CN115963213A - Method for purifying and separating dioxin, polychlorinated biphenyl and polybrominated diphenyl ether in environmental medium - Google Patents
Method for purifying and separating dioxin, polychlorinated biphenyl and polybrominated diphenyl ether in environmental medium Download PDFInfo
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- 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
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a method for purifying and separating dioxin, polychlorinated biphenyl and polybrominated diphenyl ether in an environmental medium, which comprises the following steps: preparing an environment sample solution to be purified and separated after pre-impurity removal; purifying and separating the obtained environmental sample solution into two groups of organic pollutants by using an A-B acid-base combined separation column which is used in a vertical combination manner, wherein the first group is polychlorinated biphenyl and polybrominated diphenyl ether, and the second group is dioxins; an A column in the A-B acid-base combined separation column is an acidic purification column, and glass fiber, sulfuric acid silica gel and anhydrous sodium sulfate are sequentially filled from bottom to top; the column B is an alkaline separation column, and is sequentially filled with glass fiber, florisil magnesium silicate, alkaline alumina and alkaline silica gel from bottom to top; the first group is eluted by mixed solvent of n-hexane and n-hexane-dichloromethane respectively; the second group was eluted with dichloromethane and separated by column B. The method can simultaneously purify and separate polychlorinated biphenyl, polybrominated diphenyl ethers and dioxins, and the obtained sample can meet the sample solution requirement of HRGC-HRMS determination.
Description
Technical Field
The invention belongs to the field of detection of environmental organic pollutants, and particularly relates to a method for purifying and separating dioxin, polychlorinated biphenyl and polybrominated diphenyl ether in an environmental medium.
Background
Dioxins, polychlorinated biphenyls and polybrominated diphenyl ethers all have high toxicity, persistence, bioaccumulation and long-range mobility, and are blacklists of Persistent Organic Pollutants (POPs) which are listed in the stockholm convention. The three types of POPs have similar structures, coexist in typical pollution sources such as a household garbage incinerator and electronic garbage recovery, widely exist in an environmental medium, belong to a trace content level, are unintentionally generated persistent organic pollutants (UP-POPs) with high attention at present, and belong to important monitoring objects in environmental medium pollutants.
However, due to the characteristics of similar structures and similar mass numbers of UP-POPs such as dioxins, polychlorinated biphenyls and polybrominated diphenyl ethers, mutual interference often occurs during HRGC-HRMS analysis, and particularly, polychlorinated biphenyls and polybrominated diphenyl ethers are interference items during analysis of dioxins, and thus purification, separation and separate collection of dioxins are required for detection. As reported in the existing document, "research on a method for simultaneously measuring polychlorinated biphenyl, and dioxin in a soil sample", a multi-layer silica gel column is adopted for separation, a mixture of polychlorinated biphenyl and dioxin and polybrominated biphenyl ether are collected respectively, a florisil silica column is adopted for separation of the polychlorinated biphenyl and dioxin mixture, a polychlorinated biphenyl compound is collected, and an activated carbon silica gel column is adopted for adsorption and elution to collect dioxin, so that the separation of the polychlorinated biphenyl, the polychlorinated biphenyl and the dioxin is realized.
