CN114894914B - Method for measuring dioxin substances in prochloraz technical product by isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry - Google Patents
Method for measuring dioxin substances in prochloraz technical product by isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry Download PDFInfo
- Publication number
- CN114894914B CN114894914B CN202210320060.6A CN202210320060A CN114894914B CN 114894914 B CN114894914 B CN 114894914B CN 202210320060 A CN202210320060 A CN 202210320060A CN 114894914 B CN114894914 B CN 114894914B
- Authority
- CN
- China
- Prior art keywords
- silica gel
- prochloraz
- resolution
- gel column
- dioxin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N2030/042—Standards
- G01N2030/045—Standards internal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a method for measuring dioxin substances in prochloraz original drugs by using isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry, which comprises the following steps: (1) dissolving prochloraz in mixed solvent, adding extraction internal standard EPA 1613 LCS, and adsorbing prochloraz with acidic silica gel to obtain dioxin substance; (2) purifying the extracting solution to obtain a purified solution; (3) treating the purifying liquid to obtain a sample solution; (4) and measuring dioxin substances in the sample solution by adopting a high-resolution gas chromatography-high-resolution dual-focus magnetic mass spectrometer. The method has high sensitivity, high accuracy, convenience and rapidness, can be used for quantitatively detecting dioxin substances in prochloraz original drugs, makes up the blank in the field and has great significance.
Description
Technical Field
The invention belongs to the technical field of analytical chemistry, and particularly relates to a method for measuring dioxin substances in prochloraz original drugs by using isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry (HRGC-HRMS).
Background
The dioxin-like substances mainly comprise 75 polychlorinated dibenzo-p-dioxins (PCDDs) and 135 polychlorinated dibenzofurans (PCDFs). The dioxins studied more are 17 kinds of 2,3,7, 8-chlorodioxins including 7 kinds of tetra-to octachlorodibenzo-p-dioxins and 10 kinds of tetra-to octachlorodibenzofurans. Wherein 2,3,7, 8-tetrachlorodibenzo-p-dioxin (2, 3,7,8-T for short) 4 CDD) Is the most toxic dioxin monomer (oral LD) among all the known compounds at present 50 Only 0.6 mug/kg) and also has a variety of toxic effects including extremely strong carcinogenicity (a rat liver cancer causing dose of 10 pg/g) and extremely low dose of environmental endocrine disrupting effects.
Dioxin substances belong to persistent organic pollutants, have the characteristics of high toxicity, bioaggregability and the like, and have great harm to ecological environment and human health. Currently, there have been reported literature on the detection of dioxin-like substances in water bodies, gases, solid wastes, soil and sediments, and foods (see literature 1 to literature 5).
Prochloraz (see document 6) is widely used as a low-toxicity bactericide for preventing and controlling anthracnose, leaf spot, fusarium wilt and the like of vegetables and fruits. At present, most of commercial prochloraz raw materials are prepared by taking 2,4, 6-trichlorophenol as a raw material and sequentially reacting with 1, 2-dichloroethane, propylamine, phosgene, imidazole and the like. In the synthetic route, dioxin byproducts generated by condensation reaction with chlorine-containing compounds as precursors are diffused into the ecological environment through the production and use of prochloraz raw medicines, so that pollution is caused to a certain extent.
Therefore, detection of dioxin substances in prochloraz technical is a technical problem which needs to be solved in the field. At present, relevant literature reports on detection of dioxin substances in prochloraz technical products are not found.
Document 1: national environmental protection standard HJ 77.1-2008 high resolution gas chromatography-high resolution Mass Spectrometry for measuring isotope dilution of Water quality dioxins, publication date 2008, 12 months and 31 days.
Document 2: national environmental protection standard HJ 77.2-2008, isotope dilution high resolution gas chromatography-high resolution mass spectrometry for determination of environmental air and waste gas dioxins, published on 12 months and 31 days of 2008.
Document 3: national environmental protection standard HJ 77.3-2008 high resolution gas chromatography-high resolution Mass Spectrometry for measuring isotope dilution of solid wastes dioxins, published 12 months 31 days 2008.
Document 4: national environmental protection standard HJ 77.4-2008, measuring isotope dilution high resolution gas chromatography-high resolution mass spectrometry of dioxins in soil and sediment, published on 12 months and 31 days in 2008.
