A rapid detection method for multiple polybrominated biphenyls in water

Abstract

The invention discloses a method for rapid detection of multiple polybrominated biphenyls in water quality. The method comprises the following steps: collecting a first water sample, performing a dechlorination treatment on the first water sample to obtain a sample to be extracted; filtering the sample to be extracted; performing a pH adjustment treatment on the sample to be extracted after the filtering treatment to obtain a sample to be enriched; enriching the sample to be enriched to obtain a liquid to be tested; configuring a standard solution, setting a first chromatographic condition, and confirming a calibration curve according to the standard solution and the first chromatographic condition; detecting the content of polybrominated biphenyls in the sample according to the liquid to be tested, the first chromatographic condition and the calibration curve; the method can establish a fully automatic solid phase extraction-gas chromatography method for determining 20 polybrominated biphenyls in water quality, and focuses on optimizing and exploring gas chromatography conditions and solid phase extraction conditions. The method has high automation degree in sample pretreatment, low organic solvent dosage, simple operation, good analytical sensitivity, and high recovery rate and precision.

Description

Technical Field

[0001] The present invention relates to the field of compound detection technology. Specifically, the present invention is applied to the field of compound detection in water quality, and in particular to a method for rapid detection of multiple polybrominated biphenyls in water quality. Background Art

[0002] Polybrominated biphenyls (PBBs) are a class of bromine-substituted biphenyl homologues, synthesized by bromination via the Friedel-Crafts reaction. Depending on the number and position of bromine atoms substituted on the benzene ring, they can be subdivided into 209 isomers ranging from monobromobiphenyl to decabromobiphenyl. Some of these isomers are widely used as additive flame retardants in electronic devices, textiles, printing and other fields. Most of the polybrominated biphenyls in the environment today come from brominated flame retardants.

[0003] Furthermore, polybrominated biphenyls have very obvious characteristics of persistent organic pollutants (POPs). They are highly chemically inert and stable in nature. They are difficult to degrade after entering the ecological environment. Moreover, polybrominated biphenyls can exist for a long time in media such as water bodies. Thus, with the natural migration, polybrominated biphenyls will gradually accumulate and enrich in terrestrial systems, thereby causing potential harm to environmental organisms. According to the existing animal experiments and human exposure cases, polybrominated biphenyls will cause certain damage to human health and may cause a series of symptoms such as cancer, reproductive toxicity and developmental delay. Although the production of polybrominated biphenyls has been completely stopped worldwide since 2000, with the use and disposal of a large number of products containing polybrominated biphenyls, there are still reports of polybrominated biphenyls being detected in environmental media from time to time. This shows that the pollution hazards of polybrominated biphenyls in the human living environment still exist.

[0004] In the existing schemes, the main analytical methods for polybrominated biphenyls are gas chromatography-mass spectrometry (GC-MS) and high-resolution gas chromatography-high-resolution mass spectrometry (HRGC-HRMS). These two analytical methods are mostly applicable to electronic and electrical products, rubber products, and textile dyeing and finishing auxiliaries. The following are some of the existing analytical methods as examples:

[0005] The first method is the EPA1614 method of the United States Environmental Protection Agency. In this method, solid phase extraction (SPE), liquid-liquid extraction (LLE), and continuous liquid-liquid extraction (CLLE) are used to extract liquid samples (solid content less than 1%), and then the samples are determined by high-resolution gas chromatography-high-resolution mass spectrometry. This method is theoretically applicable to the analysis of bromine-containing organic matter, but no separate analytical method standard for polybrominated biphenyls has been published, so the analysis of polybrominated biphenyls is subject to some restrictions.

