CN106501431B - A kind of method of Polychlorinated biphenyls in post detection dairy products using silica gel chromatograph - Google Patents
A kind of method of Polychlorinated biphenyls in post detection dairy products using silica gel chromatograph Download PDFInfo
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- CN106501431B CN106501431B CN201610915107.8A CN201610915107A CN106501431B CN 106501431 B CN106501431 B CN 106501431B CN 201610915107 A CN201610915107 A CN 201610915107A CN 106501431 B CN106501431 B CN 106501431B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/60—Construction of the column
- G01N30/6034—Construction of the column joining multiple columns
- G01N30/6039—Construction of the column joining multiple columns in series
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/08—Preparation using an enricher
Abstract
The invention provides a kind of silica gel chromatographic column for being used in gas chromatography-mass spectrometry detect Polychlorinated biphenyls, the silica gel chromatographic column purifies chromatographic column by acidic silica gel, compound silica gel purifies chromatographic column and alkali alumina purification chromatographic column forms, and specifically discloses the preparation method of each chromatographic column.The present invention additionally provides a kind of method using Polychlorinated biphenyls in above-mentioned silica gel chromatograph post detection dairy products simultaneously, the modified silica-gel superior performance prepared in this method, and in this method filler fill order it is with strong points, fill order is reasonable, therefore, multilayer silica gel purification chromatographic column prepared by this method can overcome the matrix effect of complexity, the plurality of impurities in the organic pollution matrix of class containing polychlorinated biphenyl can be removed, eliminate to interference caused by follow-up polychlorinated biphenyl class organic contamination analyte detection, so as to improve gas chromatography-mass spectrometry accurate quantitative analysis polychlorinated biphenyl, it is simple to operate, it is reproducible, precision is high.
Description
Technical field
The preparation method of the silica gel chromatographic column of Polychlorinated biphenyls is detected the present invention relates to a kind of gas chromatography-mass spectrometry, with
And the detection method of the silica gel chromatograph post detection Polychlorinated biphenyls, the detection technique field in dairy products.
Background technology
Chlordiphenyl (PCBs) be it is a kind of using biphenyl be raw material under metallic catalyst effect, the chloro of high-temp chlorination synthesis is fragrant
Hydrocarbon.Number and the difference of the position of substitution are substituted according to chlorine atom, PCBs shares 209 kinds of homologues.Because PCBs has well
The advantages that chemical inertness, heat resistance, incombustible, low-steam pressure and high-k, therefore it is used for heat exchanging agent, lubrication
Dielectric, plasticizer, paraffin in agent, transformer and capacitor expand agent, binder, organic diluent, dedusting agent, desinsection
The important chemical products such as agent, cutting oil, pressure-sensitive carbon paper and fire retardant, and it is widely used in power industry, plastic processing
The fields such as industry, chemical industry and printing.PCBs has persistence and extended residual, once it is discharged into environment, it is difficult to be degraded, because
This can have many decades or longer time in the media such as water body, soil, and contained chlorine atom makes its tool in PCBs structures
There is the characteristics of low aqueous solubility and fat-solubility, it is thus possible to biological accumulation, and the life for passing through food chain occur in adipose tissue
Thing amplification reaches the concentration of poisoning.
The organism kinds of dairy products are various, and the matrix residing for this kind of organic pollution is also sufficiently complex, if impurity
Without processing, then larger interference can be produced to the testing result of follow-up organic pollution, influence the result of detection.This method uses
Silica gel chromatograph column purification, different according to absorption affinity of the material on silica gel and separated, the generally larger thing of polarity
Matter is easily not easy by silica gel absorption by silica gel absorption, the weaker material of polarity, whole chromatography process is Adsorption and desorption, adsorb again,
Desorption process again, successively using acidic silica gel column purification, compound silica gel column purification, alkali alumina column purification.Due to ordinary silicon
Disturbed caused by the detection to follow-up polychlorinated biphenyl of glue chromatographic column very big.Therefore, prepared by common silica gel chromatographic column
Silica gel chromatographic column prepared by method cannot be used for polychlorinated biphenyl compound class organic pollution in detection of complex matrix.
