CN106950301B - Determination method of dioxin in sediment and rapid pretreatment method of sediment - Google Patents
Determination method of dioxin in sediment and rapid pretreatment method of sediment Download PDFInfo
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- CN106950301B CN106950301B CN201710152293.9A CN201710152293A CN106950301B CN 106950301 B CN106950301 B CN 106950301B CN 201710152293 A CN201710152293 A CN 201710152293A CN 106950301 B CN106950301 B CN 106950301B
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- 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
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Abstract
The invention provides a rapid pretreatment method of sediments and a determination method of dioxin. The rapid pretreatment method of the sediment comprises the following steps: extracting a sample, purifying the sample, and blowing nitrogen for concentration; the silver ion modified amino silica gel in the method has excellent performance, and the problems of poor stability, easy shedding and the like of silver ions in common silver nitrate silica gel are solved; the sample purification treatment is carried out by adopting a one-section method, the filling sequence of the filler in the one-section silica gel column is strong in pertinence and reasonable, the complex matrix effect is overcome, various impurities in a dioxin organic pollutant matrix can be removed, and the interference on the subsequent detection of dioxin compounds is eliminated; more importantly, tests show that the detection result obtained by the method for determining dioxin in sediments and the method for quickly pretreating sediments has the advantages of high accuracy, good reproducibility and high recovery rate.
Description
Technical Field
The invention relates to the technical field of pollutant monitoring, in particular to a method for determining dioxin in sediments and a method for quickly pretreating the sediments.
Background
The environmental toxicity of dioxins has received a great deal of attention from people all over the world. At present, the types of organic pollutants in the environment are increasing, such as dioxin, and the matrix in which such organic pollutants are located is also quite complex, and the matrix often contains various acidic compounds, basic compounds, aromatic compounds, sulfur-containing compounds, water-containing compounds and other impurities, and if the impurities are not treated, the detection results of subsequent organic pollutants are greatly interfered, and the detection results are influenced. At present, the quantitative detection of dioxin in the environment is a difficult point in the field of organic ultra-trace analysis, for environmental samples, liquid-liquid extraction is mostly used for extracting samples at home and abroad at present, and the purification process refers to the US EPA method for multi-stage chromatographic column purification, but the following defects exist: the whole purification process is long, the steps are complicated, the required time is long (about three to four days), the purification method is complex, the requirement on an analyst is high, and the requirement on laboratory conditions is high. The above problems limit the rapid development of dioxin detection work.
Although silica gel is used as a good adsorption, a silica gel chromatographic column prepared by a common silica gel chromatographic column preparation method can remove part of impurities in a matrix, when the matrix is complex and dioxin organic pollutants in the matrix are detected, various acidic compounds, basic compounds, aromatic compounds, sulfur-containing compounds, water-containing compounds and other impurities in the matrix are difficult to remove by the silica gel chromatographic column prepared by the common silica gel chromatographic column preparation method, the interference on the subsequent dioxin detection is still large, and the final detection result is directly influenced. Therefore, the silica gel chromatographic column prepared by the common silica gel chromatographic column preparation method cannot be used for detecting dioxin organic pollutants in a complex matrix.
Therefore, a method for determining dioxin in sediment and a method for quickly pretreating sediment are urgently needed to be developed, and the method can be widely applied to common organic analysis laboratories and can promote the quick development of dioxin detection work.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for determining dioxin in sediments and a method for quickly pretreating the sediments.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for rapid pretreatment of a deposit, comprising the steps of:
(1) will be provided with13Adding a C-PCDD/Fs internal standard into a sediment sample, and extracting the sediment sample by adopting an ultrasonic extraction method to obtain an extracting solution containing dioxin;
(2) concentrating the extracting solution obtained in the step (1), and purifying by using a multilayer silica gel column to obtain a purified solution, wherein the multilayer silica gel column comprises the following components from bottom to top: 1-3 cm of column height of glass fiber, 3-6 g of neutral silica gel, 5-10 g of 40% sodium hydroxide silica gel, 3-6 g of neutral silica gel, 30-40 g of 40% sulfuric acid silica gel, 3-6 g of neutral silica gel, 3-7 g of silver ion modified amino silica gel and 15-25 g of anhydrous concentrated sodium sulfate;
(3) and (3) blowing and concentrating the purified liquid nitrogen obtained in the step (2) to obtain a purified sample for instrument analysis.
