CN111487327A - Method for detecting multiple persistent organic chemical pollutants in sample - Google Patents
Method for detecting multiple persistent organic chemical pollutants in sample Download PDFInfo
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- CN111487327A CN111487327A CN201910072206.8A CN201910072206A CN111487327A CN 111487327 A CN111487327 A CN 111487327A CN 201910072206 A CN201910072206 A CN 201910072206A CN 111487327 A CN111487327 A CN 111487327A
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Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
Abstract
The invention provides a method for detecting multiple persistent organic chemical contaminants in a sample, comprising: extracting persistent organic chemical pollutants in the sample by using an extracting agent so as to obtain an extraction liquid; and detecting the extract by using a gas chromatography-mass spectrometry combined method, wherein the extracting agent is selected from ethyl acetate. The detection method is suitable for simultaneously detecting various target objects, has the advantages of high accuracy, high sensitivity, simple and quick operation and is suitable for large-scale application.
Description
Technical Field
The present invention relates to the field of biology. In particular, the present invention relates to methods for detecting a variety of persistent organic chemical contaminants in a sample.
Background
In recent years, environmental pollution is becoming more serious, and besides the common pollution of PM2.5, heavy metals and the like which people know, one kind of pollutants is often ignored by people, namely persistent organic chemical pollutants (POPs) which have the characteristics of biological enrichment, toxicity and carcinogenicity, can be persistently existed in the environment and can seriously affect the health of human beings and the environment. Persistent organic chemical pollutants are generally classified into four major groups, namely polychlorinated biphenyls, polybrominated diphenyl ethers, and polycyclic aromatic hydrocarbons.
Because POPs contaminants are present in the environment in trace or ultra trace concentrations, one is more likely to overlook their severity. POPs are used as global pollutants, and the persistent existence of the POPs in the environment influences the healthy life of people.
However, detection methods for persistent organic chemical contaminants are still under investigation.
Disclosure of Invention
The present invention aims to solve at least to some extent at least one of the technical problems of the prior art.
The present invention has been completed based on the following findings of the inventors:
at present, the detection target of persistent organic pollutants is single, and few methods for simultaneously detecting multiple targets exist, and no method for simultaneously detecting four major types of persistent organic pollutants exists. In addition, the existing sample pretreatment steps are complicated, and the detection rate of pollutants can be improved only if the concentration and enrichment times are high. Therefore, the accuracy of the detection result is low.
In view of the above, the inventor adopts ethyl acetate as an extractant to extract a plurality of persistent organic chemical pollutants (POPs) from a sample, and compared with other extractants, the application range of ethyl acetate is wide, most POPs can be extracted, the extraction effect is good, and impurities in an extraction liquid are few. Further, the gas-mass spectrometry detection conditions are researched, particularly the selection of a gas chromatographic column and the temperature rise programming are carried out, so that the qualitative or quantitative detection of multiple POPs can be accurately and rapidly carried out at the same time.
To this end, the present invention provides a method for detecting a plurality of persistent organic chemical contaminants in a sample. According to an embodiment of the invention, the method comprises: extracting persistent organic chemical pollutants in the sample by using an extracting agent so as to obtain an extraction liquid; and detecting the extract by using a gas chromatography-mass spectrometry combined method, wherein the extracting agent is selected from ethyl acetate. The inventor adopts ethyl acetate as an extracting agent so as to extract POPs from a sample, and compared with other extracting agents, the application range of the ethyl acetate is wide, most POPs can be extracted, the extraction effect is good, and impurities in an extraction liquid are few. Therefore, the method for detecting the persistent organic chemical pollutants in the sample is suitable for simultaneously detecting various target objects, has the advantages of high accuracy, high sensitivity and simplicity and convenience in operation, and is suitable for large-scale application.
According to an embodiment of the invention, the persistent organic chemical contaminant is selected from at least one of polychlorinated biphenyl, polybrominated diphenyl ether, and polycyclic aromatic hydrocarbons.