Document 5: national standard GB 5009.205-2013 determination of toxicity equivalent of dioxin and analogues thereof in food safety national standard food, publication date 2013, 11 month and 29 days.
Document 6: national standard GB 22623-2008 Prochloraz, published on 12 months and 17 days of 2008.
Disclosure of Invention
The invention aims to solve the problems and provide a method for measuring dioxin substances in prochloraz technical stock by using isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry with high sensitivity and high accuracy.
The technical scheme for realizing the aim of the invention is as follows: the method for measuring dioxin substances in prochloraz technical through isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry comprises the following steps:
(1) dissolving prochloraz in mixed solvent, adding extraction internal standard EPA 1613 LCS, and adsorbing prochloraz with acidic silica gel to obtain dioxin substance;
(2) purifying the extracting solution obtained in the step (1) to obtain a purified solution;
(3) treating the purifying liquid obtained in the step (2) to obtain a sample solution;
(4) and (3) measuring dioxin substances in the sample solution obtained in the step (3) by adopting a high-resolution gas chromatography-high-resolution dual-focus magnetic mass spectrometer.
In the step (1), the weight-volume ratio of the prochloraz technical stock and the mixed solvent is 1:10-1:50 g/mL, preferably 1:30 g/mL.
In the step (1), the mixed solvent is n-hexane+dichloromethane.
The applicant found through a number of experiments that: the less the amount of n-hexane in the mixed solvent (less than 5 times), the poorer the adsorption effect; the greater the amount of n-hexane (higher than 5 times), the poorer the solubility of prochloraz.
Therefore, in the mixed solvent adopted by the invention, the volume ratio of the normal hexane to the dichloromethane is 5:1.
In the step (1), the weight ratio of the prochloraz technical stock to the acidic silica gel is 1:4-1:6, preferably 1:5.
In the step (1), the acidic silica gel is 44% sulfuric acid-neutral silica gel.
The purification in the step (2) is multi-layer silica gel column purification and active carbon silica gel column purification.
The column packing method for purifying the multi-layer silica gel column is dry column packing, and specifically comprises the following steps: glass wool, 4g of anhydrous sodium sulfate, 3g of neutral silica gel, 5g of alkaline silica gel, 2g of neutral silica gel, 10g of acidic silica gel, 2g of neutral silica gel and 4g of anhydrous sodium sulfate are filled in sequence from bottom to top.
The purification steps of the multi-layer silica gel column are as follows: eluting the multi-layer silica gel column by using 40mL of normal hexane, transferring the extract obtained in the step (1) to the multi-layer silica gel column, eluting the multi-layer silica gel column by using 120mL of normal hexane, collecting the eluent, and concentrating to obtain a primary purifying liquid.
The multi-layer silica gel column purification can remove part of trace impurities in prochloraz original medicine extracting solution, such as raw materials 2,4, 6-trichlorophenol, 1, 2-dichloroethane and the like for prochloraz synthesis.
The column packing method for purifying the activated carbon silica gel column comprises the following steps: one end of the cable-stayed pipe is padded with glass wool with unitary coin thickness, 1g of activated carbon silica gel is filled after compaction, and then the glass wool with unitary coin thickness is padded for compaction.
The activated carbon silica gel column purification steps are as follows: the method comprises the steps of eluting an activated carbon silica gel column with 40mL of normal hexane, transferring a primary purified solution obtained by purifying a multi-layer silica gel column onto the activated carbon silica gel column, eluting the activated carbon silica gel column with 25mL of normal hexane, eluting the activated carbon silica gel column with 40mL of a mixed solvent of normal hexane and dichloromethane (v/v=3:1) [ the two-step eluent does not contain dioxin substances, and therefore does not need to be collected ], turning over the activated carbon silica gel column, eluting the activated carbon silica gel column with 60mL of toluene, collecting the toluene eluent, and concentrating to obtain a purified solution.
The active carbon silica gel column purification can remove polychlorinated biphenyl and other interfering substances.