Preferably, in the step (1), the sediment sample is prepared by freeze-drying the collected sediment to a constant weight, mixing the sediment with anhydrous sodium sulfate, and grinding to remove moisture, wherein the mass ratio of the sediment to the anhydrous sodium sulfate is 0.5-2: 1.
Preferably, in the step (1), the step of extracting the sediment by using an ultrasonic extraction method specifically includes:
extracting the sediments by using an ultrasonic cleaning pool to obtain an extracting solution, wherein the operating parameters of the ultrasonic cleaning pool are as follows: the ultrasonic power is 400-600W, the temperature is 70-100 ℃, the time is 10-45 min, and the reagent comprises one or more of hydrochloric acid, petroleum ether, acetone, dimethyl sulfoxide, toluene, n-hexane and dichloromethane.
Further preferably, in the step (1), the operation parameters of the ultrasonic cleaning pool are that the ultrasonic power is 500W, the temperature is 90 ℃, the time is 30min, the reagent is a mixed solution of petroleum ether and a hydrochloric acid solution, wherein the volume ratio of the petroleum ether to the hydrochloric acid solution is 1-8: 1, and the concentration of hydrochloric acid in the hydrochloric acid solution is 0.1-4 mol/L.
Preferably, in the step (2), the multi-layer silica gel column comprises the following components from bottom to top: glass fiber with the height of 2cm column, neutral silica gel 5g, 8% sodium hydroxide silica gel 8g, neutral silica gel 5g, 40% sulfuric acid silica gel 35g, neutral silica gel 5g, silver ion modified amino silica gel 5g, anhydrous concentrated sodium sulfate 20 g.
It can be understood that the "8% sodium hydroxide silica gel" in the invention means that the mass fraction of sodium hydroxide in the sodium hydroxide silica gel is 8%; the 40% sulfuric acid silica gel refers to 40% sulfuric acid by mass in the sulfuric acid silica gel.
Preferably, in the step (2), the silver ion-modified amino silica gel is prepared by the following method:
mixing a mixed solution of amino silica gel and absolute ethyl alcohol with a mixed solution of silver nitrate and absolute ethyl alcohol, continuously stirring for 20-28 h under normal temperature and dark conditions, filtering to remove a solvent, and activating for 1-4 h at 90-120 ℃ to obtain the silver ion modified amino silica gel, wherein the ratio of the mass of the amino silica gel to the volume of the absolute ethyl alcohol in the mixed solution of the amino silica gel and the absolute ethyl alcohol is 1: 5-10 (g/m L), the ratio of the mass of the silver nitrate to the volume of the absolute ethyl alcohol in the mixed solution of the silver nitrate and the ethyl alcohol is 1: 10-20 (g/m L), and the mass ratio of the amino silica gel to the silver nitrate is 5-15: 1 (g/g).
Further preferably, in the step (2), the amino silica gel is prepared by the following method:
soaking silica gel in hydrochloric acid solution for 10-14 h, and washing with distilled water to remove Cl-The preparation method comprises the steps of activating for 1-4 hours at 90-120 ℃, mixing 3-aminopropyltriethoxysilane with toluene, adding activated silica gel, refluxing and stirring for reaction for 6-10 hours at 50-90 ℃, filtering, extracting with toluene, and drying to obtain the amino silica gel, wherein the mass ratio of the volume of the 3-aminopropyltriethoxysilane to the silica gel is 1-4: 1(m L/g).