According to an embodiment of the invention, the persistent organic chemical contaminant is selected from at least two of the following: naphthalene, acenaphthene, acenaphthylene, 2-monochlorobiphenyl, fluorene, 2' -dichlorobiphenyl, 4-monobromobiphenyl, 2', 5-trichlorobiphenyl, phenanthrene, anthracene, 4,4' -dibromobiphenyl, 2',3,3' -tetrachlorobiphenyl, 2', 5-tribromobiphenyl, fluoranthene, pyrene, 2',3,4,4' -pentachlorodiphenyl, 2', 4-tribromobiphenyl ether, 2,4,4' -tribromobiphenyl ether, 2',5,5' -tetrabromobiphenyl, 2',3,3',4,4' -hexachlorobiphenyl, benzo (a) anthracene, chrysene, 2,3',4', 6-tetrabromobiphenyl ether, 2',4,4' -tetrabromobiphenyl ether, 2,3',4,4' -tetrabromobiphenyl ether, 2,2',3,3',4,4', 5-heptachlorobiphenyl, 2',4,5,5 '-pentabromobiphenyl, 2',3,3',4,4',5,5 '-octachlorobiphenyl, 2',4,4', 6-pentabromobiphenyl ether, benzo (b) fluoranthene, benzopyrene, 2',3,4,4 '-pentabromobiphenyl ether, 2',3,3',4,4',5,5', 6-nonachlorobiphenyl, 2',3,3',4,4',5,5',6,6' -decachlorobiphenyl, benzo (k) fluoranthene, 2',4,4', 5-pentabromobiphenyl ether, 2',4,4',5,6 '-hexabromobiphenyl ether, 2',4,4',5,5' -hexabromobiphenyl, 2,2',4,4',5,5 '-hexabromodiphenyl ether, 2',3,4,4',5' -hexabromobiphenyl ether, indeno (123-cd) pyrene, dibenzo (a, h) anthracene, benzo (g, h, i) perylene, 2',3,4,4',5', 6-heptabromobiphenyl ether, 2',3,4,4',5,5' -heptabromobiphenyl, 2,3,3',4,4',5, 6-heptabromobiphenyl ether, 2',3,3',4,4',5,5' -octabromobiphenyl, 2',3,3',4,4',5,5', 6-nonabromobiphenyl and decabromobiphenyl.
According to the embodiment of the invention, the gas chromatography-mass spectrometry combined method adopts a gas chromatography column with the model of CD-5HT and the size of 30.0 × 0.32.32 mm and 0.1 μm.
According to the embodiment of the invention, the heating program adopted by the gas chromatography-mass spectrometry combination method is that the temperature is kept at 70 ℃ for 3 minutes, the temperature is raised to 150 ℃ at 10 ℃/min and kept for 0min, the temperature is raised to 220 ℃ at 15 ℃/min and kept for 1min, and the temperature is raised to 320 ℃ at 6 ℃/min and kept for 7 min.
According to an embodiment of the invention, the mass-to-charge ratio of the detected quantitative ions by the gas chromatography-mass spectrometry is selected from at least one of the following: 128. 152, 153, 166, 178, 188, 202, 222, 228, 232, 246, 248, 252, 256, 276, 292, 311, 312, 326, 360, 386, 392, 394, 430, 464, 468, 469, 470, 486, 498, 546, 564, 634, 643, 644, 706, and 724; the qualitative ion mass to charge ratio is selected from at least one of: 76. 83, 101, 127, 129, 138, 150, 151, 152, 152.1, 153, 154, 165, 176, 179, 186, 187, 190, 200, 201, 203, 220, 226, 229, 234, 242, 246, 248, 250, 253, 256, 258, 267, 277, 290, 308, 310, 320, 324, 326, 328, 358, 362, 386, 389, 390, 392, 393, 404, 406, 428, 430, 462, 466, 482, 483, 484, 486, 488, 500, 550, 548, 562, 564, 624, 627, 628, 644, 705 and 785.
According to the embodiment of the invention, the detection conditions adopted by the gas chromatography-mass spectrometry combined method are as follows, the sample injection mode is divided into a flow injection mode and a flow division ratio is 2:1, the sample injection amount is 1.0 mu L, the sample injection port temperature is 280 ℃, the transmission line temperature is 290 ℃, the column flow rate is 1.2ml/min, the ion source is an EI source, the ion source temperature is 280 ℃, the ionization energy is 70eV, and the mass range of full Scan (Scan) is 50-1000 amu.
According to an embodiment of the invention, the extraction process comprises: mixing a sample with ethyl acetate to obtain a mixed solution; centrifuging the mixed solution to obtain supernatant and subnatant, and collecting the supernatant; mixing the lower layer liquid with ethyl acetate, centrifuging, and combining the upper layer liquid obtained twice; and drying the combined supernatant, and dissolving the obtained dried substance with n-hexane to obtain an extract.
According to the embodiment of the invention, the amount of the ethyl acetate is 0.2-0.8 ml based on 1 ml or 1g of the sample.