The content of the invention
The purpose of this method is to solve the content analysis method for improving polychlorinated biphenyl, reduces impurity in sample
And the interference of exogenous impurity, so as to improve gas chromatography-mass spectrometry accurate quantitative analysis polychlorinated biphenyl, there is provided
The assay method of the content of polychlorinated biphenyl in a kind of detection dairy products simple to operate, reproducible, precision is high.
Technical scheme is used by realizing above-mentioned purpose of the present invention：
A kind of silica gel chromatographic column for being used in gas chromatography-mass spectrometry detect Polychlorinated biphenyls, the silica gel chromatographic column is by acid
Property silica gel purification chromatographic column, compound silica gel purification chromatographic column and alkali alumina purification chromatographic column composition, the preparation of each chromatographic column
Method is as follows：
(1), each filler component is weighed according to following mass parts：
A acidic silica gels purify chromatographic column：1. 2~4 parts of activated silica gel；2. 4~6 parts of acidic silica gel；3. activated silica gel 1
~2 parts；4. 2~4 parts of anhydrous sodium sulfate；
B compound silica gels purify chromatographic column：1. 1~3 part of silver nitrate silica gel；2. 1~2 part of activated silica gel；3. alkaline silica gel
2~4 parts；4. 1~2 part of activated silica gel；5. 3~6 parts of acidic silica gel；6. 2~4 parts of activated silica gel；7. anhydrous sodium sulfate 2~
4 parts；
C alkali aluminas purify chromatographic column：1. 1~3 part of alkali alumina；2. 2~4 parts of anhydrous sodium sulfate；
(2) chromatographic column of three dried and cleans, is taken, chromatogram column internal diameter is 1 with length ratio:8~10, according to step (1)
The order of middle each component successively pours into each filler from the upper port of chromatographic column successively, and tri- kinds of proportionings of A, B and C correspond to one respectively
Individual chromatographic column, every kind of filler allows the filler poured into tile uniform after the upper port of chromatographic column pours into, and chromatogram column wall
Non-filler adheres to, and after the completion of all fillers are filling, open the rotary-piston of chromatographic column lower end, is connect in the lower port of chromatographic column
Enter vavuum pump, then open vavuum pump, the outer wall of chromatographic column is beaten when vacuumizing, when chromatographic column inner stuffing height no longer
During decline, after continuing to vacuumize at least 3 minutes, chromatographic column lower end piston is screwed；
(3) dichloromethane slowly, is injected into chromatographic column from chromatographic column upper port along chromatogram column wall, opens chromatographic column lower end
Piston, make the flow velocity of the liquid of inflow chromatographic column maximum, make all fillers all wetted and bubble-free, when in chromatographic column
Each filler clear layer, form for the moment, stop injection dichloromethane, finally with enough n-hexane elution chromatography posts, washed
The piston of chromatographic column lower end is closed after de-.
The preparation method of the activated silica gel is as follows：Filling is used into n-hexane and eluent methylene chloride twice with silica gel,
The solvent volume used every time is twice of silica gel volume, after elution, silica gel is transferred in flask, covering bottleneck with aluminium foil puts
50 DEG C are baked to dry in baking oven, then heat at 150~250 DEG C baking 8h~12h, ground reagent bottle is loaded after cooling
In, preserved in drier, that is, activated silica gel is made.
The preparation method of the silver nitrate silica gel is as follows：4~7g silver nitrates are dissolved in 15~25mL deionized waters, by
It is added dropwise in 50g activated silica gels, shaking is fitted into brown ground reagent bottle, preserved in drier to after without block, that is, is made
Silver nitrate silica gel.