Still more preferably, in the step (2), the mass ratio of the volume of the hydrochloric acid solution to the silica gel is 1-5: 1(m L/g).
Still more preferably, in the step (2), the concentration of hydrochloric acid in the hydrochloric acid solution is 0.05-0.2 mol/L.
Still more preferably, in the step (2), the mass ratio of the volume of the toluene to the silica gel is 1-5: 1(m L/g).
Preferably, in the step (2), before the step of concentrating the extract obtained in the step (1) and purifying the concentrate with a multi-layer silica gel column to obtain a purified solution, the method further comprises:
soaking a multilayer silica gel column with a first leacheate, driving out bubbles in the multilayer silica gel column with an air pump, and pre-leaching the multilayer silica gel column with the first leacheate.
Further preferably, in the step (2), the amount of the first leacheate used is 40-200 m L.
Further preferably, in the step (2), the first leaching solution includes but is not limited to one or more of toluene, n-hexane, cyclohexane and dichloromethane.
Still more preferably, the first rinse is n-hexane.
Preferably, in the step (2), the step of concentrating the extract obtained in the step (1) and purifying the concentrate with a multi-layer silica gel column to obtain a purified solution specifically includes:
concentrating the extracting solution obtained in the step (1), transferring the extracting solution to the multilayer silica gel column, and standing for 10-20 min; performing first leaching by using a second leaching solution, and performing second leaching by using a third leaching solution to obtain a purified solution, wherein the second leaching solution and the third leaching solution are the same or different organic solvents; the organic solvent includes but is not limited to one or more of toluene, n-hexane, cyclohexane and dichloromethane.
Further preferably, in the step (2), the volume ratio of the second eluent to the third eluent is 2-3: 2-3 (m L/m L).
Further preferably, in the step (2), the second eluent is cyclohexane.
Further preferably, in the step (2), the amount of the second leacheate used is 40-60 m L.
Still more preferably, in the step (2), the third eluent is a mixed solution of cyclohexane and dichloromethane, wherein the volume ratio of cyclohexane to dichloromethane is 3-5: 1(m L/m L).
Further preferably, in the step (2), the amount of the third eluent is 40-60 m L.
In a second aspect, the invention also provides a method for determining the content of dioxin in sediment, which comprises the following steps:
taking the purified sample obtained by the rapid pretreatment method for the sediment according to the first aspect, and performing instrument analysis and determination on the purified sample by using an isotope dilution high-resolution gas chromatography-high-resolution mass spectrometer to obtain a determination result of the dioxin content in the sediment.
Preferably, the purified sample is subjected to instrument analysis and measurement by adopting an isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry combined method, so that a measurement result of the dioxin content in the sediment is obtained; the parameters of the method adopted are as follows:
the gas chromatography conditions comprise that the sample injection mode is non-shunting sample injection 1 μ l, the sample injection port temperature is 260 deg.C, the carrier gas flow rate is 1.0ml/min, the gas interface temperature is 270 deg.C, the chromatographic column is SP-2331(60m × 0.32mm × 0.2.2 μm), the initial temperature is 140 deg.C, the temperature is raised to 220 deg.C at the speed of 4 deg.C/min after 2min, the temperature is raised to 260 deg.C at the speed of 3 deg.C/min after 1min, and the retention time is 25 min;
the mass spectrum conditions are as follows: the interface temperature of the chromaticness is 300 ℃, the ion source temperature is 260 ℃, the collision energy of EI source is 70eV, and the ion Selection (SIM) mode is adopted to couple [ M]+、[M+2]+And [ M +4 ]]+And monitoring the characteristic ions.