Although the prior patent CN103645086A "pretreatment method for simultaneously purifying multiple types of persistent organic pollutants in environmental medium" can separate three types of POPs, namely dioxins, polychlorinated biphenyls and organochlorine pesticides in environmental medium extract liquid at one time, the three types of POPs all belong to chloro POPs, and the pretreatment method is not suitable for brominated diphenyl ethers with larger molecular mass span and unstable physicochemical properties. In addition, polychlorinated biphenyls generally comprise monomers from monochloro to decachloro, the polarity of each monomer is different, and elution is carried out by using an eluent, and only part of polychlorinated biphenyls can be eluted generally; brominated diphenyl ethers generally comprise monobrominated to decabrominated monomers, and the distribution of the brominated diphenyl ethers in different environmental samples is different, for example, high brominated PBDEs are most abundant in soil, and low brominated PBDEs are higher in water. Therefore, a pretreatment method which is suitable for various environment media and can simultaneously purify and separate dioxins, polychlorinated biphenyl and polybrominated diphenyl ethers is researched, and the three types of UP-POPs in the environment media are favorably monitored.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a method for purifying and separating dioxin, polychlorinated biphenyl and polybrominated diphenyl ether in an environmental medium, and aims to provide an A-B acid-base combined separation column which is used in a vertical combination manner, wherein the A column is an acid purification column and is sequentially filled with glass fiber, sulfuric acid silica gel and anhydrous sodium sulfate from bottom to top; the column B is an alkaline separation column, and glass fiber, florisil magnesium silicate, alkaline alumina and alkaline silica gel are sequentially filled from bottom to top; the A-B acid-base combined separation column has different adsorption capacities on dioxin, polychlorinated biphenyl and polybrominated diphenyl ether, can enable the polychlorinated biphenyl and the polybrominated diphenyl ether in an environmental sample to be mainly adsorbed in the A column, and the dioxin is mainly adsorbed in the B column and then is respectively eluted and collected, so that the aim of simultaneously purifying and separating the dioxin, the polychlorinated biphenyl and the polybrominated diphenyl ether in environmental medium extraction liquid is fulfilled, and the technical problem that three types of POPs (persistent organic pollutants) such as the dioxin, the polychlorinated biphenyl and the polybrominated diphenyl ether in the environmental medium extraction liquid are difficult to simultaneously purify and separate in the existing method is solved.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a method for purifying and separating dioxin, polychlorinated biphenyl, and polybrominated diphenyl ether in an environmental medium, comprising the steps of:
preparing an environment sample solution to be purified and separated after pre-impurity removal;
purifying and separating the obtained environmental sample solution into two groups of organic pollutants by using an A-B acid-base combined separation column which is used in a vertical combination manner, wherein the first group is polychlorinated biphenyl and polybrominated diphenyl ether, and the second group is dioxins;
an A column in the A-B acid-base combined separation column is an acidic purification column, and glass fiber, sulfuric acid silica gel and anhydrous sodium sulfate are sequentially filled from bottom to top; the column B is an alkaline separation column, and is sequentially filled with glass fiber, florisil magnesium silicate, alkaline alumina and alkaline silica gel from bottom to top;
the first group of organic pollutants are respectively eluted by using a mixed solvent of n-hexane and n-hexane-dichloromethane;
and eluting the second group of organic pollutants by using dichloromethane, and separating by using a B column.
Preferably, in the method for purifying and separating dioxin, polychlorinated biphenyl and polybrominated diphenyl ether in the environmental medium, the sulfuric acid content in the silica gel sulfate in the A column is 30-40%, and the filling amount of the florisil silicate in the B column is 0.6-2 g.
Preferably, in the method for purifying and separating dioxin, polychlorinated biphenyl and polybrominated diphenyl ether in the environmental medium, the column A is filled with glass fiber, 6-10 cm of sulfuric acid silica gel and 1cm of anhydrous sodium sulfate from bottom to top in sequence.
Preferably, in the method for purifying and separating dioxin, polychlorinated biphenyl and polybrominated diphenyl ether in the environmental medium, the B column is filled with glass fiber, 0.6 to 2g of florisil silicate, 1 to 3g of alkaline alumina and 1 to 3g of alkaline silica gel from bottom to top in sequence.
Preferably, in the method for purifying and separating dioxin, polychlorinated biphenyl and polybrominated diphenyl ethers in the environmental medium, when the first group of organic pollutants are eluted, the acid-base combined separation column A-B is eluted by using n-hexane, after elution, the column A is removed, the column B is eluted by using a mixed solvent of n-hexane and dichloromethane, and the mixture of the first group of polychlorinated biphenyl and polybrominated diphenyl ethers is collected.
Preferably, in the method for purifying and separating dioxin, polychlorinated biphenyl and polybrominated diphenyl ether in the environment medium, the n-hexane-dichloromethane mixed solvent is prepared according to the volume ratio of dichloromethane less than or equal to 5%, and the dosage of the n-hexane-dichloromethane mixed solvent is 10-20 ml when a B column is eluted.
Preferably, in the method for purifying and separating dioxin, polychlorinated biphenyl and polybrominated diphenyl ether in the environment medium, after the first group of organic pollutants are collected, a B column is eluted by adopting dichloromethane, and the second group of organic pollutants, dioxin is collected.