According to an embodiment of the invention, the mixing process comprises vortex oscillation and/or sonication.
According to an embodiment of the invention, the sample is derived from a water body substance or soil.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 shows a chromatogram for water quality sample detection according to one embodiment of the invention; and
FIG. 2 shows a chromatogram for soil sample detection according to one embodiment of the present invention.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention.
Method for detecting multiple persistent organic chemical pollutants in sample
The invention provides a method for detecting multiple persistent organic chemical pollutants in a sample. According to an embodiment of the invention, the method comprises: extracting persistent organic chemical pollutants in the sample by using an extracting agent so as to obtain an extraction liquid; and detecting the extract by using a gas chromatography-mass spectrometry combined method, wherein the extracting agent is selected from ethyl acetate. The inventor adopts ethyl acetate as an extracting agent so as to extract POPs from a sample, the application range of the ethyl acetate is wide, most POPs can be extracted, the extraction effect is good, and impurities in an extraction liquid are few. However, other extractants are less effective than ethyl acetate, such as: the extraction efficiency of extracting agents such as normal hexane, acetone, acetonitrile and the like is between 30% and 45%, the defect of low extraction efficiency exists, and the extraction efficiency of adopting ethyl acetate can reach 65% to 116%. And the sample treatment mode is simple, and the detection time and the workload are greatly shortened. Therefore, the method for detecting persistent organic chemical pollutants in the sample is suitable for simultaneously detecting various target objects, has the advantages of high accuracy, high sensitivity, simplicity and rapidness in operation, can realize qualitative and quantitative detection, and is suitable for large-scale application.
According to an embodiment of the present invention, the persistent organic chemical contaminant is selected from at least one of polychlorinated biphenyl, polybrominated diphenyl ether, and polycyclic aromatic hydrocarbons. Preferably, the persistent organic chemical contaminant is selected from at least two of: naphthalene, acenaphthene, acenaphthylene, 2-monochlorobiphenyl, fluorene, 2' -dichlorobiphenyl, 4-monobromobiphenyl, 2', 5-trichlorobiphenyl, phenanthrene, anthracene, 4,4' -dibromobiphenyl, 2',3,3' -tetrachlorobiphenyl, 2', 5-tribromobiphenyl, fluoranthene, pyrene, 2',3,4,4' -pentachlorodiphenyl, 2', 4-tribromobiphenyl ether, 2,4,4' -tribromobiphenyl ether, 2',5,5' -tetrabromobiphenyl, 2',3,3',4,4' -hexachlorobiphenyl, benzo (a) anthracene, chrysene, 2,3',4', 6-tetrabromobiphenyl ether, 2',4,4' -tetrabromobiphenyl ether, 2,3',4,4' -tetrabromobiphenyl ether, 2,2',3,3',4,4', 5-heptachlorobiphenyl, 2',4,5,5 '-pentabromobiphenyl, 2',3,3',4,4',5,5 '-octachlorobiphenyl, 2',4,4', 6-pentabromobiphenyl ether, benzo (b) fluoranthene, benzopyrene, 2',3,4,4 '-pentabromobiphenyl ether, 2',3,3',4,4',5,5', 6-nonachlorobiphenyl, 2',3,3',4,4',5,5',6,6' -decachlorobiphenyl, benzo (k) fluoranthene, 2',4,4', 5-pentabromobiphenyl ether, 2',4,4',5,6 '-hexabromobiphenyl ether, 2',4,4',5,5' -hexabromobiphenyl, 2,2',4,4',5,5 '-hexabromodiphenyl ether, 2',3,4,4',5' -hexabromobiphenyl ether, indeno (123-cd) pyrene, dibenzo (a, h) anthracene, benzo (g, h, i) perylene, 2',3,4,4',5', 6-heptabromobiphenyl ether, 2',3,4,4',5,5' -heptabromobiphenyl, 2,3,3',4,4',5, 6-heptabromobiphenyl ether, 2',3,3',4,4',5,5' -octabromobiphenyl, 2',3,3',4,4',5,5', 6-nonabromobiphenyl and decabromobiphenyl. The method for detecting persistent organic chemical pollutants in the sample can simultaneously detect the plurality of POPs, particularly can simultaneously detect all 49 POPs, greatly shortens the detection time and the workload, has strong accuracy and high sensitivity, is simple and rapid to operate, can realize qualitative and quantitative detection, and is suitable for large-scale application.