[0006] The second method is the EPA560 series of methods of the United States Environmental Protection Agency. The United States Environmental Protection Agency introduced relevant analytical methods for polybrominated biphenyls in the EPA560 / 13-79-001, EPA560 / 13-79-002 and EPA560 / 6-77-020 series of methods. The methods can be summarized as using n-hexane-liquid extraction method to extract liquid samples and using gas chromatography-mass spectrometry or gas chromatography-high-resolution mass spectrometry to analyze polybrominated biphenyls; however, due to the lack of standard products, these standards only analyze a small number of polybrominated biphenyl monomers, such as the main components of commercial products such as hexabromobiphenyl PBB-153, octabromobiphenyl PBB-194, decabromobiphenyl PBB-209, etc., and their applicability, application range and detection breadth are relatively low;

[0007] The third method is the International Electrotechnical Commission IEC62321-6:2015. This method is the recommended analytical method for the ROHS directive in the field of electronic and electrical appliances. It introduces the application of GC-MS to determine polybrominated biphenyls and polybrominated diphenyl ethers in electronic and electrical products. The method can be summarized as follows: the sample is freeze-dried and crushed, then extracted with toluene Soxhlet, and the concentrate is directly detected by GC-MS. Ten target substances are selected (one monomer each from monobrominated to decabrominated). Since the limit value specified in the RoHS directive is not more than 1000ppm, the detection limit of this method is generally at the ppm level, so the reference value of this method is relatively small;

[0008] According to the above three existing methods, in actual application, the sensitivity of GC-MS analysis method is low, and it usually needs to be equipped with NCI ion source, which has high analysis cost. On the other hand, the instrument of HRGC-HRMS is expensive and has strict requirements on personnel and environment.

[0009] Therefore, in summary, the current determination methods for PBBs are mostly concentrated in the fields of electronic and electrical products, rubber products, textile dyeing and finishing auxiliaries, soil and sediment, etc. There is no relevant research on the determination of PBBs in environmental water quality, and the existing determination methods for PBBs have great limitations, poor applicability and high determination costs. Summary of the invention

[0010] The purpose of the present invention is to provide a rapid detection method for multiple polybrominated biphenyls in water quality in view of the above-mentioned problems in the prior art, thereby solving the problems that most of the determination methods for polybrominated biphenyls in the prior art are concentrated in the fields of electronic and electrical products, rubber products, textile dyeing and finishing auxiliaries, soil and sediment, and there is no relevant research on the determination of polybrominated biphenyls in environmental water quality, and the existing determination methods for polybrominated biphenyls have great limitations, poor applicability and high determination costs.

[0011] In order to solve the above technical problems, the specific technical solutions of the present invention are as follows:

[0012] The present invention provides a method for rapid detection of multiple polybrominated biphenyls in water, comprising the following steps:

[0013] Sample collection steps:

[0014] Collecting a first water sample, and performing a dechlorination treatment on the first water sample to obtain a sample to be extracted;

[0015] Sample enrichment steps:

[0016] The sample to be extracted is subjected to filtering treatment; the sample to be extracted after the filtering treatment is subjected to pH adjustment treatment to obtain a sample to be enriched; the sample to be enriched is subjected to enrichment treatment to obtain a liquid to be tested;

[0017] Sample testing steps:

[0018] A standard solution is prepared, a first chromatographic condition is set, and a calibration curve is confirmed according to the standard solution and the first chromatographic condition; and the polybrominated biphenyl content in the sample is detected according to the test solution, the first chromatographic condition and the calibration curve.

[0019] As an improved solution, the dechlorination treatment comprises:

[0020] According to the volume value of the first water sample, setting a first dechlorination parameter;

[0021] adding sodium thiosulfate to the first water sample according to the first dechlorination parameter;

[0022] The first water sample after the sodium thiosulfate is added is set as the sample to be extracted.

[0023] As an improved solution, the filtering process includes:

[0024] Filtering the sample to be extracted through a filter membrane with a first specification parameter to obtain a first filtered water sample;

[0025] The first filtered water sample is measured according to the first measuring parameter to obtain the water sample to be adjusted.

[0026] As an improved solution, the pH adjustment process includes:

[0027] The pH value of the water sample to be adjusted is adjusted to the first pH range using a sodium hydroxide solution of the second specification parameter, and then methanol of the third specification parameter is added and shaken to obtain the sample to be enriched;

[0028] or,

[0029] The pH value of the water sample to be adjusted is adjusted to the first pH range using a hydrochloric acid solution with a second standard ratio, and then methanol with a third specification parameter is added and shaken to obtain the sample to be enriched.