The treatment in the step (3) is to obtain the purified liquid in the step (2)
The mixture was quantitatively transferred to a 2mL full recovery sample bottle with methylene chloride, then the excess solvent was blown off with a full automatic nitrogen sweep concentrator, concentrated to near dryness, then 0.5ng of EPA 1613 ISS as an internal standard for sample injection was added, and finally the volume was fixed to 25. Mu.L with nonane as a sample solution.
The gas chromatography conditions in the above step (4) are set as follows:
sample injection mode: and the sample injection is not split.
Sample injection volume: 1 mul.
Sample inlet temperature: 280 ℃.
Carrier gas: high purity helium (99.999%).
Carrier gas flow rate: 1mL/min.
Chromatographic column: TR-Dioxin-5MS (60 m.times.0.25 mm.times.0.25 μm).
Heating program: the initial temperature is 140 ℃, the temperature is raised to 200 ℃ at the speed of 20 ℃/min after keeping for 1min, the temperature is raised to 220 ℃ at the speed of 5 ℃/min after staying for 1min, the temperature is raised to 235 ℃ at the speed of 5 ℃/min after staying for 16min, the temperature is raised to 310 ℃ at the speed of 5 ℃/min after staying for 7min, and the temperature stays for 10min.
The mass spectrum conditions in the step (4) are set as follows: the temperature of the ion source is 260 ℃; the temperature of the transmission line is 280 ℃; ionization mode is EI source, electron energy is 45eV; the detection mode is MID mode (two monitoring peak ions of the compound to be detected are selected for monitoring by using a SIM method), the mass calibration substance is FC43, and the resolution ratio is more than 10000.
The invention has the positive effects that:
(1) According to the invention, a large number of experiments show that prochloraz can be completely adsorbed and separated out by adopting acidic silica gel in a mixed solvent with a certain proportion, so that dioxin substances contained in the prochloraz can be detected.
(2) The detection limit of the method of the invention on dioxin substances in prochloraz technical stock is not more than 0.1ng/kg, especially on 2,3,7,8-T 4 CDD mostThe low detection limit can reach 0.01ng/kg, and the sensitivity is high.
(3) The method has the advantages that the isotope internal standard addition recovery rate is in the range of 77-146%, and the method has higher accuracy.
(4) According to the method, the relative standard deviation of the dioxin-like substances is 1.2% -15.8%, and the distribution rule of the dioxin-like substance detection results is consistent with the dioxin generation mechanism.
(5) The method has high sensitivity, high accuracy, convenience and rapidness, can be used for quantitatively detecting dioxin substances in prochloraz original drugs, makes up the blank in the field and has great significance.
Detailed Description
1. Experimental section.
1. Reagents and materials.
1.1, organic solvents such as normal hexane, dichloromethane, toluene, ethyl acetate and the like are pesticide residue grade reagents, and dioxin substances can not be detected after 10000 times concentration.
1.2, sodium hydroxide, concentrated sulfuric acid, anhydrous sodium sulfate and the like are all high-grade pure reagents, and blank detection should be carried out before use.
1.3, neutral silica gel and active carbon silica gel are all commercially available products of Kandong chemical, and a leaching curve is prepared to confirm the separation result before use.
The acidic silica gel was 44% sulfuric acid-neutral silica gel, and the preparation method was referred to in section 5.22 of reference 1, 44% sulfuric acid silica gel.
The alkaline silica gel was 2% sodium hydroxide-neutral silica gel, and the preparation method was referred to section 5.20 of reference 1, 2% potassium hydroxide silica gel.
1.4 extraction of internal standard EPA 1613 LCS, containing 15 isotopes 13 C 12 Labeled dioxins [ see example 2 of appendix B of document 1 ].
The sample injection internal standard EPA 1613 ISS contains 2 isotopes 13 C 12 Labeled dioxins [ see example 2 of appendix B of document 1 ].
1.5, dioxin-like standard substance is derived from Cerelliant Inc. of America.
2. Instruments and devices.
2.1, high resolution gas chromatography-high resolution double focusing magnetic mass spectrometer model Thermo DFS (thermoelectric in the United states).
2.2 electronic balance, model YP10002 (Shanghai Yue Ping scientific instruments Co., ltd.).
2.3, a strong magnetic force flat plate stirrer, the model is 98-2 (the company of the national instruments Limited of the strengthening city).