According to the embodiment of the invention, the type of the gas chromatographic column adopted by the gas chromatography-mass spectrometry combined method is CD-5HT, the size is 30.0 × 0.32.32 mm, the size is 0.1 μm, the accuracy of the detection result is influenced by the selection of the gas chromatographic column, particularly, various target objects are involved, some gas chromatographic columns can only detect one or more POPs, and the invention is suitable for single target object.
According to the embodiment of the invention, the heating program adopted by the gas chromatography-mass spectrometry combination method is that the temperature is kept at 70 ℃ for 3 minutes, the temperature is raised to 150 ℃ at 10 ℃/min and kept for 0min, the temperature is raised to 220 ℃ at 15 ℃/min and kept for 1min, and the temperature is raised to 320 ℃ at 6 ℃/min and kept for 7 min. The separation of substances with lower boiling points can be better realized by keeping the temperature at 70 ℃ for 3 minutes, then the temperature is increased by 10 ℃/min and 15 ℃/min, the analysis time is shortened on the premise of ensuring the separation effect, and finally the separation and detection of substances with higher boiling points can be realized by keeping the temperature at 320 ℃ for 7 minutes.
According to an embodiment of the invention, the mass to charge ratio of the detected quantitative ions by gas chromatography-mass spectrometry is selected from at least one of the following: 128. 152, 153, 166, 178, 188, 202, 222, 228, 232, 246, 248, 252, 256, 276, 292, 311, 312, 326, 360, 386, 392, 394, 430, 464, 468, 469, 470, 486, 498, 546, 564, 634, 643, 644, 706, and 724; the qualitative ion mass to charge ratio is selected from at least one of: 76. 83, 101, 127, 129, 138, 150, 151, 152, 152.1, 153, 154, 165, 176, 179, 186, 187, 190, 200, 201, 203, 220, 226, 229, 234, 242, 246, 248, 250, 253, 256, 258, 267, 277, 290, 308, 310, 320, 324, 326, 328, 358, 362, 386, 389, 390, 392, 393, 404, 406, 428, 430, 462, 466, 482, 483, 484, 486, 488, 500, 550, 548, 562, 564, 624, 627, 628, 644, 705 and 785. Therefore, the method can simultaneously detect various POPs, especially 49 POPs, greatly shortens the detection time and the workload, has strong accuracy, high sensitivity, simple and quick operation, can realize qualitative and quantitative detection, and is suitable for large-scale application.
According to the embodiment of the invention, the detection conditions adopted by the gas chromatography-mass spectrometry combined method are as follows, the sample injection mode comprises split sample injection with a split flow ratio of 2:1, the sample injection amount of 1.0 mu L, the sample injection port temperature of 280 ℃, the transmission line temperature of 290 ℃, the column flow of 1.2ml/min, the ion source of EI source, the ion source temperature of 280 ℃, the ionization energy of 70eV, and the full Scan (Scan) mass range of 50-1000 amu.
According to an embodiment of the invention, the extraction process comprises: mixing a sample with ethyl acetate to obtain a mixed solution; centrifuging the mixed solution to obtain supernatant and subnatant, and collecting the supernatant; mixing the lower layer liquid with ethyl acetate, centrifuging, and combining the upper layer liquid obtained twice; and drying the combined supernatant, and dissolving the obtained dried substance with n-hexane to obtain an extract. Therefore, POPs in the sample can be fully extracted, and the extraction liquid contains less impurities, so that the accuracy of the detection result is ensured.
According to the embodiment of the invention, the amount of the ethyl acetate is 0.2-0.8 ml based on 1 ml or 1g of the sample. Thus, POPs in the sample can be sufficiently extracted. If the amount of ethyl acetate is too much, POPs are diluted equivalently, so that the content of the target substance in the extract liquid is low, and the accuracy of the detection result is low.
According to an embodiment of the invention, the mixing process comprises vortex oscillation and/or sonication. Thereby, ethyl acetate is sufficiently brought into contact with the POPs, thereby improving extraction efficiency.
According to an embodiment of the invention, the sample is derived from a water body substance or soil. The method provided by the embodiment of the invention can be used for detecting various POPs in water substances or soil, especially can be used for simultaneously detecting 49 POPs, greatly shortens the detection time and workload, has the advantages of strong accuracy, high sensitivity, simplicity and convenience in operation, rapidness, capability of realizing qualitative and quantitative detection and suitability for large-scale application.