[0030] As an improved solution, the enrichment process includes:

[0031] Set up a fully automatic solid phase extraction instrument;

[0032] The solid phase extraction column of the fully automatic solid phase extraction instrument is activated by using n-hexane, ethyl acetate, methanol and experimental water, all of which have the fourth specification parameter;

[0033] The sample to be enriched is enriched based on the activated solid phase extraction column.

[0034] As an improved solution, the enrichment treatment of the sample to be enriched based on the activated solid phase extraction column includes:

[0035] First, the sample to be enriched is passed through the activated solid phase extraction column at a first flow rate, and then dried by passing nitrogen gas of a first purity for a first time;

[0036] After the drying, the solid phase extraction column is eluted with ethyl acetate of the fifth specification parameter and n-hexane of the sixth specification parameter to obtain an eluent; the eluent is concentrated to the seventh specification parameter by nitrogen blowing, and the solvent is replaced with n-hexane, and then the volume is fixed to the eighth specification parameter to obtain the test liquid.

[0037] As an improved solution, the first chromatographic condition includes:

[0038] The chromatographic column used is: DB-5MS chromatographic column, and the chromatographic column parameters of the DB-5MS chromatographic column are 15m×0.25mm×0.1μm;

[0039] The column oven temperature rising strategy was as follows: 100 °C for 1 min, then raised to 320 °C at a rate of 10 °C / min and held for 3 min;

[0040] The injection port temperature is: 280°C; the electron capture detector temperature is: 320°C; the carrier gas is: high-purity nitrogen of the second purity; the column flow rate is: 1.2mL / min; the injection method is: non-split injection; the injection volume is: 1.0μ.

[0041] As an improved solution, confirming the calibration curve according to the standard solution and the first chromatographic condition includes:

[0042] Based on the first chromatographic condition, the standard solution is measured by gas chromatography to obtain a standard measurement result;

[0043] The calibration curve is drawn according to the standard measurement results.

[0044] As an improved solution, the detection of the polybrominated biphenyl content in the sample according to the test liquid, the first chromatographic condition and the calibration curve includes:

[0045] According to the first chromatographic condition, the gas chromatography method is used to measure the liquid to be tested to obtain a sample test result;

[0046] The polybrominated biphenyl content in the sample is analyzed according to the calibration curve and the sample test result.

[0047] As an improved solution, the standard solution includes: 20 kinds of polybrominated biphenyl mixed standard working solutions, and the 20 kinds of polybrominated biphenyl mixed standard working solutions are all prepared with n-hexane.

[0048] The beneficial effects of the technical solution of the present invention are:

[0049] The invention discloses a method for rapid detection of multiple polybrominated biphenyls in water quality, and can establish a fully automatic solid phase extraction-gas chromatography method for determining 20 polybrominated biphenyls in water quality, and focuses on optimizing and exploring gas chromatography conditions and solid phase extraction conditions. The invention has a high degree of automation in sample pretreatment, a small amount of organic solvent, simple operation, good analysis sensitivity of the electron capture detector method, and high recovery rate and precision, which provides a methodological basis for the effective monitoring of polybrominated biphenyls in environmental water quality. Finally, by focusing on optimizing instrument analysis parameters and solid phase extraction conditions, the detection of 20 polybrominated biphenyls (PBB-1, PB-2, PB-3, PB-4, PB-5, PB-6, PB-7, PB-8, PB-9, PB-10, PB-11, PB-12, PB-13, PB-14, PB-15, PB-16, PB-17, PB-18, PB-19, PB-20, PB-21, PB22, PB23, PB24, PB25, PB26, PB27, PB28, PB29, PB30, PB31, PB32, PB33, PB34, PB35, PB36, PB37, PB38, PB39, PB30, PB31, PB32, PB34, PB36, PB37, PB38, PB39, PB30, PB31, PB32, PB33, PB34, PB35 The invention can be used for rapid and accurate determination of PBB-2, PBB-3, PBB-10, PBB-9, PBB-15, PBB-30, PBB-18, PBB-52, PBB-49, PBB-103, PBB-101, PBB-77, PBB-153, PBB-156, PBB-169, PBB-180, PBB-194, PBB-206, PBB-209), has extremely high applicability and a wide range of applications, low determination cost, high determination efficiency, makes up for the shortcomings of the existing technology, and has high reference significance and application value. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0051] Figure 1 It is a schematic flow chart of a method for rapid detection of multiple polybrominated biphenyls in water according to Example 1 of the present invention;

[0052] Figure 2 It is a detailed schematic diagram of a method for rapid detection of multiple polybrominated biphenyls in water according to Example 1 of the present invention;

[0053] Figure 3 It is a gas chromatogram of 20 polybrominated biphenyls in the rapid detection method of multiple polybrominated biphenyls in water quality described in Example 1 of the present invention;

[0054] The symbols in the accompanying drawings are explained as follows:

[0055] 1. PBB-1; 2. PBB-2; 3. PBB-3; 4. PBB-10; 5. PBB-9; 6. PBB-15; 7. PBB-30; 8. PBB-18; 9. PBB-52; 10. PBB-49; 11. PBB-103; 12. PBB-101; 13. PBB-77; 14. PBB-153; 15. PBB-156; 16. PBB-169; 17. PBB-180; 18. PBB-194; 19. PBB-206; 20. PBB-209. DETAILED DESCRIPTION

[0056] The preferred embodiments of the present invention are described in detail below in conjunction with the accompanying drawings so that the advantages and features of the present invention can be more easily understood by those skilled in the art, thereby making a clearer and more definite definition of the protection scope of the present invention.

[0057] In the description of the present invention, it should be noted that the embodiments described in the present invention are only part of the embodiments of the present invention, rather than all of the embodiments; based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of the present invention.

[0058] The terms "first", "second", etc. in the specification and claims of this article and the above-mentioned drawings are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence. It should be understood that the data used in this way can be interchanged where appropriate, so that the embodiments of this article described here can be implemented in an order other than those illustrated or described here. In addition, the terms "including" and "having" and any variations thereof are intended to cover non-exclusive inclusions, for example, a process, method, device, product or equipment that includes a series of steps or units is not necessarily limited to those steps or units clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or equipment.

[0059] In the description of the present invention, it should be noted that:

[0060] 1. In Example 1 of the present invention, the following listed instruments, reagents and conditions are all used as an implementation method, and the implementation method can be adapted and adjusted according to the implementation environment, objectives or conditions of the method in this example.

[0061] 2. In Example 1 of the present invention, the instruments and equipment used are as follows:

[0062] 1. GC-2030 gas chromatograph equipped with electron capture detector;

[0063] 2. AquaTrace ®ASPE899 fully automatic solid phase extractor;

[0064] 3. PS / DVB solid phase extraction column (6mL / 500mg);

[0065] 4. HSC-12B nitrogen blowdown instrument;

[0066] 5. Dura 12V ultrapure water machine.

[0067] 3. In Example 1 of the present invention, the reagent materials used and their standards are as follows:

[0068] 1. n-Hexane, chromatographic purity;

[0069] 2. Methanol, chromatographic purity;

[0070] 3. Ethyl acetate, chromatographic purity;

[0071] 2. Hydrochloric acid: ρ(HCl) = 1.19 g / mL;

[0072] 3. Sodium hydroxide, with high purity;

[0073] 4. Sodium thiosulfate, analytical grade;

[0074] 5. Experimental water: Ultrapure water, prepared by Dura 12V ultrapure water system.

[0075] Example 1

[0076] This embodiment provides a method for rapid detection of multiple polybrominated biphenyls in water. Figure 1~Figure 3 As shown, the following steps are included:

[0077] S100, sample collection steps:

[0078] S110, collecting a first water sample, and performing a dechlorination treatment on the first water sample to obtain a sample to be extracted;

[0079] As an implementation mode of the present invention, the first water sample is a water quality water sample to be detected by the method. In this embodiment, the first water sample is collected and stored in accordance with the relevant provisions of HJ / T 91 and HJ / T 164. After the first water sample is collected, it is placed in a brown glass sample bottle and waits for subsequent dechlorination treatment;

[0080] As an embodiment of the present invention, the dechlorination treatment comprises:

[0081] According to the volume value of the first water sample, a first dechlorination parameter is set; sodium thiosulfate is added to the first water sample according to the first dechlorination parameter; in this embodiment, for each liter of water sample, 80 mg of sodium thiosulfate is added to dechlorinate the water sample, and correspondingly, 80 mg is the first dechlorination parameter, and the volume value of the first water sample is how many liters of the first water sample; when performing the dechlorination treatment, it should be ensured that the water sample fills the sample bottle and no bubbles are left in the upper layer. After collecting the first water sample, it is stored in the dark below 4°C;

[0082] Correspondingly, the first water sample after adding the sodium thiosulfate is set as the sample to be extracted.

[0083] S200, sample enrichment step:

[0084] S210, filtering the sample to be extracted; performing pH adjustment on the sample to be extracted after the filtering process to obtain a sample to be enriched; performing enrichment on the sample to be enriched to obtain a liquid to be tested;

[0085] As an embodiment of the present invention, the filtration process includes: filtering the sample to be extracted through a filter membrane with a first specification parameter to obtain a first filtered water sample, the first specification parameter is 0.45µm; measuring the first filtered water sample according to a first measurement parameter to obtain a water sample to be adjusted, the first measurement parameter is 1L; the water sample to be adjusted is the measured 1L water sample after being filtered through a 0.45µm filter membrane;

[0086] As an embodiment of the present invention, the pH adjustment treatment includes: in this embodiment, two reagents are used to selectively adjust the pH value;

[0087] The first method is to use a sodium hydroxide solution of the second specification parameter to adjust the pH value of the water sample to the first pH range, and then add methanol of the third specification parameter to shake well to obtain the sample to be enriched, the second specification parameter is 0.05 g / mL, and the third specification parameter is 10 mL;

[0088] or,

[0089] The second method is to use a hydrochloric acid solution of a second ratio standard to adjust the pH value of the water sample to a first pH range, and then add methanol of a third specification parameter to shake well to obtain the sample to be enriched, and the second ratio standard is 1+1; the aforementioned first pH range is a neutral pH value, and adjusting the pH value of the water sample to the first pH range is to adjust the pH value of the water sample to neutral;

[0090] As an embodiment of the present invention, the enrichment treatment includes: setting and installing a fully automatic solid phase extractor; sequentially activating a solid phase extraction column of the fully automatic solid phase extractor using n-hexane, ethyl acetate, methanol and experimental water, all of which have specifications of the fourth specification parameter, and correspondingly, the fourth specification parameter is 10 mL; and then enriching the sample to be enriched based on the activated solid phase extraction column;

[0091] As an embodiment of the present invention, the enrichment treatment of the sample to be enriched based on the activated solid phase extraction column includes:

[0092] First, the sample to be enriched is passed through the activated solid phase extraction column at a first flow rate, and then dried by passing nitrogen of a first purity for a first time. Correspondingly, the first flow rate is 10 mL / min, the first time is 20 min, and the first purity is high purity; after the drying is performed with high-purity nitrogen, the solid phase extraction column is eluted with ethyl acetate of the fifth specification parameter and n-hexane of the sixth specification parameter to obtain an eluent, and the fifth specification parameter is 2 mL, and the sixth specification parameter is 5 mL; then the eluent is concentrated to the seventh specification parameter by nitrogen blowing, and the solvent is completely replaced with n-hexane, and then the volume is fixed to the eighth specification parameter to obtain the test solution, and the seventh specification parameter is less than 1 mL, that is, the eluent is concentrated to less than 1 mL by nitrogen blowing, and the eighth specification parameter is 1.0 mL; the test solution is the sample test solution that needs to be finally measured.

[0093] S300, sample testing steps:

[0094] S310, preparing a standard solution, setting a first chromatographic condition, and confirming a calibration curve according to the standard solution and the first chromatographic condition; and detecting the content of polybrominated biphenyls in the sample according to the test solution, the first chromatographic condition, and the calibration curve.

[0095] As an embodiment of the present invention, the first chromatographic condition designed in this method includes the following conditions: the chromatographic column used is: DB-5MS chromatographic column, and the chromatographic column parameters of the DB-5MS chromatographic column are 15m×0.25mm×0.1μm; the column oven heating strategy (program) adopts: 100℃ for 1min, then heat to 320℃ at a rate of 10℃ / min, and keep for 3min; the injection port temperature is: 280℃; the electron capture detector temperature is: 320℃; the carrier gas is: high-purity nitrogen of the second purity, and the second purity is 99.999%; the column flow rate is: 1.2mL / min; the injection method is: non-split injection; the injection volume is: 1.0μL.

[0096] As an embodiment of the present invention, the steps of preparing the standard solution are as follows: preparing a mixed standard solution of 20 polybrominated biphenyls with a concentration of 1.0 μg / mL using n-hexane, refrigerating below 4° C., sealing and storing away from light;

[0097] As an embodiment of the present invention, the step of confirming the calibration curve according to the standard solution and the first chromatographic condition comprises:

[0098] First, appropriate amounts of standard working solutions are respectively taken and diluted with n-hexane to form 20 kinds of polybrominated biphenyl mixed standard series solutions, and the standard series concentrations are 5.0μg / L, 10.0μg / L, 20.0μg / L, 50.0μg / L, and 100μg / L, respectively; then, the 20 kinds of polybrominated biphenyl mixed standard series solutions are measured by gas chromatography according to the first chromatographic condition to obtain the corresponding standard measurement results, and the calibration curve is drawn according to the content of the target compound in the standard measurement results as the horizontal axis and the chromatographic peak area as the vertical axis; in this embodiment, the gas chromatogram of 20 kinds of polybrominated biphenyls obtained by gas chromatography is as shown in Figure 3 As shown;

[0099] As an embodiment of the present invention, the detection of the polybrominated biphenyl content in the sample according to the test liquid, the first chromatographic condition and the calibration curve includes:

[0100] First, the test solution is measured by the gas chromatography method according to the first chromatographic condition which is the same as that of the detection standard solution to obtain the sample test result; then the polybrominated biphenyl content in the sample is analyzed according to the calibration curve and the sample test result.

[0101] In this embodiment, the following verification results are attached to prove the efficiency and accuracy of this method:

[0102] For the linear range and detection limit, according to the requirements of the Technical Guidelines for the Development of Environmental Monitoring Analytical Method Standards (HJ 168-2020), the blank spiked samples with a spike amount of 3 to 5 times the estimated method detection limit were repeated 9 times according to the full sample analysis procedure. The method detection limit was calculated according to the formula MDL=2.896×S, and the quantitative lower limit was calculated at 4 times the detection limit, where S is the standard deviation of the results of 9 parallel determinations; the results show that the 20 PBBs have a good linear relationship in the concentration range of 5.0~100μg / L, and the correlation coefficient r is greater than 0.998. When the sample sampling volume is 1L and the fixed volume is 1.0mL, the method detection limit of 20 PBBs is 1.1~3.5ng / L, and the quantitative limit is 4.4~14.2ng / L, which can meet the detection requirements of PBBs in water quality; the method detection limit and quantitative limit data of 20 PBBs are shown in Table 1:

[0103] Table 1

[0104]

[0105]

[0106] For the recovery rate and precision, 12 1L actual water samples were taken, and two groups of parallel spiked recovery tests with different concentrations were performed. The spiked concentrations were 20.0ng / L and 80.0ng / L, respectively. The determination was carried out according to the optimized method, and the spiked recoveries and relative standard deviations (RSDs) of the determination results were calculated. At the low and high spiked concentration levels, the spiked recoveries of the 20 PBBs were 72.8%~90.9%, and the RSDs were 3.3%~8.5%. The recovery rates and precision were high. Finally, this method was used to achieve high-precision and efficient determination of 20 polybrominated biphenyls in water quality.

[0107] Different from the prior art, the present invention adopts a rapid detection method for multiple polybrominated biphenyls in water quality, and a fully automatic solid phase extraction-gas chromatography method for determining 20 polybrominated biphenyls in water quality can be established, and the gas chromatography conditions and solid phase extraction conditions are optimized and explored. The sample pretreatment of the present invention has a high degree of automation, a small amount of organic solvent, simple operation, good analysis sensitivity of the electron capture detector method, and high recovery rate and precision, which provides a methodological basis for the effective monitoring of polybrominated biphenyls in environmental water quality. Finally, by focusing on the optimization of instrument analysis parameters and solid phase extraction conditions, the rapid and accurate determination of 20 polybrominated biphenyls in water quality is achieved. The method has extremely high applicability and a wide range of applications, low determination cost, high determination efficiency, makes up for the shortcomings of the prior art, and has high reference significance and application value.

[0108] It should be understood that in the various embodiments of this document, the size of the serial numbers of the above-mentioned processes does not mean the order of execution. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this document.

[0109] It should also be understood that in the embodiments of this article, the term "and / or" is only a description of the association relationship of the associated objects, indicating that three relationships may exist. For example, A and / or B can represent: A exists alone, A and B exist at the same time, and B exists alone. In addition, the character " / " in this article generally indicates that the associated objects before and after are in an "or" relationship.

[0110] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification and drawings, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A rapid detection method for multiple polybrominated biphenyls in water, characterized in that: The following steps are involved: Sample collection steps: Collecting a first water sample, and performing a dechlorination treatment on the first water sample to obtain a sample to be extracted; Sample enrichment steps: Filtering the sample to be extracted; adjusting the pH of the sample to be extracted after the filtration to obtain a sample to be enriched; Carrying out enrichment treatment on the sample to be enriched to obtain a liquid to be tested; The dechlorination treatment includes: setting a first dechlorination parameter according to the volume value of the first water sample; adding sodium thiosulfate to the first water sample according to the first dechlorination parameter; setting the first water sample after adding the sodium thiosulfate as the sample to be extracted; The filtration process includes: filtering the sample to be extracted through a filter membrane with a first specification parameter to obtain a first filtered water sample; measuring the first filtered water sample according to a first measurement parameter to obtain a water sample to be adjusted; The pH adjustment treatment includes: using a sodium hydroxide solution with a second specification parameter to adjust the pH value of the water sample to be adjusted to a first pH range, and then adding methanol with a third specification parameter to shake well to obtain the sample to be enriched; or, using a hydrochloric acid solution with a second ratio standard to adjust the pH value of the water sample to the first pH range, and then adding methanol with a third specification parameter to shake well to obtain the sample to be enriched; The enrichment treatment comprises: setting up a fully automatic solid phase extractor; sequentially using n-hexane, ethyl acetate, methanol and experimental water, all of which have the fourth specification parameter, to activate the solid phase extraction column of the fully automatic solid phase extractor; and performing enrichment treatment on the sample to be enriched based on the activated solid phase extraction column; The method comprises: firstly passing the sample to be enriched through the activated solid phase extraction column at a first flow rate, and then drying it by passing nitrogen of a first purity for a first time; after drying, eluting the solid phase extraction column with ethyl acetate of a fifth specification parameter and n-hexane of a sixth specification parameter to obtain an eluent; concentrating the eluent to a seventh specification parameter by nitrogen blowing, replacing the solvent with n-hexane, and then fixing the volume to an eighth specification parameter to obtain the liquid to be tested; The sample enrichment step further comprises: measuring 1L of the water sample to be adjusted after being filtered through a 0.45µm filter membrane, adjusting the pH of the water sample to be adjusted to neutral with a 0.05g / mL sodium hydroxide solution or a 1+1 hydrochloric acid solution with a standard ratio, and then adding 10mL of methanol to shake well to obtain the sample to be enriched; sequentially activating a solid phase extraction column with 10mL of n-hexane, 10mL of ethyl acetate, 10mL of methanol and 10mL of experimental water, after activation, allowing the sample to be enriched to pass through the solid phase extraction column at a flow rate of 10mL / min, and then passing high-purity nitrogen to dry for 20min; then eluting the solid phase extraction column with 2mL of ethyl acetate and 5mL of n-hexane in turn, concentrating the eluent to less than 1mL by nitrogen blowing, completely replacing the solvent with n-hexane, and fixing the volume to 1.0mL to obtain the liquid to be tested; Sample testing steps: A standard solution is prepared, a first chromatographic condition is set, and a calibration curve is confirmed according to the standard solution and the first chromatographic condition; and the content of polybrominated biphenyls in the sample is detected according to the test solution, the first chromatographic condition and the calibration curve; The first chromatographic conditions include: a chromatographic column: a DB-5MS chromatographic column, the chromatographic column parameters of the DB-5MS chromatographic column are 15m×0.25mm×0.1μm; a column oven temperature increase strategy: 100°C for 1min, then heated to 320°C at a rate of 10°C / min, and maintained for 3min; an injection port temperature of 280°C; an electron capture detector temperature of 320°C; a carrier gas of the second purity high-purity nitrogen; a column flow rate of 1.2mL / min; an injection method of non-split injection; and an injection volume of 1.0μL. The solid phase extraction column is a PS / DVB solid phase extraction column with a specification of 6mL / 500mg; The polybrominated biphenyls include: 2-bromobiphenyl, 3-bromobiphenyl, 4-bromobiphenyl, 2,6-dibromobiphenyl, 2,5-dibromobiphenyl, 4,4'-dibromobiphenyl, 2,4,6-tribromobiphenyl, 2,2',5-tribromobiphenyl, 2,2',5,5'-tetrabromobiphenyl, 2,2',4,5'-tetrabromobiphenyl, 2,2',4,5',6-pentabromobiphenyl, 2,2',4,5,5'-pentabromobiphenyl, 3,3', 4,4'-Tetrabromobiphenyl, 2,2',4,4',5,5'-Hexabromobiphenyl, 2,3,3',4,4',5-Hexabromobiphenyl, 3,3',4,4',5,5'-Hexabromobiphenyl, 2,2',3,4,4',5,5'-Hexabromobiphenyl, 2,2',3,3',4,4',5,5'-Hexabromobiphenyl, 2,2',3,3',4,4',5,5'-Octabromobiphenyl, 2,2',3,3',4,4',5,5',6-Nonabromobiphenyl and Decabromobiphenyl.

2. The method for rapid detection of multiple polybrominated biphenyls in water according to claim 1, characterized in that: The step of confirming the calibration curve according to the standard solution and the first chromatographic condition comprises: Based on the first chromatographic condition, the standard solution is measured by gas chromatography to obtain a standard measurement result; The calibration curve is drawn according to the standard measurement results.

3. The rapid detection method of multiple polybrominated biphenyls in water according to claim 2, characterized in that: The method of detecting the content of polybrominated biphenyls in the sample according to the test liquid, the first chromatographic condition and the calibration curve comprises: According to the first chromatographic condition, the gas chromatography method is used to measure the liquid to be tested to obtain a sample test result; The polybrominated biphenyl content in the sample is analyzed according to the calibration curve and the sample test result.

4. The method for rapid detection of multiple polybrominated biphenyls in water according to claim 3, characterized in that: The standard solution comprises: 20 kinds of polybrominated biphenyl mixed standard working solutions, and the 20 kinds of polybrominated biphenyl mixed standard working solutions are all prepared by using n-hexane.

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