Preferably, in the method for purifying and separating dioxin, polychlorinated biphenyl and polybrominated diphenyl ether in the environment medium, the dosage of dichloromethane is 40-60 ml when dioxin organic pollutants are eluted.
Preferably, in the method for purifying and separating dioxin, polychlorinated biphenyl and polybrominated diphenyl ether in the environmental medium, the n-hexane sample solution is obtained as follows:
and (3) adding the environment medium extraction liquid concentrated to be nearly dry according to the volume ratio of normal hexane to concentrated sulfuric acid of less than or equal to 7.
Preferably, the method for purifying and separating dioxin, polychlorinated biphenyl and polybrominated diphenyl ether in the environment medium comprises any one of ambient air, flue waste gas, soil, sediment, raw water, waste water and solid waste samples.
In general, compared with the prior art, the above technical solutions conceived by the present invention can achieve the following beneficial effects:
the method for purifying and separating dioxin, polychlorinated biphenyl and polybrominated diphenyl ethers in an environmental medium adopts an A-B acid-base combined separation column for purification and separation, wherein the A column is an acidic purification column, and is filled with glass fiber, sulfuric acid silica gel and anhydrous sodium sulfate from bottom to top in sequence, so that the polychlorinated biphenyl and the polybrominated diphenyl ethers have large adsorption effect; the column B is an alkaline separation column, glass fiber, florisil magnesium silicate, alkaline alumina and alkaline silica gel are sequentially filled from bottom to top, the adsorption effect on dioxin is large, dioxin, polychlorinated biphenyl and polybrominated diphenyl ether in an environment medium can be adsorbed in different separation columns, then two groups of elution samples are obtained through elution and separation, the first group is a mixture of the polychlorinated biphenyl and the polybrominated diphenyl ether, the second group is dioxin, and the elution samples can meet the sample solution requirement of high-resolution gas chromatography-high-resolution mass spectrometry determination. The method can separate three types of UP-POPs (UP-POPs) of dioxin, polychlorinated biphenyl and polybrominated diphenyl ether into two groups of organic pollutants, wherein the dioxin is separately collected, and the polychlorinated biphenyl, the polybrominated diphenyl ether and the dioxin in the environment medium extraction liquid can be purified and effectively separated simultaneously.
In addition, compared with the existing domestic and foreign standard analysis and test method, the polychlorinated biphenyl, polybrominated diphenyl ether and dioxin in the existing method respectively adopt different pretreatment methods, toluene is generally used for eluting dioxin compounds, and the materials and organic reagents are repeatedly used, so that serious waste and secondary pollution are caused.
Drawings
FIG. 1 is a schematic diagram of the composition and structure of an A-B acid-base combination separation column of example 1;
FIG. 2 is a schematic diagram of a purification and separation technique route of polychlorinated biphenyl, polybrominated diphenyl ethers and dioxin in an environmental medium in example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Although UP-POPs of dioxins, polychlorinated biphenyls and polybrominated diphenyl ethers have similar structures and similar mass numbers, and can affect each other during detection, experiments show that when HRGC-HRMS is used for detecting and analyzing polychlorinated biphenyls and polybrominated diphenyl ethers, the mass number difference is large, so that mutual interference can be reduced or avoided, joint detection can be realized, but dioxins need to be collected separately for detection.
Through the improvement of the separation column, the research discovers that a self-made UP-down combined A-B acid-base separation column is adopted, when the A column is an acid column, glass fiber, sulfuric acid silica gel and anhydrous sodium sulfate are sequentially filled from bottom to top, the residual interfering substances after the sulfuric acid treatment can be effectively removed, and three UP-POPs (UP-POPs) including dioxins, polychlorinated biphenyl and polybrominated diphenyl ethers are further purified; the column B is an alkaline column, glass fiber, florisil, alkaline alumina and alkaline silica gel are sequentially filled from bottom to top, the adsorption effect on dioxin compounds is large, the adsorption on polychlorinated biphenyl and polybrominated diphenyl ether is small, three types of UP-POPs can be distributed in different columns, the dioxin, the polychlorinated biphenyl and the polybrominated diphenyl ether in an environmental medium can be simultaneously separated through elution of solvents with different polarity levels, the three types of UP-POPs are separated into two groups of pollutants, wherein the first group is the polychlorinated biphenyl and the polybrominated diphenyl ether, and the second group is the dioxin.