The invention has the beneficial effects that:
the invention provides a method for determining dioxin in sediments and a method for quickly pretreating the sediments, wherein the silver ion modified amino silica gel adopted in the method has excellent performance, and the problems of poor stability, easy falling off and the like of silver ions in common silver nitrate silica gel are solved; the method has the advantages that a one-section method is adopted for purifying the sample, the filling sequence of the filler in the one-section silica gel column is strong in pertinence and reasonable, the complex matrix effect is overcome, various impurities in a dioxin organic pollutant matrix can be removed, and the interference on the subsequent dioxin detection result is eliminated; more importantly, tests show that the detection results obtained by using the method for determining dioxin in sediments and the method for quickly pretreating sediments have the advantages of high accuracy, good reproducibility and high recovery rate.
Detailed Description
The invention is further described in detail below with reference to specific examples in order to clearly understand the technical solutions protected by the present invention.
Example 1
The invention provides a method for determining dioxin in sediments and a method for quickly pretreating the sediments, which comprises the following steps:
(1) extraction: weighing 10g of collected sediment (collected within 5 km around a garbage incineration plant), and freeze-drying the sediment at-65 ℃ to constant weight; 1.0ng13Adding a C-PCDD/Fs internal standard into a sediment sample, and extracting the sediment sample by using an ultrasonic cleaning pool to obtain an extracting solution containing dioxin, wherein the operating parameters of the ultrasonic cleaning pool are that the ultrasonic power is 500W, the temperature is 90 ℃, the time is 30min, a reagent is a mixed solvent of petroleum ether and a hydrochloric acid solution (wherein the volume ratio of the petroleum ether to the hydrochloric acid solution is 4:1, and the concentration of hydrochloric acid in the hydrochloric acid solution is 1 mol/L);
(2) cleaning, namely soaking a multilayer silica gel column by using normal hexane, driving bubbles in the column completely by using an air pump, connecting a column pipe of the multilayer silica gel column with a liquid receiving tank by using a connector, placing a waste liquid tank below the multilayer silica gel column, fixing a first liquid separating funnel containing 50m L normal hexane on the liquid receiving tank, opening a valve of the first liquid separating funnel, adjusting the leaching speed to enable the normal hexane in the first liquid separating funnel to drip at the speed of 2d/s, closing the valve of the multilayer silica gel column when the normal hexane in the liquid separating funnel flows out and the liquid level of the normal hexane in the multilayer silica gel column reaches 1cm above the column layer, removing the liquid separating funnel, taking away the waste liquid tank, and replacing a conical flask;
collecting the extracting solution obtained in the step (1), concentrating to 2m L by using a rotary evaporation concentrator, opening a valve of the multilayer silica gel column, transferring the concentrated extracting solution into the multilayer silica gel column by using a dropper, washing a container containing the concentrated extracting solution three times by using a small amount of normal hexane, transferring the washing solution into the multilayer silica gel column together, standing for 15min, fixing a second separating funnel containing 50m L cyclohexane on a liquid receiving tank, opening the valve of the second separating funnel, adjusting the leaching speed to enable the cyclohexane in the second separating funnel to drip at the speed of 2d/s, stopping the valves of the second separating funnel and the multilayer silica gel column, pouring the mixed liquid of 40m L cyclohexane and 10m L dichloromethane which is prepared in situ into the second separating funnel, opening the valve of the second separating funnel, adjusting the leaching speed to enable the mixed liquid in the second separating funnel to drip at the speed of 2d/s, and taking down the conical flask after the multilayer silica gel column is completely eluted, wherein the purified sample is collected in the conical flask;
the multilayer silica gel column adopted in the step (2) is as follows: the following reagents were sequentially filled into the glass column:
glass fiber, 5g of neutral silica gel, 8g of 40% sodium hydroxide silica gel, 5g of neutral silica gel, 35g of 40% sulfuric acid silica gel, 5g of neutral silica gel, 5g of silver ion modified amino silica gel and 20g of anhydrous concentrated sodium sulfate;
