CN112834669A - High-efficient sample purification and separation column of dioxin suitable for mass spectrometry - Google Patents
High-efficient sample purification and separation column of dioxin suitable for mass spectrometry Download PDFInfo
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- CN112834669A CN112834669A CN202011620967.1A CN202011620967A CN112834669A CN 112834669 A CN112834669 A CN 112834669A CN 202011620967 A CN202011620967 A CN 202011620967A CN 112834669 A CN112834669 A CN 112834669A
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- 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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- G—PHYSICS
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- 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 discloses a high-efficiency dioxin sample purification and separation column suitable for mass spectrometry, which comprises an acid column, a composite column and a carbon column; the filling materials of the acid column from bottom to top are neutral silica gel, 44% of acidic silica gel, 22% of acidic silica gel, neutral silica gel and anhydrous sodium sulfate in sequence; the filler under the composite column is neutral silica gel, alkaline silica gel, neutral silica gel, 22% acidic silica gel, neutral silica gel and anhydrous sodium sulfate in sequence; the filling material of the carbon column from bottom to top is activated carbon powder and anhydrous sodium sulfate in sequence; and the dioxin sample is subjected to purification pretreatment through an acid column, a composite column and a carbon column in sequence to obtain polychlorinated biphenyl and dioxin samples. The pretreatment column combination provided by the invention can meet the pretreatment of dioxin and dioxin-like polychlorinated biphenyl in samples of different types of feeds and livestock and poultry products.
Description
Technical Field
The invention relates to the field of chemical analysis and biological research, in particular to a high-efficiency dioxin sample purification and separation column suitable for mass spectrometry.
Background
The problem of environmental pollution has become a social focus of public and government concern. Persistent Organic Pollutants (POPs) represented by dioxins are particularly spotlighted, and such compounds have the characteristics of persistence, long-distance migration, biological accumulation and the like, are widely distributed in the global range, and are important risks affecting human health.
Dioxin is a compound with strong carcinogenic, teratogenic and mutagenic effects, has strong toxicity (the international center for cancer research ranks the dioxin as human grade I carcinogen), and has the characteristics of difficult degradation and accumulation in organisms. Generally, dioxins refer to polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) related in structure and chemical properties. Certain dioxin-like polychlorinated biphenyls (PCBs) have similar toxicity and are classified under the name of "dioxins". Approximately 419 dioxin-like compounds were identified, of which approximately 30 were considered to be quite toxic to dioxins, with 2,3,7,8-TCDD being the most toxic and typical persistent organic pollutants, ubiquitous in soil, water, atmosphere, and food and feed. In recent years, the problems of hairy crabs polluted by dioxin, native eggs polluted by dioxin and the like which occur domestically make public increasingly pay attention to health risks brought by dioxin.
The isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry is a 'gold standard' for detecting dioxin samples, the pretreatment process of the method comprises sample extraction, purification and concentration, the pretreatment step is complex, the analysis period is long, the requirement on an analyst is high, and the pretreatment effect is related to the accuracy and the sensitivity of dioxin detection data. The purification link is a key step in the pretreatment process and directly influences the pretreatment effect. Common purification modes include manual purification, semi-automatic purification and full-automatic purification, wherein the manual purification mode is still the most widely applied purification mode for pretreatment of dioxin samples in the fields of environment, food and agriculture at present. Aiming at different sample matrixes, different fillers are used for forming, and purifying columns such as an acid silica gel column, a composite silica gel column, a Flori silica column, an activated carbon column and the like are manually prepared so as to improve the purifying effect of the samples.
In the prior art, there are two common pretreatment methods, one is that the sample extract sequentially passes through (1) a mixed silica gel column (from bottom to top, glass wool, neutral silica gel, 33% basic silica gel, neutral silica gel, 44% acidic silica gel, neutral silica gel, anhydrous sodium sulfate), (2) a basic alumina column and (3) an active silica gel column. The volume ratio of the purification column (1) is 97: 3, eluting with a mixed solvent of n-hexane and dichloromethane, and sequentially eluting the column (2) with n-hexane in a volume ratio of 98: eluting with a mixed solvent of n-hexane and dichloromethane, and mixing the solvent with the volume ratio of 1: 1, recovering dioxin from a normal hexane/dichloromethane mixed solvent, leaching the column (3) by using the normal hexane to remove impurities, and mixing the solvent with the volume ratio of 95: and 5, recovering dioxin from the n-hexane/dichloromethane mixed solvent. The method is suitable for detecting environmental samples such as soil and atmospheric dust fall, and has poor effect of removing impurities in more fat samples such as feeds, livestock and poultry products and the like; the separation effect of dioxin polychlorinated biphenyls (PCBs) is not clear.