Wherein, the sulfuric acid content in the sulfuric acid silica gel in the column A is 30-40%, so that the simultaneous purification of dioxin, polychlorinated biphenyl and polybrominated diphenyl ether can be further completed, and residual matrix interfering substances after the sulfuric acid treatment step and a small amount of sulfuric acid solution in the sample solution are removed; the column B is an alkaline column, so that acidic substances in a sample solution can be further removed, the damage of the acidic substances to the column B is reduced or avoided, and the column B is favorable for further realizing the adsorption and separation of dioxins, polychlorinated biphenyl and polybrominated diphenyl ethers.
Particularly, the column A is filled with glass fiber, 6-10 cm of sulfuric acid silica gel and 1cm of anhydrous sodium sulfate from bottom to top in sequence; the column B is filled with glass fiber, 0.6 to 2g of Froris magnesium silicate, 1 to 3g of alkaline alumina and 1 to 3g of alkaline silica gel from bottom to top in sequence; when the device is used, the lower end of the A column is connected with the upper end opening of the B column to form an A-B acid-base combined separation column, and is eluted by the A-B acid-base combined separation column, because dioxins can be well adsorbed in the Frori magnesium silicate of the B column, polychlorinated biphenyl and polybrominated diphenyl ether are preferentially eluted after short-time adsorption, so that a good purification and separation effect is achieved, and in view of the fact that polychlorinated biphenyl and polybrominated diphenyl ether cannot interfere with each other when HRGC-HRMS is adopted for detection and analysis, the polychlorinated biphenyl and polybrominated diphenyl ether mixed components and dioxin components can be respectively eluted and collected by adopting corresponding eluents.
Furthermore, n-hexane is firstly adopted to elute most polychlorinated biphenyl and polybrominated diphenyl ether in the A-B column, after the A column is removed, n-hexane-dichloromethane with larger polarity is adopted to elute a small amount of polychlorinated biphenyl and polybrominated diphenyl ether in the B column, so that more monomers can be obtained and dioxin substances can not be eluted; preferably, the volume ratio of the dichloromethane in the n-hexane-dichloromethane is less than or equal to 5 percent, and the dosage is 10 to 20ml.
The invention provides a method for purifying and separating dioxin, polychlorinated biphenyl and polybrominated diphenyl ether in an environmental medium, which specifically comprises the following steps:
(1) Pre-impurity removal treatment: concentrating the environmental sample extract to near dryness, redissolving, pre-removing impurities, and collecting the environmental sample solution to be purified and separated;
in some embodiments, n-hexane is adopted for re-dissolving, concentrated sulfuric acid is added for washing and impurity removal, and the upper-layer n-hexane sample solution is collected after standing or centrifugal layering, namely the environment sample solution to be purified and separated;
wherein the normal hexane and the concentrated sulfuric acid are added according to the volume ratio of less than or equal to 7; adding n-hexane repeatedly for multiple times to wash the sulfuric acid layer, and collecting an n-hexane phase, namely a sample to be purified and separated; preferably, adding n-hexane and concentrated sulfuric acid for 3 times, washing and removing impurities, fully sulfonating, and collecting an upper-layer n-hexane phase;
when the environmental medium extraction liquid is concentrated to be nearly dry, n-hexane is used for redissolving, concentrated sulfuric acid is used for removing impurities, and the environmental medium extraction liquid is pretreated by the concentrated sulfuric acid, compared with a chromatographic column, sulfuric acid can react with the impurities to be thoroughly removed, the impurity removal effect is better, but the target object is damaged due to the reaction easily caused by overhigh sulfuric acid content, and the detection result is lower; too low a sulfuric acid content makes it difficult to remove the basic impurities well. Experiments show that when the volume ratio of n-hexane to concentrated sulfuric acid is less than or equal to 7, the sulfonation reaction of sulfuric acid can be sufficiently completed by matching vortex oscillation, and most matrix interference substances including pigments, proteins, grease, fatty acids, aromatic hydrocarbon organic matters and various polar substances in sample extraction liquid are removed. The normal hexane solution after the sulfuric acid treatment is clear and has no obvious impurities.