2.4, rotary evaporator model YRE-201D (incorporated by reference, instrument Co., ltd.).
2.5, a full-automatic nitrogen-air purging concentrator, the model of which is YGC-16A (Tianjin Ewei Europe technology development Co., ltd.).
3. Experimental procedure.
3.1, weighing 10g of prochloraz technical sample, putting the prochloraz technical sample into a 500 mL round bottom flask, adding 300mL of normal hexane-dichloromethane (v/v=5:1) mixed solvent, stirring until the prochloraz technical sample is completely dissolved, adding 0.5ng to extract an internal standard EPA 1613 LCS, adding 50g of acid silica gel [ 44% sulfuric acid-neutral silica gel ], stirring at room temperature for 30min, standing for layering, at the moment, enabling the lower layer of acid silica gel to be yellowish, filtering the upper layer of colorless transparent solution by using an anhydrous sodium sulfate small column, and concentrating the filtrate to obtain an extract.
3.2.1 purifying by a multi-layer silica gel column.
3.2.1.1, column packing: glass wool, 4g of anhydrous sodium sulfate, 3g of neutral silica gel, 5g of alkaline silica gel, 2g of neutral silica gel, 10g of acidic silica gel, 2g of neutral silica gel and 4g of anhydrous sodium sulfate are filled in sequence from bottom to top.
3.2.1.2, purifying: eluting the multi-layer silica gel column with 40mL of normal hexane, transferring the obtained extract to the multi-layer silica gel column, eluting the multi-layer silica gel column with 120mL of normal hexane, collecting the eluent, and concentrating to obtain a primary purification liquid.
3.2.2, purifying by an activated carbon silica gel column.
3.2.2.1, column packing: one end of the cable-stayed pipe is padded with glass wool with unitary coin thickness, 1g of activated carbon silica gel is filled after compaction, and then the glass wool with unitary coin thickness is padded for compaction.
3.2.2.2, purifying: the method comprises the steps of eluting an activated carbon silica gel column with 40mL of normal hexane, transferring a primary purified solution obtained by purifying a multi-layer silica gel column onto the activated carbon silica gel column, eluting the activated carbon silica gel column with 25mL of normal hexane, eluting the activated carbon silica gel column with 40mL of a mixed solvent of normal hexane and dichloromethane (v/v=3:1) [ the two-step eluent does not contain dioxin substances, and therefore does not need to be collected ], turning over the activated carbon silica gel column, eluting the activated carbon silica gel column with 60mL of toluene, collecting the toluene eluent, and concentrating to obtain a purified solution.
And 3.3, quantitatively transferring the obtained purified solution into a 2mL full-recovery sample injection bottle by using dichloromethane, blowing off redundant solvent by using a full-automatic nitrogen-air blowing concentrator, concentrating to near dryness, adding 0.5ng of sample injection internal standard EPA 1613 ISS, and finally, fixing the volume to 25 mu L by using nonane to obtain a sample solution.
And 3.4, measuring dioxin substances in the obtained sample solution by adopting a high-resolution gas chromatography-high-resolution dual-focus magnetic mass spectrometer.
The gas chromatography conditions were set as follows:
the sample injection mode is non-split sample injection, the sample injection volume is 1 mu L, and the sample injection temperature is 280 ℃.
The carrier gas was high purity helium (99.999%) with a carrier gas flow of 1mL/min.
The column was TR-Dioxin-5MS (60 m. Times.0.25 mm. Times.0.25 μm).
Heating program: the initial temperature is 140 ℃, the temperature is raised to 200 ℃ at the speed of 20 ℃/min after keeping for 1min, the temperature is raised to 220 ℃ at the speed of 5 ℃/min after staying for 1min, the temperature is raised to 235 ℃ at the speed of 5 ℃/min after staying for 16min, the temperature is raised to 310 ℃ at the speed of 5 ℃/min after staying for 7min, and the temperature stays for 10min.
The mass spectrometry conditions were set as follows: the temperature of the ion source is 260 ℃; the temperature of the transmission line is 280 ℃; ionization mode is EI source, electron energy is 45eV; the detection mode is MID mode (two monitoring peak ions of the compound to be detected are selected for monitoring by using a SIM method), the mass calibration substance is FC43, and the resolution ratio is more than 10000.