It should be noted that the term "water substance" used in the present invention mainly refers to water sources, such as tap water, underground water, river mouths and sea water, and persistent organic chemical pollutants in the water sources can be detected by the method of the present invention.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are conventional products which are commercially available, and are not known to manufacturers.
Example 1
In this example, persistent organic contaminants in water samples were detected as follows:
(1) sample pretreatment
From an acquired water sample, uniformly shaking and accurately measuring a water sample of 20.00m L (accurate to 0.01m L) to 50m L centrifuge tube A, adding 5ml of ethyl acetate, carrying out vortex oscillation for 60s, placing the mixture into a water bath at 37 ℃ for ultrasonic treatment for 30min, centrifuging the mixture at 4500r/min and 4 ℃ for 5min, taking an upper organic phase, placing the upper organic phase into a 10m L centrifuge tube B, adding 5m L ethyl acetate into a lower layer of the centrifuge tube A, repeatedly extracting for 1 time according to the steps, combining the upper organic phase, placing the upper organic phase into a 10m L centrifuge tube B, carrying out nitrogen blow-drying, dissolving 400 mu L n-hexane, fully carrying out vortex oscillation, filtering the obtained solution by using a 0.22 mu m organic phase type microporous filter membrane after redissolution, preparing a liquid to be detected, and injecting 100 mu L into a sample injection vial to be.
(2) Preparation of blank and spiked samples
And (3) replacing the sample with experimental water, and preparing a water quality blank sample according to the step (1).
And (3) adding the mixed standard substance into the experimental water, and preparing the water quality standard sample according to the step (1).
The 49 persistent organic pollutant standard substance substances are diluted by n-hexane step by step to prepare standard substance solutions with the concentrations of 250.00, 100.00, 50.00, 10.00, 5.00 and 1.00ng/m L.
(3) GC-MS detection
Performing GC-MS detection on the solution to be detected, the blank sample, the standard sample and the standard solution under the following detection conditions:
the method comprises the following steps of (1) preparing a gas chromatographic column, wherein the gas chromatographic column comprises CD-5HT (30.0 × 0.32.32 mm, 0.1 mu m), a sample feeding mode comprises a split-flow sample feeding mode, a split-flow ratio of 2:1, a sample feeding amount of 1.0 mu L, a sample feeding port temperature of 280 ℃, a transmission line temperature of 290 ℃, a column flow rate of 1.2ml/min, an ion source, an EI source, an ion source temperature of 280 ℃, an ionization energy of 70eV, a full Scan (Scan) mass range of 50-1000 amu, a Selective Ion (SIM) Scan, ions and a temperature raising program, wherein the selected ions are shown in a table 1:
table 1: analytical parameters of GC-MS for 49 target Compounds
(4) And (3) qualitative analysis:
the detected ion spectrum is shown in figure 1, and after the retention time of the chromatographic peak detected by the sample is compared with that of the chromatographic peak of the standard substance, the sample is determined to contain naphthalene, phenanthrene, 2',5,5' -tetrabromobiphenyl, benzo (a) anthracene, chrysene, 2',3,3',4,4',5,5' -octachlorobiphenyl.
(5) Quantitative analysis:
and (5) drawing a standard curve by taking the concentration of the standard substance as an abscissa and the quantitative ion area as an ordinate. And (3) quantifying by adopting an external standard-working curve method, and calculating a mass spectrogram of a sample after background subtraction, wherein the detected naphthalene content is 46ppb, the phenanthrene content is 100ppb, the 2,2',5,5' -tetrabromobiphenyl content is 98ppb, the benzo (a) anthracene content is 32ppb, the chrysene content is 48ppb, and the octachlorobiphenyl content is 36 ppb.
Example 2
In this example, persistent organic contaminants in soil samples were detected as follows:
(1) sample pretreatment
Stirring and mixing soil collected from an industrial area by using a glass rod, grinding 30g of the ground soil in a clean mortar, sieving, weighing 20.00g (accurate to 0.01g) of the ground soil to 50m L centrifuge tube A, adding 5ml of ethyl acetate, carrying out vortex oscillation for 60s, putting the centrifuge tube A in a water bath at 37 ℃ for 30min, carrying out ultrasonic treatment at 4500r/min and 4 ℃ for 5min, taking an upper organic phase in a 10m L centrifuge tube B, adding 5m L of ethyl acetate to a lower layer of the centrifuge tube A, repeatedly extracting for 1 time according to the steps, taking an upper organic phase, combining the upper organic phase in a 10m L centrifuge tube B, carrying out blow-drying by using nitrogen, dissolving 400 mu L of n-hexane, carrying out full vortex oscillation, carrying out re-dissolution, filtering by using a 0.22 mu m organic phase type microporous filter membrane to prepare a liquid to be detected, and injecting 100 mu L into a small bottle.