(2) Purifying and separating by an A-B acid-base combined separation column: purifying and separating the obtained n-hexane sample solution into two groups of organic pollutants by utilizing an A-B acid-base combined separation column which is used in a vertical combination manner, wherein the first group is polychlorinated biphenyl and polybrominated diphenyl ether, and the second group is dioxins;
an A column in the A-B acid-base combined separation column is an acidic purification column, and glass fiber, sulfuric acid silica gel and anhydrous sodium sulfate are sequentially filled from bottom to top; the column B is an alkaline separation column, and is sequentially filled with glass fiber, florisil magnesium silicate, alkaline alumina and alkaline silica gel from bottom to top;
the first group of organic pollutants are respectively eluted by using a mixed solvent of n-hexane and n-hexane-dichloromethane; and eluting the second group of organic pollutants by using dichloromethane, and separating by using a B column.
The lower end of an A column in the A-B acid-base combined separation column is connected with an opening at the upper end of a B column, so that effluent liquid of the A column completely flows into the B column and flows out from the lower end of the B column; wherein the A column is an acid purification column which is a glass column and is filled with glass fiber, sulfuric acid silica gel and anhydrous sodium sulfate from bottom to top in sequence; the sulfuric acid content in the sulfuric acid silica gel is 30-40%, namely the ratio of sulfuric acid to neutral silica gel is more than 3, but not more than 4; the sulfuric acid silica gel is used for treating residual matrix interfering substances after concentrated sulfuric acid pretreatment and a small amount of concentrated sulfuric acid solution in the sample solution, and the generated sulfonation effect can perform destructive impurity removal. In addition, the acidic column can slow down the impact of acidic substances in the sample on the alkaline column, and the separation effect of the alkaline column is prevented from being reduced or damaged.
The column B is an alkaline separation column, the inner diameter of the column B is the same as that of the column A, the column B is a glass column, and glass fiber, 0.6 g-2 g of florisil magnesium silicate, alkaline alumina and alkaline silica gel are sequentially filled from bottom to top.
Because the adsorption capacity of the florisil magnesium silicate on dioxins is obviously greater than that of polychlorinated biphenyl and polybrominated diphenyl ether, the florisil compounds can be adsorbed in the column B, and then the dioxins, the polychlorinated biphenyl and the polybrominated diphenyl ether are eluted and separated.
Preferably, the column A has an inner diameter of 10mm, and is sequentially filled with glass fiber, 6-10 cm of 40% sulfuric acid silica gel and 1cm of anhydrous sodium sulfate from bottom to top
More preferably, the inner diameter of the column A is 10mm, and the column A is sequentially filled with glass fiber, 8cm of 40% sulfuric acid silica gel and 1cm of anhydrous sodium sulfate from bottom to top; on the premise of ensuring the purification effect, the dosage of the reagent is small, which is beneficial to saving the cost;
preferably, the inner diameter of the column B is 10mm, and the column B is sequentially filled with glass fiber, 0.6 to 2g of florisil magnesium silicate, 1 to 3g of alkaline alumina and 1 to 3g of alkaline silica gel from bottom to top;
more preferably, the column B has an inner diameter of 10mm and is filled with glass fiber, 1g of florisil magnesium silicate, 1g of alkaline alumina and 2g of alkaline silica gel in this order from bottom to top; the florisil magnesium silicate, the alkaline alumina and the alkaline silica gel have small using amount on the premise of ensuring the separation effect, and are favorable for saving the cost.
More preferably, after eluting the acid-base combined separation column A-B with n-hexane, removing the column A, eluting the column B with a mixed solvent of n-hexane and dichloromethane, and collecting the column B in a sample bottle A, wherein the component A in the sample bottle A is purified polychlorinated biphenyl and polybrominated diphenyl ether; the acid-base combined separation column A-B is leached by the n-hexane, and the optimal dosage is 7ml; the volume ratio of the dichloromethane of the n-hexane-dichloromethane mixed solvent is less than or equal to 5%, the dosage is 10-20 ml, in some embodiments, the volume ratio of the n-hexane to the dichloromethane is 95;
after the first group of polychlorinated biphenyl and polybrominated diphenyl ether is collected, eluting a column B by adopting dichloromethane, and collecting the column B in a sample bottle B, wherein the component B in the sample bottle B is a purified dioxin substance, the amount of dichloromethane used for elution is 40-60 ml, and in some embodiments, the amount of dichloromethane used for elution is 50ml.
