and can be popularized and applied to the daily routine monitoring work of environmental water pollution control.

[0105] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, makes equivalent substitutions or changes, and should be covered by the protection scope of the present invention.

Claims

1. A method for monitoring polybrominated diphenyl ethers in environmental water, characterized in that: The following steps are involved: S1. Collect environmental water samples using extraction bottles; S2, subjecting the environmental water sample to solid phase microextraction pretreatment to obtain a sample to be tested; S3. Use gas chromatography-tandem mass spectrometry to determine and analyze polybrominated diphenyl ethers in the sample.

2. The monitoring method according to claim 1, characterized in that: The polybrominated diphenyl ethers include 2,4,4'-tribromodiphenyl ether, 2,2',4,4'-tetrabromodiphenyl ether, 2,2',4,4',6-pentabromodiphenyl ether, 2,2',4,4',5-pentabromodiphenyl ether, 2,2',4,4',5,6'-hexabromodiphenyl ether, 2,2',4,4',5,5'-hexabromodiphenyl ether and 2,2',3,4,4',5',6-heptabromodiphenyl ether.

3. The monitoring method according to claim 1, characterized in that: In the above-mentioned S1, the extraction bottle is a silicone rubber film solid phase extraction bottle; the thickness of the silicone rubber film is 300-500 μm, and the silicone rubber film is attached to the wall of the extraction bottle in a ring shape.

4. The monitoring method according to claim 1, characterized in that: In the above-mentioned S2, the solid phase microextraction pre-treatment includes: vortex extraction, ultrasonic elution, concentration, and constant volume.

5. The monitoring method according to claim 4, characterized in that: The solid phase microextraction pretreatment specifically includes: vortexing the extraction bottle containing the environmental water sample, removing the solution, adding an elution solvent to the extraction bottle for ultrasonic elution to obtain an eluent, and concentrating and fixing the eluent to obtain the product.

6. The monitoring method according to claim 4, characterized in that: The vortex extraction time is 5-20 minutes; the elution solvent of the ultrasonic elution is selected from one or more of n-hexane and ethyl acetate; the ultrasonic elution time is 5-20 minutes; and the constant volume solvent is n-hexane.

7. The monitoring method according to claim 1, characterized in that: In the S3, the chromatographic detection conditions in the gas chromatography tandem mass spectrometer include: the chromatographic column is a DB-5MS capillary chromatographic column with specifications of 30m×250μm, 0.25μm; the use conditions of the chromatographic column include: injection mode: non-split injection; injection volume: 1.0μL; carrier gas: high-purity helium; constant flow mode 1.0mL / min; column temperature program: initial temperature 90-120℃, maintained for 1-2min, increased to 210-220℃ at 10-20℃ / min, and finally increased to 280-300℃ at 20-30℃ / min, maintained for 10-15min; injection port temperature 250-270℃.

8. The monitoring method according to claim 1, characterized in that: In the S3, the mass spectrometry detection conditions in the gas chromatography tandem mass spectrometer include: 290-310°C; quadrupole temperature: 150-160°C; auxiliary heating zone temperature: 270-280°C; ionization mode: EI ionization source; electron energy: 70eV; collision gas: Ar; transmission line temperature: 280-300°C; acquisition mode: Timed mode; solvent delay 2-4min; the full scan range is mass-to-charge ratio 50-800.

9. The monitoring method according to claim 1, characterized in that: In the above-mentioned S3, the analysis includes qualitative analysis and quantitative analysis.

10. Application of the monitoring method according to any one of claims 1 to 9 in environmental water pollution control.

Images