The acidic silica gel is sulfuric acid silica gel, and the preparation method of sulfuric acid silica gel is as follows：By sulfuric acid：Silica gel=8:8~12
Mass ratio, the concentrated sulfuric acid that mass percent concentration is 95%~97% is added drop-wise in silica gel under agitation, is often added dropwise one
The drop concentrated sulfuric acid will be stirred to after being uniformly dispersed is added dropwise next drop concentrated sulfuric acid again, will be dense with oscillator after the concentrated sulfuric acid is added dropwise
Mixed system sustained oscillation to the reaction of sulfuric acid and silica gel finishes, and is fitted into ground reagent bottle, is preserved in drier, that is, sulphur is made
Sour silica gel.
The alkaline silica gel is sodium hydroxide silica gel, and the preparation method of sodium hydroxide silica gel is as follows：By sodium hydroxide solution：
Silica gel=1:2~3 mass ratio, the sodium hydroxide solution that concentration is 0.8mol/L~1.2mol/L is added dropwise under agitation
Into silica gel, often the drop of dropwise addition one sodium hydroxide solution will be stirred to after being uniformly dispersed is added dropwise next drop sodium hydroxide solution again,
After being added dropwise, mixed system sustained oscillation to the reaction of sodium hydroxide solution and silica gel is finished with oscillator, loads ground
In reagent bottle, preserved in drier, that is, sodium hydroxide silica gel is made.
The time shaken in above-mentioned steps with oscillator is 6~8 hours.
The alkali alumina is using the pretreated alkali alumina of following methods：By alkali alumina 600~
After toasting 4~8h at 700 DEG C, it is fitted into ground reagent bottle, is preserved in drier.
The anhydrous sodium sulfate is by the pretreated anhydrous sodium sulfate of following methods：By anhydrous sodium sulfate use just oneself
Alkane and eluent methylene chloride 2~5 times, the solvent volume used every time are twice of anhydrous sodium sulfate volume, will be anhydrous after elution
Sodium sulphate is transferred in flask, be baked at 50 DEG C it is dry, then at 150~250 DEG C toast 8h~12h, after cooling dry
Preserved in device.
The present invention additionally provides a kind of method using Polychlorinated biphenyls in above-mentioned silica gel chromatograph post detection dairy products simultaneously, wraps
Include following steps：
(1), dairy products sample, which is put into refrigerator, freezes, it is to be frozen completely after, frozen dairy product is put into freeze drier,
- 20 DEG C~-40 DEG C of freeze drier precooling temperature, -30 DEG C~-40 DEG C of temperature is freeze-dried, the sample after freezing loads
Surname extraction filter cylinder simultaneously places soxhlet type apparatus, and water-bath extraction 5h~8h, siphonage time is 3~4 times/h, and the sample of concentration is made
Product extract solution；
(2) acid silica gel purification chromatographic column, compound silica gel purification, are rinsed respectively with the mixed liquor of n-hexane and dichloromethane
Chromatographic column and alkali alumina purification chromatographic column, the flow velocity of flushing is maximum, makes liquid level equal with silica gel；
(3), the sample extracting solution of concentration is injected into acidic silica gel purification chromatographic column, eluted with n-hexane, control is solidifying
The flow velocity of glue post is 1.0~3.0mL/min, and eluent is concentrated into 0.5~1.5mL；
By through acidic silica gel purify chromatogram column purification after extract solution be injected into compound silica gel purification chromatographic column in, use just oneself
Alkane and dichloromethane are according to 97:1~97:The 4 mixed solution of volume ratio elutes in advance；Acidic silica gel purification chromatogram will be passed through again
Concentrate eluant is fully transferred in compound silica gel purification chromatographic column after column purification；Added when liquid level is down to anhydrous sodium sulfate layer
N-hexane and dichloromethane are according to 97:1~97:The 4 mixed solution of volume ratio is eluted, and eluent is concentrated into 0.5
~1.0mL；
The extract solution that chromatogram column purification is purified through compound silica gel is injected into alkali alumina purification chromatographic column, will be through multiple
Concentrate eluant is fully transferred in alkali alumina purification chromatographic column after closing silica gel purification chromatogram column purification, when liquid level is down to nothing
N-hexane elution alkali alumina purification chromatographic column is added during aqueous sodium persulfate layer, two are added when liquid level is down to anhydrous sodium sulfate layer
The mixed solution of chloromethanes and n-hexane is eluted, then eluent is concentrated into near do；
(4), the concentrate eluant in step (3) is analyzed using gas chromatography-mass spectrometry；
(5), quantitative analysis, using double internal standard quanitations, 8 kinds of Polychlorinated biphenyls Isotopic Internal Standards (13C12-labelled
PCBs 28,52,118,153,180,202,206 and 209) and 2 kinds of Polychlorinated biphenyls isotopes reclaim internal standards (13C12-PCB101、13C12- PCB194) quantify, Isotopic Internal Standard is used for calibrating the determinands of 33 kinds of Polychlorinated biphenyls.