(2) Preparation of blank samples
A soil blank sample is prepared by using an experimental soil sample according to the same operation steps of sample preparation.
(3) Preparation of standard solution
The 49 persistent organic pollutant standard substance substances are diluted by normal hexane step by step to prepare standard substance solutions with the concentrations of 1000.00, 500.00, 250.00, 100.00, 50.00, 10.00, 5.00 and 1.00ng/m L.
(4) GC-MS detection conditions
Performing GC-MS detection on the solution to be detected, the blank sample, the standard sample and the standard solution under the following detection conditions:
the method comprises the following steps of (1) preparing a gas chromatographic column, wherein the gas chromatographic column comprises CD-5HT (30.0 × 0.32.32 mm, 0.1 mu m), a sample feeding mode comprises split sample feeding with a split flow ratio of 2:1, a sample feeding amount of 1.0 mu L, a sample feeding port temperature of 280 ℃, a transmission line temperature of 290 ℃, a column flow rate of 1.2ml/min, an ion source of EI source, an ion source temperature of 280 ℃, an ionization energy of 70eV, a full Scan (Scan) mass range of 50-1000 amu, a Selective Ion (SIM) Scan, ions and a programmed temperature rise, wherein the selected ions are shown in a table 1:
(5) and (3) qualitative analysis:
the detected ion spectrum is shown in figure 2, and the retention time of the chromatographic peak detected by the sample is compared with that of the chromatographic peak of the standard substance, so that the sample is determined to contain naphthalene, acenaphthylene, fluoranthene, benzo (a) anthracene, benzo (b) fluoranthene, 2',4,4', 5-pentabromodiphenyl ether and indeno (123-cd) pyrene.
(6) Quantitative analysis:
and (5) drawing a standard curve by taking the concentration of the standard substance as an abscissa and the quantitative ion area as an ordinate. And quantifying by adopting an external standard-working curve method, calculating a mass spectrogram of a sample after background subtraction, and detecting that the content of naphthalene is 37ppb, the content of acenaphthylene is 92ppb, the content of fluoranthene is 92ppb, the content of benzo (a) anthracene is 100ppb, the content of benzo (b) fluoranthene is 80ppb, the content of 2,2',4,4', 5-pentabromobiphenyl ether is 9ppb, and the content of indeno (123-cd) pyrene is 51 ppb.
And simultaneously, the samples are sent to a third-party detection mechanism for detection according to the related standard of national standard and international standard (ZEK 01.4-08). The naphthalene content is 35ppb, the acenaphthylene content is 90ppb, the fluoranthene content is 95ppb, the benzo (a) anthracene content is 103ppb, the benzo (b) fluoranthene content is 82ppb, the 2,2',4,4', 5-pentabromobiphenyl ether content is 7ppb, and the indeno (123-cd) pyrene content is 48 ppb. The error between the detection result and the result of the method is not more than 20 percent, and the method meets the statistical requirement.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Moreover, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method for detecting a plurality of persistent organic chemical contaminants in a sample, comprising:
extracting persistent organic chemical pollutants in the sample by using an extracting agent so as to obtain an extraction liquid; and
detecting the extract by using a gas chromatography-mass spectrometry,
wherein the extractant is selected from ethyl acetate.