2. Results and analysis.
1. Testing and selection of extraction methods.
1.1, because the prochloraz has a low melting point, the prochloraz has a temperature of 46.5-49.3 ℃, so that Soxhlet extraction and accelerated solvent extraction cannot be adopted.
1.2, the solubility of prochloraz in water is very small, only 34.4mg/L (25 ℃), and the liquid-liquid extraction method cannot be adopted.
1.3, the applicant finds through a plurality of experiments: the acidic silica gel can effectively adsorb prochloraz and does not adsorb dioxin substances.
However, there is a large difference in adsorption effect of different solvents.
1.3.1, in a single solvent such as ethyl acetate, normal hexane, dichloromethane and the like, the acidic silica gel is difficult to effectively adsorb prochloraz, the bottle bottom is oily liquid before treatment, and the bottle bottom is oily liquid after treatment.
1.3.2, in a mixed solvent of normal hexane and dichloromethane with the equal volume ratio (1:1), the acidic silica gel still has difficulty in effectively adsorbing prochloraz, the bottle bottom is oily liquid before treatment, and the bottle bottom is oily liquid after treatment.
1.3.3, when the volume ratio of n-hexane to dichloromethane is 5:1, prochloraz can be completely and effectively adsorbed, and the bottle bottom after treatment has no oily liquid (dioxin belongs to ultra-trace detection and is little to be hardly visible to naked eyes).
1.3.4, when the volume ratio of n-hexane to dichloromethane is 10:1, the prochloraz technical is difficult to dissolve completely.
The feasibility of the various extraction methods is shown in Table 1.
TABLE 1
| Extraction method | Solvent(s) | Whether or not to make it possible | |
| 1 | Soxhlet extraction method | / | Whether or not |
| 2 | Accelerated solvent extraction process | / | Whether or not |
| 3 | Liquid-liquid extraction method | / | Whether or not |
| 4 | Acidic silica gel extraction method | Acetic acid ethyl ester | Whether or not |
| 5 | Acidic silica gel extraction method | N-hexane | Whether or not |
| 6 | Acidic silica gel extraction method | Dichloromethane (dichloromethane) | Whether or not |
| 7 | Acidic silica gel extraction method | N-hexane-dichloromethane (v/v=1:1) | Whether or not |
| 8 | Acidic silica gel extraction method | N-hexane-dichloromethane (v/v=10:1) | Whether or not |
| 9 | Acidic silica gel extraction method | N-hexane-dichloromethane (v/v=5:1) | Is that |
2. A detection limit.
The detection limit was measured according to the method of the present invention, and the results are shown in Table 2.
The measurement steps are as follows: dioxin standard substances (the addition amount is 0.5 pg of tetrachlorodioxins, 2.5 pg of pentachlorodioxins to heptachlorodioxins and 5.0 pg of octachlorodioxins) are added into a mixed solvent of normal hexane and dichloromethane, and then extraction, purification, instrument analysis and quantitative calculation which are the same as sample treatment are carried out. The measurement was repeated 5 times, and the standard deviation of the measured value was calculated, taking 3 times the standard deviation as the method detection limit.
TABLE 2
| PCDDs | Detection limit (ng/kg) | PCDFs | Detection limit (ng/kg) |
| 2,3,7,8-T 4 CDD | 0.01 | 2,3,7,8-T 4 CDF | 0.03 |
| 1,2,3,7,8-P 5 CDD | 0.1 | 1,2,3,7,8-P 5 CDF | 0.1 |
| 1,2,3,4,7,8-H 6 CDD | 0.08 | 2,3,4,7,8-P 5 CDF | 0.1 |
| 1,2,3,6,7,8-H 6 CDD | 0.1 | 1,2,3,4,7,8-H 6 CDF | 0.1 |
| 1,2,3,7,8,9-H 6 CDD | 0.1 | 1,2,3,6,7,8-H 6 CDF | 0.1 |
| 1,2,3,4,6,7,8-H 7 CDD | 0.1 | 2,3,4,6,7,8-H 6 CDF | 0.1 |
| O 8 CDD | 0.1 | 1,2,3,7,8,9-H 6 CDF | 0.09 |
| 1,2,3,4,6,7,8-H 7 CDF | 0.07 | ||
| 1,2,3,4,7,8,9-H 7 CDF | 0.07 | ||
| O 8 CDF | 0.1 |
As can be seen from table 2: the method of the invention is specific to 2,3,7,8-T 4 The lowest detection limit of CDD is 0.01ng/kg, and the detection limit of other 16 2,3,7, 8-chloro dioxin substances is not more than 0.1ng/kg, which shows that the method has higher sensitivity.