The other is that the sample extract passes through (1) florisil (1% water) column (2 g anhydrous sodium sulfate, 2g activated florisil (1% water), 2g anhydrous sodium sulfate from bottom to top) and (2) nitrate silica gel column (2 g anhydrous sodium sulfate, 2g silver nitrate silica gel (10%), 2g anhydrous sodium sulfate from bottom to top). The purifying column (1) is eluted by n-hexane and dichloromethane in sequence, and the purifying column (2) is eluted by n-hexane and a volume ratio of 1: 1 n-hexane/dichloromethane. The method is suitable for detecting the environment such as bottom mud, soil, atmosphere, bark and the like and biological samples, and has poor effect of removing impurities in different media such as feeds, livestock and poultry products and the like and samples containing more fat.
Therefore, the development of a purifying and separating column for the pretreatment of dioxin samples in agricultural product matrixes such as feeds, livestock and poultry products and the like, which is suitable for isotope dilution high-resolution gas chromatography-high-resolution mass spectrometry and gas chromatography-tandem mass spectrometry, is urgently needed, and the improvement of the analysis efficiency of the dioxin samples in the agricultural field is facilitated.
Disclosure of Invention
The invention aims to solve the problems, provides a high-efficiency dioxin sample purifying and separating column suitable for mass spectrometry, and is beneficial to improving the analysis efficiency of dioxin samples in the agricultural field.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a high-efficiency dioxin sample purifying and separating column suitable for mass spectrometry comprises an acid column, a composite column and a carbon column; the filling materials of the acid column from bottom to top are neutral silica gel, 44% of acidic silica gel, 22% of acidic silica gel, neutral silica gel and anhydrous sodium sulfate in sequence; the filler under the composite column is neutral silica gel, alkaline silica gel, neutral silica gel, 22% acidic silica gel, neutral silica gel and anhydrous sodium sulfate in sequence; the filling material of the carbon column from bottom to top is activated carbon powder and anhydrous sodium sulfate in sequence; and the dioxin sample is subjected to purification pretreatment through an acid column, a composite column and a carbon column in sequence, and finally polychlorinated biphenyl and dioxin samples are obtained.
As an improvement to the above technical scheme, the neutral silica gel, 44% acidic silica gel, 22% acidic silica gel, neutral silica gel, and anhydrous sodium sulfate in the acid column are respectively 1g, 10g, 2g, 1g, and 2cm high; the neutral silica gel, the alkaline silica gel, the neutral silica gel, the 22% acidic silica gel, the neutral silica gel and the anhydrous sodium sulfate in the composite column are respectively 1g, 4g, 1g, 8g, 1g and 2cm high; the activated carbon powder and the anhydrous sodium sulfate in the carbon column are respectively 1.5g and 2cm high.
As an improvement to the technical scheme, the acid column and the composite column are pre-leached by 70mL of n-hexane, and are eluted by 100mL of n-hexane after sample loading; the carbon column is pre-leached by 10mL of toluene and 10mL of n-hexane in sequence, after the sample is loaded, 50mL of n-hexane is used for eluting polychlorinated biphenyl, and 80mL of toluene is used for eluting dioxin.
The working principle of the high-efficiency dioxin sample purification and separation column applicable to mass spectrometry is as follows:
1) the matrixes of the feed and the livestock and poultry products (meat, eggs, milk and the like) are complex and various, and efficient and universal pretreatment columns of the feed and the livestock and poultry product samples are lacked. The pretreatment column combination provided by the invention can meet the pretreatment of dioxin and dioxin-like polychlorinated biphenyl in samples of different types of feeds and livestock and poultry products;
(2) the existing pretreatment column is developed aiming at a high-resolution gas chromatography-high-resolution mass spectrometry method, and a corresponding pretreatment method and a high-efficiency pretreatment column are lacked in the development and application of a gas chromatography-tandem mass spectrometry (GC-MS/MS) method. The pretreatment column provided by the invention can provide matched pretreatment for HRGC-HGMS, GC-MS/MS and other methods;
(3) the existing composite silica gel column, active carbon column and the like need the processes of collecting filtrate, concentrating and loading sample each time the column passes, and have the disadvantages of complex operation and long period. The pretreatment column provided by the invention can realize the direct connection of the composite silica gel column and the activated carbon column, and the processes of collecting, concentrating and sampling the filtrate after the treatment of the composite silica gel column are omitted;
(4) the existing pretreatment column is manually filled, manually added with sample and leached, and cannot be automated. The pretreatment column provided by the invention can realize automatic pretreatment of samples by matching with an automatic pretreatment instrument.