The dioxin-like substances in the column B are eluted after the column A is removed, so that the elution reagent and the elution time are saved when the dioxin-like substances are completely eluted, and the phenomenon that other adsorbed interference substances in the column A are eluted again by dichloromethane eluting solution with high polarity and collected in the sample bottle B to cause interference is avoided.
The following are examples:
EXAMPLE 1 preparation of A-B acid-base Combined separation column and purification separation thereof
(1) Preparation of chromatography packing
(1) Neutral silica gel: 70-230 mesh, available from Merck (Darmstadt, germany). Baking at 550 deg.C for more than 8 hr before use, cooling in a drier, sealing, and storing.
(2) Sulfuric acid silica gel: 120g of dried neutral silica gel is weighed in a glass flask, 80g of concentrated sulfuric acid is added, a plug is added, the mixture is shaken until the silica gel is in a uniform flowing state, and the mixture is sealed and stored.
(3) Basic silica gel: 67g of dried neutral silica gel was weighed in a glass flask, 33g of 1mol/L sodium hydroxide solution was added, the flask was stoppered and shaken until the silica gel became a uniform flow state, and the flask was sealed and stored.
(4) Basic alumina: 150 mesh, available from Aldrich (Milwaukee, USA) with an activity grade of Brockman I. Baking at 550 deg.C for more than 8 hr, cooling in a drier, adding 3g pure water per 97g alkaline alumina, mixing, sealing, and storing.
(5) Flory silica magnesium: 60-100 mesh, available from Merck (Darmstadt, germany). Baking at 550 deg.C for more than 12 hr before use, cooling in a drier, sealing, and storing.
(6) Anhydrous sodium sulfate: the super pure was purchased from Guangzhou reagent factory. Baking at 450 deg.C for more than 4 hr before use, cooling in a drier, sealing, and storing.
(7) Silanized glass fiber: purchased from Shanghai' an spectral laboratory science and technology, inc. Baking at 450 deg.C for more than 4 hr before use, cooling in a drier, sealing, and storing.
(2) Sulfuric acid treatment of environmental medium extract
And (3) concentrating 150-300 ml of the environmental matrix sample extract under reduced pressure until the environmental matrix sample extract is nearly dry, re-dissolving the sample solution by using 7ml of n-hexane, and transferring the re-dissolved sample solution into a 40ml sample bottle. Accurately measuring 8ml of concentrated sulfuric acid, adding the concentrated sulfuric acid into a sample bottle, screwing a bottle cap, oscillating the concentrated sulfuric acid by using a vortex instrument for about 10 seconds, carefully opening the bottle cap, discharging heat generated by the reaction of the sulfuric acid, repeatedly oscillating the concentrated sulfuric acid for 2 to 3 times, and standing the concentrated sulfuric acid for about 30 minutes. The n-hexane layer was removed with a dropper and transferred to a clean sample bottle. Adding 7ml of n-hexane into the original sulfuric acid treatment sample bottle, repeating the steps for 2 times, and combining the n-hexane sample solution.
(3) Preparation of A-B acid-base combined separation column
Preparing a glass chromatographic column with the inner diameter of 10mm and the column height of 250mm and a lower closing-in part, sequentially filling a small amount of silanized glass fiber, 8cm of silica sulfate and 1cm of anhydrous sodium sulfate from bottom to top, and filling the column A;
a glass chromatography column with an inner diameter of 10mm and a column height of 250mm and a lower closed end is prepared, and a small amount of silanized glass fiber, 1g of florisil magnesium silicate, 1g of alkaline alumina and 2g of alkaline silica gel are filled in the column from bottom to top to fill the column B. And (3) connecting the column A and the column B in series, enabling the column A to be located above the column B, preparing an A-B acid-base combined separation column, and pre-washing the A-B acid-base combined separation column by using 20ml of n-hexane after the completion as shown in figure 1.