3. Recovery rate.
3 sample batches of prochloraz technical (3 replicates per batch) were tested according to the method of the invention and recovery rates of the extracted internal standard substances for a total of 9 samples are shown in table 3.
TABLE 3 Table 3
As can be seen from table 3: the recovery rate of the method is between 77 and 146 percent, wherein the recovery rate of PCDFs is slightly better than that of PCDDs, and the overall recovery rate meets the recovery rate requirement of an ultra-trace detection method, which indicates that the method has high accuracy.
4. Precision.
3 sample batches of prochloraz technical (3 replicates per batch) were tested according to the method of the present invention and the measured mass concentrations and total toxicity equivalent (I-TEQ) are shown in table 4.
TABLE 4 Table 4
As can be seen from table 4: the measured mass concentration and the total relative standard deviation of the toxicity equivalent (I-TEQ) are 1.2-15.8%, and the relative standard deviation of low-chlorinated dioxins and high-chlorinated dioxins is low.
In addition, the PCDDs of the detection results of dioxin substances in prochloraz raw medicines in different batches are higher than the PCDFs, the distribution rule of the dioxin substances basically accords with the synthetic mechanism of dioxin, namely, the precursor reaction mainly generates the PCDDs, and the detection results of the method are accurate and reliable through side verification.
Claims (8)
1. The method for measuring dioxin substances in prochloraz technical through isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry is characterized by comprising the following steps of:
(1) dissolving prochloraz in mixed solvent, adding extraction internal standard EPA 1613 LCS, and adsorbing prochloraz with acidic silica gel to obtain dioxin substance; the mixed solvent is n-hexane and dichloromethane; the volume ratio of the n-hexane to the dichloromethane is 5:1; the acidic silica gel is 44% sulfuric acid-neutral silica gel;
(2) purifying the extracting solution obtained in the step (1) to obtain a purified solution;
(3) treating the purifying liquid obtained in the step (2) to obtain a sample solution;
(4) and (3) measuring dioxin substances in the sample solution obtained in the step (3) by adopting a high-resolution gas chromatography-high-resolution dual-focus magnetic mass spectrometer.
2. The method for measuring dioxin-like substances in prochloraz technical by isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry according to claim 1, which is characterized in that: in the step (1), the weight-volume ratio of the prochloraz technical stock and the mixed solvent is 1:10-1:50 g/mL; the weight ratio of prochloraz technical to the acidic silica gel is 1:4-1:6.
3. The method for measuring dioxin-like substances in prochloraz technical through isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry according to claim 1 or 2, characterized in that: the purification in the step (2) is multi-layer silica gel column purification and active carbon silica gel column purification.
4. The method for determining dioxin-like substances in prochloraz technical through isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry according to claim 3, wherein the method for purifying the multi-layer silica gel column is a dry column packing method, which comprises the following steps: sequentially filling glass wool, 4g of anhydrous sodium sulfate, 3g of neutral silica gel, 5g of alkaline silica gel, 2g of neutral silica gel, 10g of acidic silica gel, 2g of neutral silica gel and 4g of anhydrous sodium sulfate from bottom to top; the purification steps of the multi-layer silica gel column are as follows: eluting the multi-layer silica gel column by using 40mL of normal hexane, transferring the extract obtained in the step (1) to the multi-layer silica gel column, eluting the multi-layer silica gel column by using 120mL of normal hexane, collecting the eluent, and concentrating to obtain a primary purifying liquid.