Compared with the prior art, the invention has the advantages and positive effects that:
the invention relates to a high-efficiency dioxin sample purification and separation column suitable for mass spectrometry, which comprises (1) establishing a series of pretreatment columns suitable for dioxin and dioxin polychlorinated biphenyl in feed and livestock products by the ratio of fillers in a modularized combined acid column and a composite silica gel column; the method realizes the high-efficiency pretreatment and purification of dioxin and dioxin-like polychlorinated biphenyl in feeds and livestock and poultry products by using a mode of combining an acid column, a composite silica gel column and a carbon column; (2) the treatment column combination provided by the invention can be applied to sample pretreatment of two dioxin detection methods, namely HRGC-HGMS and GC-MS/MS; (3) the treatment column can be further applied to the matching use of an automatic and high-flux automatic pretreatment instrument by improving the column type or other modes; (4) the detection of dioxin and dioxin polychlorinated biphenyl in various sample matrixes can be realized by changing the column type of the pretreatment column and the proportion of the filler.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic diagram of the structure of an acid column according to the present invention;
FIG. 2 is a schematic structural view of a composite column according to the present invention;
FIG. 3 is a schematic structural view of a carbon column according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived from the embodiments of the present invention by a person skilled in the art without any creative effort, should be included in the protection scope of the present invention.
As shown in fig. 1 to 3, the dioxin high-efficiency sample purification and separation column suitable for mass spectrometry of the present invention comprises an acid column 1, a composite column 2 and a carbon column 3; the filling materials of the acid column 1 from bottom to top are neutral silica gel, 44% of acidic silica gel, 22% of acidic silica gel, neutral silica gel and anhydrous sodium sulfate in sequence; the filler under the composite column 2 is neutral silica gel, alkaline silica gel, neutral silica gel, 22% acidic silica gel, neutral silica gel and anhydrous sodium sulfate in sequence; the fillers of the carbon column 3 from bottom to top are activated carbon powder and anhydrous sodium sulfate in sequence; and the dioxin sample is subjected to purification pretreatment through an acid column 1, a composite column 2 and a carbon column 3 in sequence to obtain polychlorinated biphenyl and dioxin samples.
The neutral silica gel, the 44% acidic silica gel, the 22% acidic silica gel, the neutral silica gel and the anhydrous sodium sulfate in the acid column 1 are respectively 1g, 10g, 2g, 1g and 2cm high; the neutral silica gel, the alkaline silica gel, the neutral silica gel, the 22% acidic silica gel, the neutral silica gel and the anhydrous sodium sulfate in the composite column 2 are respectively 1g, 4g, 1g, 8g, 1g and 2cm high; the activated carbon powder and the anhydrous sodium sulfate in the carbon column 3 are respectively 1.5g and 2cm high. Pre-leaching the acid column 1 and the composite column 2 by using 70mL of n-hexane, and eluting by using 100mL of n-hexane after sample loading; the carbon column 3 is pre-leached by 10mL of toluene and 10mL of n-hexane in sequence, 50mL of n-hexane is used for eluting polychlorinated biphenyl after sample loading, and 80mL of toluene is used for eluting dioxin.