(4) Sucking the normal hexane sample solution treated by sulfuric acid by using a dropper, transferring the normal hexane sample solution to a column A, collecting all the sample solution in a sample bottle A after the sample solution passes through an A-B acid-base combined separation column, adding 7ml of normal hexane after the sample solution on the column is nearly dry, and continuously collecting the sample solution in the sample bottle A;
and after elution, removing the upper column A, reserving the column B, adding 15ml of a mixed solvent of n-hexane and dichloromethane with the volume ratio of 95 to elute the column B, continuously collecting the column B in a sample bottle A, and collecting a sample solution containing pure polychlorinated biphenyl and polybrominated diphenyl ether in the sample bottle A through detection.
(5) And after the sample bottle A is collected, adding 50ml of dichloromethane to the upper end of the column B for leaching, collecting effluent liquid passing through the column B into the sample bottle B, and collecting pure sample solution of dioxins in the sample bottle B through detection.
Example 2 purification and separation of dioxins, polychlorinated biphenyls, polybrominated diphenyl ethers from ambient air, sediment and solid waste extracts
In this embodiment, the environmental air, the sediments and the solid waste are taken as examples, the purification and separation method provided by the present invention is adopted to purify and separate dioxins, polychlorinated biphenyls and polybrominated diphenyl ethers in the environmental matrix (the environmental air, the sediments and the solid waste) extraction liquid, the sample injection internal standard is respectively added to the final concentrated solution, the high resolution gas chromatography-high resolution double focusing magnetic mass spectrometer (HP 6890N GC/Autospec Premier, waters, USA) is used for instrument analysis, and the isotope dilution internal standard method is used for qualitative and quantitative determination, and the specific technical route is shown in fig. 2.
(1) Blank matrix labeling sample
Respectively preparing 3 blank matrixes for each environment matrix, wherein the blank matrixes of the environment air are a filter membrane and a PUF (physical unclonable function) for sampling; the sediment and the solid waste gas adopt quartz sand. Adding a certain amount of mixed standard solution of dioxins, polychlorinated biphenyls and polybrominated diphenyl ethers into a blank matrix, and adding a certain amount of isotope extraction internal standards of dioxins, polychlorinated biphenyls and polybrominated diphenyl ethers before extraction. After extraction is finished, the method is adopted to purify and separate samples, the obtained sample concentrated solution is analyzed by an instrument, and the experimental results are shown in tables 1-4.
As can be seen from tables 1 to 4, when the purification and separation method provided by the invention is adopted for pretreatment, the standard recovery rates of dioxins, polychlorinated biphenyls and polybrominated diphenyl ethers of the blank matrixes meet the requirements of an analysis and determination method, and the effects of synchronously realizing purification and separation are achieved.
(2) Actual sample
2 actual samples were prepared for each environmental substrate. The samples are subjected to Soxhlet extraction by adopting toluene, and a certain amount of isotope extraction internal standards of dioxins, polychlorinated biphenyls and polybrominated diphenyl ethers are respectively added before extraction. After extraction is finished, the method is adopted to purify and separate samples, the obtained sample concentrated solution is analyzed by an instrument, and the experimental results are shown in tables 5-7.
As can be seen from tables 5 to 7, when the purification and separation method provided by the invention is used for pretreatment, the standard recovery rates of various environmental media meet the requirements of the analytical determination method, and the effects of synchronously realizing purification and separation can be achieved.
Note that the sulfur-containing sediment sample was purified after sulfur removal. For some samples containing large molecular interference, monochlorobiphenyl may be interfered when measuring polychlorinated biphenyl, and Gel Permeation Chromatography (GPC) column can be used for further purification treatment.
TABLE 1 result of recovery of dioxins from sediment and solid waste blank matrix in normalized ratio (unit:%)
Remarking: allowable ranges for dioxin recovery are found in EPA Method 1613 and HJ 77.4.
Table 2 environmental air blank matrix dioxins spiking recovery results (unit:%)
Remarking: allowable ranges for dioxin recovery are found in EPA Method 23 and HJ 77.2.
TABLE 3 recovery of polychlorinated biphenyls (PPC) in sediment, ambient air blank matrix results (unit:%)
Remarking: the allowable range of the polychlorinated biphenyl recovery rate is shown in EPAMethod 1668C.
TABLE 4 recovery of polybrominated diphenyl ethers in sediment, ambient air blank matrix (unit:%)
Remarking: the allowable range of polybrominated diphenyl ether recovery is shown in EPA Method 1614.