(3) concentrating, namely adding 2m of L toluene or isooctane serving as a protective agent into the second purification obtained in the step (2), and then carrying out nitrogen blowing concentration on the obtained second purification solution to obtain a purified sample for instrument analysis;
(4) and (3) determination: taking the purified sample obtained in the step (3), and carrying out instrument analysis and determination on the purified sample by adopting an isotope dilution high-resolution gas chromatography-high-resolution mass spectrometer to obtain a determination result of the content of the chlorodioxin in the environmental sample; wherein, the measurement parameters of the isotope dilution high-resolution gas chromatography-high-resolution mass spectrometer are as follows:
the gas chromatography conditions comprise that the sample injection mode is non-shunting sample injection 1 μ l, the sample injection port temperature is 260 deg.C, the carrier gas flow rate is 1.0ml/min, the gas interface temperature is 270 deg.C, the chromatographic column is SP-2331(60m × 0.32mm × 0.2.2 μm), the initial temperature is 140 deg.C, the temperature is raised to 220 deg.C at the speed of 4 deg.C/min after 2min, the temperature is raised to 260 deg.C at the speed of 3 deg.C/min after 1min, the time is 25 min;
the mass spectrum conditions are as follows: the interface temperature of the color matter is 300 ℃, the ion source temperature is 260 ℃, the collision energy of the EI source is 70eV, and the selection is adoptedIon Selection (SIM) mode pair [ M]+、[M+2]+And [ M +4 ]]+And monitoring the characteristic ions.
In embodiment 1 of the present invention, the silver ion-modified amino silica gel is prepared by the following method:
(1) preparation of amino silica gel comprises soaking silica gel in 0.1 mol/L hydrochloric acid solution for 12 hr, washing with distilled water to remove Cl-Then activating for 2 hours at the temperature of 110 ℃ for later use, mixing 3-aminopropyltriethoxysilane and toluene, adding activated silica gel, refluxing and stirring for reaction for 8 hours at the temperature of 70 ℃, filtering, extracting toluene and drying to obtain amino silica gel for later use, wherein the mass ratio of the volume of the 3-aminopropyltriethoxysilane to the silica gel is 3:1(m L/g), the mass ratio of the volume of the hydrochloric acid solution to the silica gel is 3:1(m L/g), and the mass ratio of the volume of the toluene to the silica gel is 4:1(m L/g);
(2) the preparation method of the silver ion modified amino silica gel comprises the steps of mixing the aminosilane and absolute ethyl alcohol (wherein the mass ratio of the aminosilane to the absolute ethyl alcohol is 1:6.25(g/m L)), stirring at normal temperature for 30min, adding a mixed solution of silver nitrate and the absolute ethyl alcohol (wherein the mass ratio of the silver nitrate to the absolute ethyl alcohol is 1:12.5(g/m L)), stirring continuously at normal temperature and in the dark for 24h, filtering by using a Buchner funnel to remove the absolute ethyl alcohol, activating at 90 ℃ for 4h, quickly filling the activated silver ion modified amino silica gel into a brown bottle, and storing in a dryer for later use, wherein the mass ratio of the amino silica gel to the silver nitrate is 10:1 (g/g).
The results of the measurement method of example 1 of the present invention applied to the measurement of the deposit sample are shown in Table 1. By adopting the pretreatment method, the recovery rate of the dioxin isotope internal standard is between 78 and 104 percent of the sediment, and is completely within the recovery rate range specified by the HJ77.4-2008 standard.
Table 1 results of measuring dioxin content in sediment samples
Example 2
In order to further illustrate the beneficial effects of the method, 10g of standard sediment sample (product number EDF-5184, purchased from Cambridge Isotope L laboratories, Inc) is weighed, the dioxin content in the standard sample is detected according to the steps (1) to (4) of the embodiment 1 of the invention, the detection result is shown in Table 2, the method for pretreating the soil or sediment sample and the method for detecting the dioxin provided by the invention can be used for detecting the dioxin content in the sediment sample with higher dioxin concentration, the detection range is large, and the average recovery rate of Isotope labeled dioxin internal standard in the sediment sample is between 86% and 97%, and is completely within the recovery rate range specified by the HJ77.4-2008 standard.