The operating parameter of gas chromatography-mass spectrometry is in above-mentioned steps (4)：Sample (5%- phenyl)-methyl polysilicon oxygen
The capillary chromatographic column of alkane filler, mineral wool shunting is filled with the dottle pin and graphite grazing pad of high temperature resistant low-bleed, deactivation processing
With regardless of flowing universal bushing pipe；The program of column oven is：Maintained 2 minutes at 100 DEG C first, then the heating speed with 15 DEG C/min
Rate is raised to 180 DEG C from 100 DEG C；Then 240 DEG C are raised to from 180 DEG C with 3 DEG C/min heating rate；Finally with 10 DEG C/min liter
Warm speed is raised to 285 DEG C from 240 DEG C, and maintains 10min at 285 DEG C；Total run time is 42min；Carrier gas uses purity>
99.999% high-purity helium, constant flow rate 1mL/min；Sample and the sample size of standard liquid are 2.0 μ L, using Splitless injecting samples
Pattern, injector temperature are 300 DEG C；Mass spectrometer parameters are：Ionization pattern, electron bombardment ionization source (EI), energy 70eV；Ion gun
Temperature is 230 DEG C, 150 DEG C of level Four bar temperature, and transmission line temperature is 300 DEG C, solvent delay 4min.
Compared with prior art, its advantage and advantage are the present invention：
The modified silica-gel superior performance prepared in this method, and in this method filler fill order it is with strong points,
Fill order is reasonable, and therefore, multilayer silica gel purification chromatographic column prepared by this method can overcome the matrix effect of complexity, can remove and contain
Plurality of impurities in polychlorinated biphenyl class organic pollution matrix, eliminate has to follow-up polychlorinated biphenyl class
Disturbed caused by organic pollutants detection.Importantly, multilayer silica gel purification chromatographic column prepared by this method is simple to operate, through examination
Test and show, the organic pollution such as multilayer silica gel chromatograph post detection polychlorinated biphenyl prepared using this method has sensitive
The advantages of degree is high, the degree of accuracy is high, favorable reproducibility and the rate of recovery are high.
Embodiment
It is provided by the present invention to be used to detect the silica gel chromatographic column of Polychlorinated biphenyls in gas chromatography-mass spectrometry by acidity
Silica gel purification chromatographic column, compound silica gel purification chromatographic column and alkali alumina purification chromatographic column composition, the following institute of its preparation method
Show：
(1), each filler component is weighed according to following mass parts：
A acidic silica gels purify chromatographic column：1. 2~4 parts of activated silica gel；2. 4~6 parts of acidic silica gel；3. activated silica gel 1
~2 parts；4. 2~4 parts of anhydrous sodium sulfate；
B compound silica gels purify chromatographic column：1. 1~3 part of silver nitrate silica gel；2. 1~2 part of activated silica gel；3. alkaline silica gel
2~4 parts；4. 1~2 part of activated silica gel；5. 3~6 parts of acidic silica gel；6. 2~4 parts of activated silica gel；7. anhydrous sodium sulfate 2~
4 parts；
C alkali aluminas purify chromatographic column：1. 1~3 part of alkali alumina；2. 2~4 parts of anhydrous sodium sulfate；
Wherein：The preparation method of the silver nitrate silica gel is as follows：4~7g silver nitrates are dissolved in 15~25mL deionized waters
In, it is added dropwise in 50g activated silica gels, vibrates 6~8 hours to after without block with oscillator, load brown ground reagent bottle
In, preserved in drier, that is, silver nitrate silica gel is made.