TABLE 5 determination results of dioxins in sediment and ash deposition sample extraction liquid
TABLE 6 measurement results of polychlorinated biphenyls in samples of sediments, dust and ambient air
TABLE 7 measurement results of polybrominated diphenyl ethers in the extraction of sediment, dust sample and ambient air sample
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for purifying and separating dioxin, polychlorinated biphenyl and polybrominated diphenyl ether in an environmental medium is characterized by comprising the following steps:
preparing an environment sample solution to be purified and separated after pre-impurity removal;
purifying and separating the obtained environmental sample solution into two groups of organic pollutants by using an A-B acid-base combined separation column which is used in an up-down combined manner, wherein the first group is polychlorinated biphenyl and polybrominated diphenyl ether, and the second group is dioxins;
an A column in the A-B acid-base combined separation column is an acidic purification column, and glass fiber, sulfuric acid silica gel and anhydrous sodium sulfate are sequentially filled from bottom to top; the column B is an alkaline separation column, and glass fiber, florisil magnesium silicate, alkaline alumina and alkaline silica gel are sequentially filled from bottom to top;
the first group of organic pollutants are respectively eluted by using a mixed solvent of n-hexane and n-hexane-dichloromethane;
and eluting the second group of organic pollutants by using dichloromethane, and separating by using a B column.
2. The method for purifying and separating dioxin, polychlorinated biphenyl and polybrominated diphenyl ethers in an environmental medium according to claim 1, wherein the sulfuric acid content in the silica gel sulfate in the A column is 30 to 40%, and the filling amount of the Froris magnesium silicate in the B column is 0.6 to 2g.
3. The method for purifying and separating dioxin, polychlorinated biphenyl, and polybrominated diphenyl ethers in an environmental medium according to claim 2, wherein the a column is filled with glass fibers, 8 to 10cm of sulfuric acid silica gel, and 1cm of anhydrous sodium sulfate in this order from bottom to top.
4. The method for purifying and separating dioxin, polychlorinated biphenyl, and polybrominated diphenyl ethers in an environmental medium according to claim 2, wherein the column B is sequentially filled with glass fiber, 0.6g to 2g of florisil silicate, 1g to 3g of alkaline alumina, and 1g to 3g of alkaline silica gel from bottom to top.
5. The method for purifying and separating dioxin, polychlorinated biphenyl and polybrominated diphenyl ethers in environmental media according to any one of claims 1 to 4, wherein the first group of organic pollutants is eluted by eluting the A-B acid-base combined separation column with n-hexane, removing the A column after elution and eluting the B column with a mixed solvent of n-hexane and dichloromethane, and the first group of polychlorinated biphenyl and polybrominated diphenyl ethers is collected.
6. The method for purifying and separating dioxin, polychlorinated biphenyl, and polybrominated diphenyl ethers in environmental media according to claim 5, wherein the n-hexane-dichloromethane mixed solvent is prepared in a volume ratio of dichloromethane of 5% or less, and the amount of the solvent used for eluting the B column is 10 to 20ml.
7. The method for purifying and separating dioxin, polychlorinated biphenyl, and polybrominated diphenyl ethers in environmental media according to claim 5, wherein after the first group of organic pollutants are collected, the dioxin and the dioxin are collected as the second group of organic pollutants by eluting B column with dichloromethane.
8. The method for purifying and separating dioxin, polychlorinated biphenyl, and polybrominated diphenyl ethers in environmental media according to claim 7, wherein the amount of dichloromethane used is 40 to 60ml when eluting dioxin-like organic pollutants.
9. The method for purifying and separating dioxin, polychlorinated biphenyl, and polybrominated diphenyl ethers in environmental media according to any one of claims 1 to 8, wherein the sample solution of the n-hexane sample solution is obtained as follows:
and (3) adding the environment medium extraction liquid concentrated to be nearly dry according to the volume ratio of normal hexane to concentrated sulfuric acid of less than or equal to 7.
10. The method for purifying and separating dioxin, polychlorinated biphenyl, and polybrominated diphenyl ethers in environmental media according to any one of claims 1 to 8, wherein the environmental media include any one of ambient air, flue gas, soil, sediments, raw water, wastewater, and solid waste samples.
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