Table 2 results of measurement of dioxin content in sediment sample
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. A rapid pretreatment method for sediment is characterized by comprising the following steps:
(1) will be provided with13Adding a C-PCDD/Fs internal standard into a sediment sample, and extracting the sediment sample by adopting an ultrasonic extraction method to obtain an extracting solution containing dioxin;
(2) concentrating the extracting solution obtained in the step (1), and purifying by using a multilayer silica gel column to obtain a purified solution, wherein the multilayer silica gel column comprises the following components from bottom to top: 1-3 cm of column height of glass fiber, 3-6 g of neutral silica gel, 5-10 g of 40% sodium hydroxide silica gel, 3-6 g of neutral silica gel, 30-40 g of 40% sulfuric acid silica gel, 3-6 g of neutral silica gel, 3-7 g of silver ion modified amino silica gel and 15-25 g of anhydrous concentrated sodium sulfate;
(3) blowing and concentrating the purified liquid nitrogen obtained in the step (2) to obtain a purified sample for instrument analysis;
in the step (2), the silver ion modified amino silica gel is prepared by the following method:
mixing a mixed solution of amino silica gel and absolute ethyl alcohol with a mixed solution of silver nitrate and absolute ethyl alcohol, continuously stirring for 20-28 h under normal temperature and dark conditions, filtering to remove a solvent, and activating for 1-4 h at 90-120 ℃ to obtain silver ion modified amino silica gel, wherein the ratio of the mass of the amino silica gel to the volume of the absolute ethyl alcohol in the mixed solution of the amino silica gel and the absolute ethyl alcohol is 1: 5-10 g/m L, the ratio of the mass of the silver nitrate to the volume of the absolute ethyl alcohol in the mixed solution of the silver nitrate and the ethyl alcohol is 1: 10-20 g/m L, and the mass ratio of the amino silica gel to the silver nitrate is 5-15: 1 g/g;
the amino silica gel is prepared by the following method:
soaking silica gel in a hydrochloric acid solution for 10-14 hours, washing with distilled water to remove chloride ions, activating at 90-120 ℃ for 1-4 hours, mixing 3-aminopropyltriethoxysilane with toluene, adding activated silica gel, refluxing and stirring at 50-90 ℃ for reaction for 6-10 hours, filtering, extracting with toluene, and drying to obtain the amino silica gel, wherein the mass ratio of the volume of the 3-aminopropyltriethoxysilane to the silica gel is 1-4: 1m L/g.
2. The method for rapidly pretreating sediment according to claim 1, wherein in the step (1), the sediment sample is prepared by freeze-drying the collected sediment to a constant weight, mixing the sediment with anhydrous sodium sulfate, and then grinding to remove water, wherein the mass ratio of the sediment to the anhydrous sodium sulfate is 0.5-2: 1 g/g.
3. The method for rapidly pretreating sediments according to claim 1, wherein in the step (1), the step of extracting sediments by adopting an ultrasonic extraction method comprises the following steps:
extracting the sediments by using an ultrasonic cleaning pool to obtain an extracting solution, wherein the operating parameters of the ultrasonic cleaning pool are as follows: the ultrasonic power is 400-600W, the temperature is 70-100 ℃, the time is 10-45 min, and the reagent comprises one or more of hydrochloric acid, petroleum ether, acetone, dimethyl sulfoxide, toluene, n-hexane and dichloromethane.
4. The method for rapidly pretreating sediments according to claim 3, wherein in the step (1), the operation parameters of the ultrasonic cleaning pool are that the ultrasonic power is 500W, the temperature is 90 ℃, the time is 30min, the reagent is a mixed solution of petroleum ether and hydrochloric acid solution, the volume ratio of the petroleum ether to the hydrochloric acid solution is 1-8: 1m L/m L, and the concentration of hydrochloric acid in the hydrochloric acid solution is 0.1-4 mol/L.