The working principle of the high-efficiency dioxin sample purification and separation column suitable for the mass spectrometry is as follows:
1) the matrixes of the feed and the livestock and poultry products (meat, eggs, milk and the like) are complex and various, and efficient and universal pretreatment columns of the feed and the livestock and poultry product samples are lacked. The pretreatment column combination provided by the invention can meet the pretreatment of dioxin and dioxin-like polychlorinated biphenyl in samples of different types of feeds and livestock and poultry products;
(2) the existing pretreatment column is developed aiming at a high-resolution gas chromatography-high-resolution mass spectrometry method, and a corresponding pretreatment method and a high-efficiency pretreatment column are lacked in the development and application of a gas chromatography-tandem mass spectrometry (GC-MS/MS) method. The pretreatment column provided by the invention can provide matched pretreatment for HRGC-HGMS, GC-MS/MS and other methods;
(3) the existing composite silica gel column, active carbon column and the like need the processes of collecting filtrate, concentrating and loading sample each time the column passes, and have the disadvantages of complex operation and long period. The pretreatment column provided by the invention can realize the direct connection of the composite silica gel column and the activated carbon column, and the processes of collecting, concentrating and sampling the filtrate after the treatment of the composite silica gel column are omitted;
(4) the existing pretreatment column is manually filled, manually added with sample and leached, and cannot be automated. The pretreatment column provided by the invention can realize automatic pretreatment of samples by matching with an automatic pretreatment instrument.
The invention relates to a high-efficiency dioxin sample purification and separation column suitable for mass spectrometry, which comprises (1) establishing a series of pretreatment columns suitable for dioxin and dioxin polychlorinated biphenyl in feed and livestock products by the ratio of fillers in a modularized combined acid column and a composite silica gel column; the method realizes the high-efficiency pretreatment and purification of dioxin and dioxin-like polychlorinated biphenyl in feeds and livestock and poultry products by using a mode of combining an acid column, a composite silica gel column and a carbon column; (2) the treatment column combination provided by the invention can be applied to sample pretreatment of two dioxin detection methods, namely HRGC-HGMS and GC-MS/MS; (3) the treatment column can be further applied to the matching use of an automatic and high-flux automatic pretreatment instrument by improving the column type or other modes; (4) the detection of dioxin and dioxin polychlorinated biphenyl in various sample matrixes can be realized by changing the column type of the pretreatment column and the proportion of the filler.
Claims (3)
1. A high-efficient sample purification and separation post of dioxin suitable for mass spectrometry is characterized in that: comprises an acid column, a composite column and a carbon column; the filling materials of the acid column from bottom to top are neutral silica gel, 44% of acidic silica gel, 22% of acidic silica gel, neutral silica gel and anhydrous sodium sulfate in sequence; the filler under the composite column is neutral silica gel, alkaline silica gel, neutral silica gel, 22% acidic silica gel, neutral silica gel and anhydrous sodium sulfate in sequence; the filling material of the carbon column from bottom to top is activated carbon powder and anhydrous sodium sulfate in sequence; and the dioxin sample is subjected to purification pretreatment through an acid column, a composite column and a carbon column in sequence, and finally polychlorinated biphenyl and dioxin samples are obtained.
2. The high-efficiency sample purification and separation column for dioxin in mass spectrometry according to claim 1, characterized in that: the neutral silica gel, the 44% acidic silica gel, the 22% acidic silica gel, the neutral silica gel and the anhydrous sodium sulfate in the acid column are respectively 1g, 10g, 2g, 1g and 2cm high; the neutral silica gel, the alkaline silica gel, the neutral silica gel, the 22% acidic silica gel, the neutral silica gel and the anhydrous sodium sulfate in the composite column are respectively 1g, 4g, 1g, 8g, 1g and 2cm high; the activated carbon powder and the anhydrous sodium sulfate in the carbon column are respectively 1.5g and 2cm high.
3. The high-efficiency sample purification and separation column for dioxin in mass spectrometry according to claim 2, characterized in that: pre-leaching the acid column and the composite column by using 70mL of n-hexane, and eluting by using 100mL of n-hexane after sampling; the carbon column is pre-leached by 10mL of toluene and 10mL of n-hexane in sequence, 50mL of n-hexane is used for eluting polychlorinated biphenyl after sample loading, and 80mL of toluene is used for eluting dioxin.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116908356A (en) * | 2023-07-19 | 2023-10-20 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Purifying device and method for brominated dioxin compounds in environmental sample |
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| US20020035303A1 (en) * | 2000-06-02 | 2002-03-21 | Chu Michael D. | Methods and apparatus for separating and detecting specific polyhalogenated diaromatic hydrocarbons |
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| CN116908356A (en) * | 2023-07-19 | 2023-10-20 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Purifying device and method for brominated dioxin compounds in environmental sample |
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