The acidic silica gel is sulfuric acid silica gel, and the preparation method of sulfuric acid silica gel is as follows：By sulfuric acid：Silica gel=8:8~12
Mass ratio, the concentrated sulfuric acid that mass percent concentration is 95%~97% is added drop-wise in silica gel under agitation, is often added dropwise one
The drop concentrated sulfuric acid will be stirred to after being uniformly dispersed is added dropwise next drop concentrated sulfuric acid again, will be dense with oscillator after the concentrated sulfuric acid is added dropwise
The mixed system sustained oscillation of sulfuric acid and silica gel finishes for 6~8 hours to reaction, is fitted into ground reagent bottle, is preserved in drier,
Sulfuric acid silica gel is made.
The alkaline silica gel is sodium hydroxide silica gel, and the preparation method of sodium hydroxide silica gel is as follows：By sodium hydroxide solution：
Silica gel=1:2~3 mass ratio, the sodium hydroxide solution that concentration is 0.8mol/L~1.2mol/L is added dropwise under agitation
Into silica gel, often the drop of dropwise addition one sodium hydroxide solution will be stirred to after being uniformly dispersed is added dropwise next drop sodium hydroxide solution again,
After being added dropwise, the mixed system sustained oscillation 6~8 hours of sodium hydroxide solution and silica gel to reaction is finished with oscillator,
It is fitted into ground reagent bottle, is preserved in drier, that is, sodium hydroxide silica gel is made.
The preparation method of the activated silica gel is as follows：Filling is used into n-hexane and eluent methylene chloride twice with silica gel,
The solvent volume used every time is twice of silica gel volume, after elution, silica gel is transferred in flask, covering bottleneck with aluminium foil puts
50 DEG C are baked to dry in baking oven, then heat at 150~250 DEG C baking 8h~12h, ground reagent bottle is loaded after cooling
In, preserved in drier, that is, activated silica gel is made.
The alkali alumina is using the pretreated alkali alumina of following methods：By alkali alumina 600~
After toasting 4~8h at 700 DEG C, it is fitted into ground reagent bottle, is preserved in drier.
The anhydrous sodium sulfate is by the pretreated anhydrous sodium sulfate of following methods：By anhydrous sodium sulfate use just oneself
Alkane and eluent methylene chloride 2~5 times, the solvent volume used every time are twice of anhydrous sodium sulfate volume, will be anhydrous after elution
Sodium sulphate is transferred in flask, be baked at 50 DEG C it is dry, then at 150~250 DEG C toast 8h~12h, after cooling dry
Preserved in device.
(2) chromatographic column of three dried and cleans, is taken, chromatogram column internal diameter is 1 with length ratio:8~10, according to step (1)
The order of middle each component successively pours into each filler from the upper port of chromatographic column successively, and tri- kinds of proportionings of A, B and C correspond to one respectively
Individual chromatographic column, every kind of filler allows the filler poured into tile uniform after the upper port of chromatographic column pours into, and chromatogram column wall
Non-filler adheres to, and after the completion of all fillers are filling, open the rotary-piston of chromatographic column lower end, is connect in the lower port of chromatographic column
Enter vavuum pump, then open vavuum pump, the outer wall of chromatographic column is beaten when vacuumizing, when chromatographic column inner stuffing height no longer
During decline, after continuing to vacuumize at least 3 minutes, chromatographic column lower end piston is screwed；
(3) dichloromethane slowly, is injected into chromatographic column from chromatographic column upper port along chromatogram column wall, opens chromatographic column lower end
Piston, make the flow velocity of the liquid of inflow chromatographic column maximum, make all fillers all wetted and bubble-free, when in chromatographic column
Each filler clear layer, form for the moment, stop injection dichloromethane, finally with enough n-hexane elution chromatography posts, washed
The piston of chromatographic column lower end is closed after de-.