5. The method for determining dioxin-like substances in prochloraz technical through isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry according to claim 3, which is characterized in that the column packing method for purifying the activated carbon silica gel column comprises the following steps: one end of the cable-stayed pipe is padded with glass wool with unitary coin thickness, 1g of activated carbon silica gel is filled after compaction, and then the glass wool with unitary coin thickness is padded for compaction; the activated carbon silica gel column purification steps are as follows: eluting the activated carbon silica gel column by using 40mL of normal hexane, transferring the primary purification liquid obtained by purifying the multi-layer silica gel column onto the activated carbon silica gel column, eluting the activated carbon silica gel column by using 25mL of normal hexane, eluting the activated carbon silica gel column by using 40mL of normal hexane-dichloromethane mixed solvent, turning over the activated carbon silica gel column, eluting the activated carbon silica gel column by using 60mL of toluene, collecting the toluene eluent, and concentrating to obtain the purification liquid.
6. The method for measuring dioxin-like substances in prochloraz technical through isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry according to claim 1 or 2, characterized in that: the treatment in the step (3) is to quantitatively transfer the purified liquid obtained in the step (2) into a 2mL full-recovery sample injection bottle by using methylene dichloride, then blow off redundant solvent by using a full-automatic nitrogen air purge concentrator, concentrate to near dryness, then add 0.5ng of sample injection internal standard EPA 1613 ISS, and finally fix the volume to 25 mu L by using nonane as a sample solution.
7. The method for measuring dioxin-like substances in prochloraz technical by isotope dilution high resolution gas chromatography-high resolution mass spectrometry according to claim 1 or 2, characterized in that the gas chromatography conditions in the above step (4) are set as follows:
sample injection mode: sample introduction without diversion;
sample injection volume: 1 μl;
sample inlet temperature: 280 ℃;
carrier gas: 99.999% high purity helium;
carrier gas flow rate: 1mL/min;
chromatographic column: TR-Dioxin-5MS, 60 m.times.0.25 mm.times.0.25 μm in specification;
heating program: the initial temperature is 140 ℃, the temperature is raised to 200 ℃ at the speed of 20 ℃/min after keeping for 1min, the temperature is raised to 220 ℃ at the speed of 5 ℃/min after staying for 1min, the temperature is raised to 235 ℃ at the speed of 5 ℃/min after staying for 16min, the temperature is raised to 310 ℃ at the speed of 5 ℃/min after staying for 7min, and the temperature stays for 10min.
8. The method for measuring dioxin-like substances in prochloraz technical by using isotope dilution high resolution gas chromatography-high resolution mass spectrometry according to claim 1 or 2, characterized in that the mass spectrometry conditions in the step (4) are set as follows: the temperature of the ion source is 260 ℃; the temperature of the transmission line is 280 ℃; ionization mode is EI source, electron energy is 45eV; the detection mode is MID mode, the quality calibration substance is FC43, and the resolution ratio is more than 10000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210320060.6A CN114894914B (en) | 2022-03-29 | 2022-03-29 | Method for measuring dioxin substances in prochloraz technical product by isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210320060.6A CN114894914B (en) | 2022-03-29 | 2022-03-29 | Method for measuring dioxin substances in prochloraz technical product by isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114894914A CN114894914A (en) | 2022-08-12 |
| CN114894914B true CN114894914B (en) | 2023-06-30 |
Family
ID=82714556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210320060.6A Active CN114894914B (en) | 2022-03-29 | 2022-03-29 | Method for measuring dioxin substances in prochloraz technical product by isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114894914B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101895342B1 (en) * | 2018-03-07 | 2018-10-18 | (주) 한국환경진단연구소 | Method for Pre-treating a Sample Containing Dioxine and Furane Using Multi-Layer Silica Gel Column |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009097886A (en) * | 2007-10-12 | 2009-05-07 | Chubu Electric Power Co Inc | Simplified measuring method of dioxins |