2. The method of claim 1, wherein the persistent organic chemical contaminant is selected from at least one of polychlorinated biphenyl, polybrominated diphenyl ethers, and polycyclic aromatic hydrocarbons,
preferably, the persistent organic chemical contaminant is selected from at least two of:
naphthalene, acenaphthene, 2-monochlorobiphenyl, fluorene, 2' -dichlorobiphenyl, 4-monobromobiphenyl, 2', 5-trichlorobiphenyl, phenanthrene, anthracene, 4,4' -dibromobiphenyl, 2',3,3' -tetrachlorobiphenyl, 2', 5-tribromobiphenyl, fluoranthene, pyrene, 2',3,4,4' -pentachlorodiphenyl, 2', 4-tribromobiphenyl ether, 2,4,4' -tribromobiphenyl ether, 2',5,5' -tetrabromobiphenyl, 2',3,3',4,4' -hexachlorobiphenyl, benzo (a) anthracene, chrysene, 2,3',4', 6-tetrabromobiphenyl ether, 2',4,4' -tetrabromobiphenyl ether, 2,3',4,4' -tetrabromobiphenyl ether, 2,2',3,3',4,4', 5-heptachlorobiphenyl, 2',4,5,5' -pentabromobiphenyl, 2',3,3',4,4',5,5' -octachlorobiphenyl, 2',4,4', 6-pentabromobiphenyl ether, benzo (b) fluoranthene, benzopyrene, 2',3,4,4' -pentabromobiphenyl ether, 2',3,3',4,4',5,5', 6-nonachlorobiphenyl, 2',3,3',4,4',5,5',6,6' -decachlorobiphenyl, benzo (k) fluoranthene, 2',4,4', 5-pentabromobiphenyl ether, 2',4,4',5,6' -hexabromobiphenyl ether, 2',4,4',5,5' -hexabromobiphenyl, 2',4,4',5,5' -hexabromobiphenyl ether, 2',3,4,4',5' -hexabromobiphenyl ether, indeno (123-cd) pyrene, dibenzo (a, h) anthracene, benzo (g, h, i) perylene, 2',3,4,4',5', 6-heptabromobiphenyl ether, 2',3,4,4',5,5' -heptabromobiphenyl, 2,3,3',4,4',5, 6-heptabromobiphenyl ether, 2',3,3',4,4',5,5' -octabromobiphenyl, 2',3,3',4,4',5,5', 6-nonabromobiphenyl and decabromobiphenyl.
3. The method of claim 1, wherein the GC-MS is performed using a GC column having a size of 30.0 × 0.32.32 mm, 0.1 μm, CD-5 HT.
4. The method according to claim 1, wherein the heating program used in the GC-MS method is 70 ℃ for 3 minutes, 10 ℃/min to 150 ℃ for 0min, 15 ℃/min to 220 ℃ for 1min, 6 ℃/min to 320 ℃ for 7 min.
5. The method of claim 1, wherein the mass-to-charge ratio of the detected quantitative ions is selected from at least one of the following: 128. 152, 153, 166, 178, 188, 202, 222, 228, 232, 246, 248, 252, 256, 276, 292, 311, 312, 326, 360, 386, 392, 394, 430, 464, 468, 469, 470, 486, 498, 546, 564, 634, 643, 644, 706, and 724;
the qualitative ion mass to charge ratio is selected from at least one of: 76. 83, 101, 127, 129, 138, 150, 151, 152, 152.1, 153, 154, 165, 176, 179, 186, 187, 190, 200, 201, 203, 220, 226, 229, 234, 242, 246, 248, 250, 253, 256, 258, 267, 277, 290, 308, 310, 320, 324, 326, 328, 358, 362, 386, 389, 390, 392, 393, 404, 406, 428, 430, 462, 466, 482, 483, 484, 486, 488, 500, 550, 548, 562, 564, 624, 627, 628, 644, 705 and 785.
6. The method of claim 1, wherein the combined gas chromatography-mass spectrometry is performed under the following detection conditions:
the sample injection mode comprises split sample injection with a split ratio of 2:1, a sample injection amount of 1.0 mu L, a sample injection port temperature of 280 ℃, a transmission line temperature of 290 ℃, a column flow rate of 1.2ml/min, an ion source of EI source, an ion source temperature of 280 ℃, an ionization energy of 70eV, and a total scanning (Scan) mass range of 50-1000 amu.
7. The method of claim 1, wherein the extraction process comprises:
mixing a sample with ethyl acetate to obtain a mixed solution;
centrifuging the mixed solution to obtain supernatant and subnatant, and collecting the supernatant;
mixing the lower layer liquid with ethyl acetate, centrifuging, and combining the upper layer liquid obtained twice; and
the combined supernatant was subjected to drying treatment, and the resultant dried product was dissolved with n-hexane to obtain an extract.
8. The method according to claim 7, wherein the amount of the ethyl acetate is 0.2 to 0.8 ml based on 1 ml or 1g of the sample.
9. The method of claim 7, wherein the mixing process comprises vortexing and/or sonication.
10. The method of claim 1, wherein the sample is derived from a body of water material or soil.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112051347A (en) * | 2020-09-30 | 2020-12-08 | 浙江大学 | GC-MS quantitative method capable of simultaneously and rapidly analyzing 41 persistent organic matters in soil |
| CN112946155A (en) * | 2021-02-07 | 2021-06-11 | 杭州华东医药集团新药研究院有限公司 | Method for determining content of 4-chlorobiphenyl and 4, 4-dichlorobiphenyl serving as oritavancin intermediate impurities |
| CN112964821A (en) * | 2021-04-30 | 2021-06-15 | 厦门泓益检测有限公司 | Method for simultaneously detecting multiple organic pollutants in water body by gas chromatography-mass spectrometry |
| CN113219091A (en) * | 2021-04-28 | 2021-08-06 | 广东省中鼎检测技术有限公司 | Detection method for rapidly determining content of five persistent biological accumulated toxic substances in consumer product |
| CN113702518A (en) * | 2021-07-12 | 2021-11-26 | 河北省地质实验测试中心(国土资源部保定矿产资源监督检测中心、河北省金银宝玉饰品质量监督检验站) | Monitoring method for atmospheric settlement of persistent organic pollutants POPs |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102279231A (en) * | 2011-06-28 | 2011-12-14 | 中国科学院生态环境研究中心 | Quick qualitative detection method for polychlorinated biphenyl pollutants |
| CN104280485A (en) * | 2014-10-24 | 2015-01-14 | 南京大学 | Method for synchronously extracting and purifying various chlorinated polycyclic aromatic hydrocarbons in soil |
| CN107132305A (en) * | 2017-07-18 | 2017-09-05 | 泉州出入境检验检疫局综合技术服务中心 | The detection method of organochlorine class compound in leather |
| WO2018088716A1 (en) * | 2016-11-11 | 2018-05-17 | 주식회사 엘지화학 | Pretreatment method for analyzing dioxin compounds and analysis method using same |
| CN108195982A (en) * | 2017-12-19 | 2018-06-22 | 浙江省海洋水产研究所 | The detection method of persistence organic pollutant in a kind of aquatic products |
-
2019
- 2019-01-25 CN CN201910072206.8A patent/CN111487327A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102279231A (en) * | 2011-06-28 | 2011-12-14 | 中国科学院生态环境研究中心 | Quick qualitative detection method for polychlorinated biphenyl pollutants |
| CN104280485A (en) * | 2014-10-24 | 2015-01-14 | 南京大学 | Method for synchronously extracting and purifying various chlorinated polycyclic aromatic hydrocarbons in soil |
| WO2018088716A1 (en) * | 2016-11-11 | 2018-05-17 | 주식회사 엘지화학 | Pretreatment method for analyzing dioxin compounds and analysis method using same |
| CN107132305A (en) * | 2017-07-18 | 2017-09-05 | 泉州出入境检验检疫局综合技术服务中心 | The detection method of organochlorine class compound in leather |
| CN108195982A (en) * | 2017-12-19 | 2018-06-22 | 浙江省海洋水产研究所 | The detection method of persistence organic pollutant in a kind of aquatic products |
Non-Patent Citations (7)
| Title |
|---|
| JUAN SÁNCHEZ-AVILA 等: "Development of a multi-residue method for the determination of organic micropollutants in water，sediment and mussels using gas chromatography-tandem mass spectrometry", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| ZHANG H 等: "Co-extraction and simultaneous determination of multi-class hydrophobic organic contaminants in marine sediments and biota using GC-EI-MS/MS and LC-ESI-MS/MS", 《TALANTA》 * |
| 侯圣军 等: "气相色谱/质谱选择离子检测法同时测定大米中的25种持久性有机污染物", 《色谱》 * |
| 叶曦雯 等: "气相色谱-质谱法测定压敏胶及其制品中的多溴联苯与多溴二苯醚", 《分析测试学报》 * |
| 李樱 等: "凝胶渗透色谱-气相色谱同时测定糙米中拟除虫菊酯、有机氯农药和多氯联苯的残留量", 《色谱》 * |
| 范磊 等: "气相色谱-三重四极杆质谱法测定水中持久性有机氯污染物", 《中国环境监测》 * |
| 边照阳 等: "《QuEChERS技术及应用》", 31 December 2017, 中国轻工业出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112051347A (en) * | 2020-09-30 | 2020-12-08 | 浙江大学 | GC-MS quantitative method capable of simultaneously and rapidly analyzing 41 persistent organic matters in soil |
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| CN113702518A (en) * | 2021-07-12 | 2021-11-26 | 河北省地质实验测试中心(国土资源部保定矿产资源监督检测中心、河北省金银宝玉饰品质量监督检验站) | Monitoring method for atmospheric settlement of persistent organic pollutants POPs |
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