5. The method for rapid pretreatment of sediment according to claim 1, wherein in the step (2), the multi-layer silica gel column comprises the following components from bottom to top: glass fiber with the height of 2cm column, neutral silica gel 5g, 40% sodium hydroxide silica gel 8g, neutral silica gel 5g, 40% sulfuric acid silica gel 35g, neutral silica gel 5g, silver ion modified amino silica gel 5g, anhydrous concentrated sodium sulfate 20 g.
6. The method for rapidly pretreating sediments according to claim 1, wherein the step (2) comprises the following steps of concentrating the extract obtained in the step (1), and purifying the concentrate by a multi-layer silica gel column to obtain a purified solution:
soaking a multilayer silica gel column with a first leacheate, driving out bubbles in the multilayer silica gel column with an air pump, and pre-leaching the multilayer silica gel column with the first leacheate.
7. The method for rapidly pretreating sediments according to claim 1, wherein in the step (2), the step of concentrating the extracting solution obtained in the step (1) and then purifying the concentrated extracting solution by a multi-layer silica gel column to obtain the purified solution specifically comprises the following steps:
concentrating the extracting solution obtained in the step (1), transferring the extracting solution to the multilayer silica gel column, and standing for 10-20 min; performing first leaching by using a second leaching solution, and performing second leaching by using a third leaching solution to obtain a purified solution, wherein the second leaching solution and the third leaching solution are the same or different organic solvents; the organic solvent comprises one or more of toluene, n-hexane, cyclohexane and dichloromethane.
8. A method for measuring the content of dioxin in sediment is characterized by comprising the following steps:
taking a purified sample obtained by the rapid pretreatment method of the sediment according to any one of claims 1 to 7, and performing instrument analysis and determination on the purified sample by using an isotope dilution high-resolution gas chromatography-high-resolution mass spectrometer to obtain a determination result of the content of dioxin in the sediment; the parameters of the method adopted are as follows:
the gas chromatography conditions comprise that the sample injection mode is non-shunting sample injection 1 μ l, the sample injection port temperature is 260 ℃, the carrier gas flow rate is 1.0ml/min, the gas interface temperature is 270 ℃, the chromatographic column is SP-233160m × 0.32mm × 0.2.2 μm, the initial temperature is 140 ℃, the temperature is increased to 220 ℃ at the speed of 4 ℃/min after the initial temperature is maintained for 2min, the temperature is increased to 260 ℃ at the speed of 3 ℃/min after the initial temperature is maintained for 1min, and the initial temperature is maintained for 25 min;
the mass spectrum conditions are as follows: the interface temperature of the chromaticness is 300 ℃, the ion source temperature is 260 ℃, the collision energy of EI source is 70eV, and the ion SIM mode is selected to couple M]+、[M+2]+And [ M +4 ]]+And monitoring the characteristic ions.
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| CN104487840A (en) * | 2013-05-27 | 2015-04-01 | 三浦工业株式会社 | Fractionation method for dioxins |
| CN104458925A (en) * | 2013-09-16 | 2015-03-25 | 中国科学院大连化学物理研究所 | Detection method for -2,3,4,7,8-PeCDF in incinerator fly ash and flue gas |
| CN103962091A (en) * | 2013-11-28 | 2014-08-06 | 大连工业大学 | Method for separating EPA (eicosapentaenoic acid) and DHA (docosahexaenoic acid) by using silver ion modified amino silica gel |
| CN104749287A (en) * | 2015-04-14 | 2015-07-01 | 中持依迪亚（北京）环境检测分析股份有限公司 | Determination method for bromo-dioxin in environment sample |
| CN105974001A (en) * | 2016-04-21 | 2016-09-28 | 广州普诺环境检测技术服务有限公司 | Method for pretreating soil or sediment sample and method for determining dioxin |
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