| CN104391067B (en) * | 2014-10-30 | 2016-03-30 | 中山出入境检验检疫局检验检疫技术中心 | A kind of method measuring Prochloraz or its metabolic product in plant-derived food |
| CN107037163B (en) * | 2017-04-13 | 2019-05-17 | 浙江省农业科学院 | The pre-treating method of more pesticide residues during a kind of determination of the environment is biological |
| CN107817305B (en) * | 2017-10-27 | 2020-08-07 | 广东产品质量监督检验研究院 | Method for detecting dioxin and dioxin polychlorinated biphenyl in poultry eggs |
| CN109298114B (en) * | 2018-09-29 | 2020-12-11 | 浙江省农业科学院 | Pretreatment method for detecting pesticide residue in biological sample and application thereof |
| CN112697909A (en) * | 2020-12-11 | 2021-04-23 | 深圳市疾病预防控制中心（深圳市卫生检验中心、深圳市预防医学研究所） | Detection method of dioxin compound |
| CN112666295A (en) * | 2020-12-30 | 2021-04-16 | 生态环境部华南环境科学研究所 | Method for extracting, cooperatively separating and detecting polychlorinated biphenyl and dioxin in soil |
-
2022
- 2022-03-29 CN CN202210320060.6A patent/CN114894914B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101895342B1 (en) * | 2018-03-07 | 2018-10-18 | (주) 한국환경진단연구소 | Method for Pre-treating a Sample Containing Dioxine and Furane Using Multi-Layer Silica Gel Column |
Non-Patent Citations (1)
| Title |
|---|
| 同位素稀释 /高分辨气相色谱-质谱联用同时测定空气中二噁英、多氯联苯、多溴联苯醚和溴代二噁英;高丹;刘劲松;朱国华;巩宏平;周欣;王玲;莫卫民;李菲;;分析化学;第41卷(第12期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114894914A (en) | 2022-08-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Roerdink et al. | Sensitive method for the determination of roxarsone using solid-phase microextraction with multi-detector gas chromatography | |
| CN107300598B (en) | A kind of pre-treating method for Multiple Pesticides residue detection in tealeaves | |
| CN107655991A (en) | The assay method of 6 kinds of phthalic acid esters in soil | |
| CN112697909A (en) | Detection method of dioxin compound | |
| CN111487327A (en) | Method for detecting multiple persistent organic chemical pollutants in sample | |
| Fan et al. | Simultaneous determination of chlorinated aromatic hydrocarbons in fly ashes discharged from industrial thermal processes | |
| Han et al. | Simultaneous determination of brominated phenols in soils | |
| Jakovljević et al. | Pollution levels and deposition processes of airborne organic pollutants over the central Adriatic area: Temporal variabilities and source identification | |
| CN114894914B (en) | Method for measuring dioxin substances in prochloraz technical product by isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry | |
| KR20040076387A (en) | Improved solid phase microextraction fiber, preparation method thereof and determination method of alkylphenols and bisphenol-a in water samples with the spme fiber | |
| Jin et al. | Simultaneous determination of 42 organic chemicals in bottled water by combining C18 extraction disk with GC-MS and LC/MS/MS technique | |
| Kuzmin et al. | Assessment of stable carbon isotope 13С/12С ratio in phthalates from surface waters using HPLC-HRMS-TOF approach | |
| Balinova et al. | Determination of herbicide residues in soil in the presence of persistent organochlorine insecticides | |
| CN111089918B (en) | Method for detecting dioxin substances in waste gas | |
| CN108593804A (en) | The Gas Chromatography-Mass Spectrometry method of phenolic compound in Surface Sediments | |
| CN113820421A (en) | Method for measuring 6 phenolic compounds in water | |
| CN115406990B (en) | Method for detecting dioxin in chlorinated paraffin industrial products | |
| Rahman et al. | Chlorobiphenyls in sewage sludge; comparison of extraction methods | |
| KR100504303B1 (en) | Determination Method of Ethylenethiourea, Maleic Hydrazide and Isopropylmethylphosphonate in Water Samples | |
| CN115184499B (en) | Synergistic detection method of organic chlorine pesticide, halogenated flame retardant and organic phosphate and application | |
| CN115406990A (en) | Method for detecting dioxin in chlorinated paraffin industrial product | |
| CN111879879B (en) | Method for detecting methamidophos and octachlorodipropyl ether in plant food | |
| RU2395804C2 (en) | METHOD FOR SIMULTANEOUS DETERMINATION OF TOTAL CONTENT OF F-, Cl-, Br-, I- S- AND P-ORGANIC COMPOUNDS IN WATER AND AQUEOUS SOLUTIONS | |
| Cai et al. | LC–MS analysis of antifouling agent Irgarol 1051 and its decyclopropylated degradation product in seawater from marinas in Hong Kong | |
| CN109164192B (en) | Method for determining content of methyl phosphine dichloride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |