Method for determining bromo-dioxin in sediment by high-resolution gas chromatography-magnetic mass spectrometry
Through high-resolution gas chromatography-high resolution mass spectrometry combined with multi-layer silica gel column and isotope dilution technology, the problems of cumbersome detection steps and waste of materials were solved, and bromodiodin detection with high sensitivity and high accuracy was achieved.
Patent Information
- Application Number
- CN202410188259.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-02-08
- Publication Date
- 2025-08-08
AI Technical Summary
In the prior art, the detection methods of brominated dioxin in sediments are cumbersome, and the amount of solvents and experimental materials is large, so it is impossible to effectively clarify the pollution situation, and there is a lack of detection methods with high sensitivity and high accuracy.
High-resolution gas chromatography-high-resolution mass spectrometry combined with multi-layer silica gel column and isotope dilution technology, and rapid solvent extraction, sulfur removal purification and nitrogen blowing concentration are simplified to establish high accuracy and high sensitivity detection methods.
The efficient separation and accurate quantification of brominated dioxins are achieved, the analysis steps are simplified, solvents and experimental materials are saved, and the accuracy and sensitivity of detection are improved.
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Figure CN120446322A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of environmental detection, and in particular relates to a method for determining brominated dioxins in sediments by high-resolution gas chromatography-mass spectrometry. Background Art
[0002] Brominated dioxins (PBDD / Fs) are highly toxic environmental pollutants primarily derived from the production, use, and recycling of brominated flame retardants and polymers containing brominated flame retardants. Brominated dioxins are aryl hydrocarbon receptor (AhR) agonists and can cause reproductive toxicity, carcinogenicity, immunotoxicity, and endocrine toxicity. With the widespread use of brominated flame retardants (such as polybrominated diphenyl ethers, tetrabromobisphenol A, and polybrominated biphenyls), the concentration of brominated dioxins in the environment has gradually increased. Consequently, human exposure to PBDD / Fs has increased, and the potential risks they pose to the ecological environment and human health have become a research hotspot in fields such as environmental science and public health.
[0003] However, research on brominated dioxins in China is still quite weak, and there is currently no standard method for their detection. Due to the low water solubility of brominated dioxins, few studies have examined their presence in sediments, either domestically or internationally. This has hindered the elucidation of their contamination patterns and characteristics in sediments, and thus, has failed to provide a basis for their control. For sediments, the existing literature on brominated dioxin detection procedures suffer from cumbersome procedures and the high use of solvents and experimental materials. Summary of the Invention
[0004] The object of the present invention is to solve the above problems and provide a simple, highly sensitive and accurate method for determining brominated dioxins in sediments by high-resolution gas chromatography-mass spectrometry.
[0005] The present invention achieves its purpose through the following steps, including:
[0006] Step 1: After adding the internal standard EDF-5408LCS to the sediment sample to be tested, use a rapid solvent extractor to extract and concentrate the extract;
[0007] Step 2: Add n-hexane to the concentrated extract obtained in step 1, then add an appropriate amount of copper particles (powder / beads), shake thoroughly, filter with a triangular funnel filled with anhydrous sodium sulfate, and concentrate the filtrate to obtain a purified concentrate;
[0008] Step 3: Add the concentrated extract obtained in step 2 to a multilayer silica gel column, elute with n-hexane, and concentrate the eluate to obtain a purified concentrate;
[0009] Step 4: The concentrated solution obtained in step 3 was further concentrated by purging with high-purity nitrogen, and the internal standard EDF-5409-A ISS was added, and nonane was added to make up the volume to obtain the final analysis sample.
[0010] Step 5: Analyze and determine the analytical sample using isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry to obtain the content of brominated dioxins in the sediment sample to be tested.
[0011] The beneficial effects of the present invention are that during the purification process, matrix interference is effectively removed through sulfur removal and multi-layer silica gel column treatment, and an instrumental method of isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry is established, which simplifies the analysis steps, saves solvents and experimental materials, and has high accuracy and sensitivity. BRIEF DESCRIPTION OF THE DRAWINGS
[0012] Figure 1 It is an analysis flow chart of the present invention;
[0013] Figure 2 It is a total ion current chromatogram of 14 PBDD / Fs target compounds provided in the examples of the present invention. DETAILED DESCRIPTION
[0014] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. All other embodiments derived by ordinary technicians in this field based on the embodiments of the present invention without creative work are within the scope of protection of the present invention.
[0015] In order to further facilitate the understanding of the implementation steps and advantages of the present invention, the present invention is further explained in conjunction with the following specific embodiments and drawings.
[0016] Figure 1 The present invention provides a method for determining brominated dioxins in sediments using isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry, and the specific steps are as follows:
[0017] Step 1: After adding the internal standard EDF-5408 LCS to the sediment sample to be tested, extraction was performed using a rapid solvent extractor (extraction conditions: pressure 1500 psi, temperature 150°C, 3 cycles, static time 10 min), and the extract was concentrated;
[0018] Step 2: Add n-hexane to the concentrated extract obtained in step 1, then add an appropriate amount of copper particles (powder / beads), shake thoroughly, filter with a triangular funnel filled with anhydrous sodium sulfate, and concentrate the filtrate to obtain a purified concentrate;
[0019] Step 3: Add the concentrated solution obtained in step 2 to a multilayer silica gel column, elute with n-hexane, and concentrate the eluate to obtain a purified concentrated solution;
[0020] Step 4: The concentrated solution obtained in step 3 was further concentrated by purging with high-purity nitrogen, and the internal standard EDF-5409-A ISS was added, and nonane was added to make up the volume to obtain the final analysis sample.
[0021] Step 5: Analyze and determine the analytical sample using isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry to obtain the content of brominated dioxins in the sediment sample to be tested.
[0022] In the above-mentioned determination steps, step 1 specifically includes: adding 13C-PBDD / Fs diluted with nonane to the sediment sample to be tested to extract the internal standard EDF-5408LCS solution; after the sediment sample to be tested is extracted by a rapid solvent extractor, the extract is concentrated by a rotary evaporator.
[0023] In the above-mentioned determination step, in step 2, 50 mL of n-hexane is added to the concentrated extract obtained in step 1, and then an appropriate amount of copper particles (powder / beads) is added, and the mixture is fully shaken until the copper particles (powder / beads) do not change color. The mixture is allowed to stand for 30 minutes, filtered with a triangular funnel filled with anhydrous sodium sulfate, and the filtrate is concentrated to obtain a purified concentrate.
[0024] In the above determination steps, the multilayer silica gel column in step 3 is packed using the dry method, and the filling order is 1g of anhydrous sodium sulfate, 1g of silica gel, 4g of 2% sodium hydroxide silica gel, 1g of silica gel, 8g of 44% sulfuric acid silica gel, 2g of silica gel, and 5g of anhydrous sodium sulfate. Use 80mL of n-hexane to elute the multilayer silica gel column, discard the eluent, and close the piston when the n-hexane liquid level reaches 1 cm above the chromatography column. Transfer the sample to the multilayer silica gel column with a Pasteur pipette, and rinse the sample bottle 3 times with a small amount of n-hexane solvent, and transfer it to the multilayer silica gel column. After the sample is completely transferred, elute with 100mL of n-hexane. Use a flask to collect all the eluent, and after collection, rotary evaporation is concentrated to 1-2mL.
[0025] In the above assay steps, step 4 involves concentrating the concentrate from step 3 to 1-2 mL by rotary evaporation. The concentrate is then transferred to a nitrogen purging pipette using a Pasteur pipette. The sample bottle is rinsed three times with a small amount of n-hexane solvent and then transferred to the nitrogen purging pipette. The sample is concentrated to near dryness using high-purity nitrogen purge. The sample is then added to a solution of 13C-PBDD / Fs extracted with the internal standard EDF-5408 LCS diluted with nonane to prepare the sample for instrument analysis.
[0026] The isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry (HRGC-HRMS) method used in the above determination steps was as follows: a DB-5HT column (15 m long, 0.25 mm inner diameter, 0.1 μm film thickness), and a carrier gas of high-purity helium at a rate of 1.0 mL / min. Pulsed mode was used; the inlet temperature was 280°C, and pulsed splitless injection was used. Each injection volume was 2 μL, and the transfer line temperature was 280°C. The temperature program was 130°C for 2 min, then 30°C / min to 230°C for 0 min, and then 10°C / min to 325°C for 3 min.
[0027] The mass spectrometry conditions were as follows: resolution R ≥ 10000; electron energy 45 eV; ion source temperature 280°C, electron multiplier voltage 1600 V; and selective ion monitoring to monitor characteristic ions such as [M]+, [M+2]+, and [M+4]+.
[0028] Accurate determination of 17 4- to 8-substituted brominated dioxins with a single injection.
[0029] The analytical method of the present invention can effectively separate brominated dioxins during the sample purification process, greatly simplifying the analytical steps, saving time and cost, and establishing a highly accurate and highly sensitive isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry method for determining brominated dioxins in sediments.
[0030] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the present invention. Any person skilled in the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be based on the scope of the claims.
Claims
1. A method for determining brominated dioxins in sediments by high-resolution gas chromatography-mass spectrometry, characterized in that: The following steps are included Step 1: After adding the internal standard EDF-5408 LCS to the sediment sample to be tested, use a rapid solvent extractor to extract and concentrate the extract; Step 2: Add n-hexane to the concentrated extract obtained in step 1, then add an appropriate amount of copper particles (powder / beads), shake thoroughly, filter with a triangular funnel filled with anhydrous sodium sulfate, and concentrate the filtrate to obtain a purified concentrate; Step 3: Add the concentrated solution obtained in step 2 to a multilayer silica gel column, elute with n-hexane, and concentrate the eluate to obtain a purified concentrated solution; Step 4: The concentrated solution obtained in step 3 was further concentrated by purging with high-purity nitrogen, and the internal standard EDF-5409-A ISS was added, and nonane was added to make up the volume to obtain the final analysis sample. Step 5: Analyze and determine the analytical sample using isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry to obtain the content of brominated dioxins in the sediment sample to be tested.
2. The method for determining brominated dioxins in sediments according to claim 1, characterized in that: Step 1 specifically includes: A 13C-PBDD / Fs solution diluted with nonane was added to the sediment sample to extract the internal standard EDF-5408 LCS solution. After the sediment sample was extracted using a rapid solvent extractor (extraction conditions: pressure 1200-1600 psi, temperature 100-180°C, 2-4 cycles, static time 3-10 min), the extract was concentrated using a rotary evaporator.
3. The method for determining brominated dioxins in sediment according to claim 1, characterized in that In step 2, an appropriate amount of n-hexane is added to the concentrated extract obtained in step 1, and then an appropriate amount of copper particles (powder / beads) are added, and the mixture is fully shaken until the copper particles (powder / beads) do not change color. The mixture is allowed to stand and filtered using a triangular funnel filled with anhydrous sodium sulfate.
4. The method for determining brominated dioxins in sediment according to claim 1, characterized in that In step three, the multilayer silica gel column is packed by a dry method, and the packing order is 1-2 g of anhydrous sodium sulfate, 1-2 g of silica gel, 3-5 g of alkaline silica gel, 1-2 g of silica gel, 8-10 g of sulfuric acid silica gel, 2-3 g of silica gel, and 1-6 g of anhydrous sodium sulfate.
5. The method for determining brominated dioxins in sediments according to claim 1, characterized in that In step 5, the chromatographic conditions for the high-resolution gas chromatography-mass spectrometry determination are as follows: a chromatographic column with a stationary phase of 5% phenyl-95% methylpolysiloxane, 15 to 30 m in length, an inner diameter of 0.25 mm, and a film thickness of 0.1 μm; a carrier gas of high-purity helium at 1.0 to 1.2 mL / min; splitless / pulsed splitless mode; an inlet temperature of 240 to 290°C; an injection volume of 1 μL to 2 μL per injection; and a transfer line temperature of 250 to 290°C. The temperature program is 90 to 150°C for 2 to 5 minutes, then increasing to 220 to 280°C at 25 to 35°C / min and holding for 5 to 8 minutes, and finally increasing to 300 to 350°C at 30 to 40°C / min and holding for 5 to 8 minutes. Mass spectrometry conditions included a resolution of R ≥ 10,000, an electron energy of 35 to 45 eV, an ion source temperature of 250 to 350°C, an electron multiplier voltage of 1000 to 2000 V, and selective ion monitoring of characteristic ions such as [M]+, [M+2]+, and [M+4]+. Fourteen brominated dioxins were accurately determined with a single injection.