Below to examine the feasibility and superiority of the silica gel chromatographic column of detection Polychlorinated biphenyls provided by the invention, made in breast
Product add polychlorinated biphenyl compound standard liquid, sample extraction provided by the invention will be used in the dairy products containing standard liquid
Method and silica gel purification chromatographic column are separated, and the content of the polychlorinated biphenyl compound in dairy products are detected, according to the knot of detection
The difference of fruit concentration and known organic concentration, sample extraction, purification and elution feasibility and superiority in this method are entered
Row is assessed.
Embodiment
Acidic silica gel purification chromatographic column filling is as follows in the present embodiment：Glass column bottom blocked with mineral wool after from bottom to
4g activated silica gels, 10g acidifyings silica gel, 2g activated silica gels, 4g anhydrous sodium sulfates are inserted in top successively.
Compound silica gel purification chromatographic column filling is as follows：Glass column bottom blocked with mineral wool after from bottom to top according to inserting
1.5g silver nitrates silica gel, 1g activated silica gels, 2g alkaline silica gels, 1g activated silica gels, 4g acidifyings silica gel, 2g activated silica gels, 2g are anhydrous
Sodium sulphate.
Alkali alumina purification chromatographic column filling is as follows：Glass column bottom blocked with mineral wool after from bottom to top according to filling out
Enter alkali aluminas of the 2.5g through overbaking, 2g anhydrous sodium sulfates.
Take 4.0mL mixed standard solution (PCB 1, PCB 3, PCB 4, PCB 15, PCB 19, PCB 23, PCB 34,
PCB 37、PCB 54、PCB 77、PCB 81、PCB 104、PCB 105、PCB 114、PCB 118、 PCB 123、PCB 126、
PCB 155、PCB 156、PCB 157、PCB 167、PCB 169、PCB 170、PCB 180、PCB 182、PCB 187、PCB
188th, PCB 189, PCB 202, PCB 205, PCB 206, PCB 208 and PCB 209, concentration are 20 μ g mL-1, Polychlorinated biphenyls
Isotopic Internal Standard, include homologue13C12- labelled PCBs 28,52,118,153,180,202,206 and 209, concentration are
2μg mL-1) in the dairy products sample that is added separately to, the dairy products sample carried out following pre-treatment in advance：Dairy products
Sample is put into refrigerator (- 18 DEG C) freezings, it is to be frozen completely after, frozen dairy product is put into freeze drier, freeze drier
- 20 DEG C~-40 DEG C of precooling temperature, it is freeze-dried -30 DEG C~-40 DEG C of temperature.Then surname extraction is carried out, by pretreating specimen
5.0g loads surname extraction filter cylinder and places soxhlet type apparatus, and 5h-8h is extracted in 60 DEG C of water-baths, and siphonage time is 3-4 times/h,
The sample extracting solution of concentration is made.
Rinse acid silica gel purification chromatographic column, compound silica gel purification chromatogram respectively with the mixed liquor of n-hexane and dichloromethane
Post and alkali alumina purification chromatographic column, the flow velocity of flushing is maximum, makes liquid level equal with silica gel.
Sample 0.5~1.5mL extract solutions of concentration are injected into acidic silica gel purification chromatographic column, with 80~120mL just
Hex, the flow velocity for controlling gel column is 1.0~3.0mL/min, and eluent is concentrated into 0.5~1.5mL；
Extract solution after acidic silica gel purifies chromatogram column purification is injected into compound silica gel purification chromatographic column, with 20~
50mL n-hexanes and dichloromethane are according to 97:1~97:The 4 mixed solution of volume ratio elutes in advance；Acidic silica gel will be passed through again
Concentrate eluant is fully transferred in compound silica gel purification chromatographic column after purification chromatogram column purification, and eggplant is rinsed with 3~6mL n-hexanes
Shape bottle 3 times~4 times, washing lotion is transferred on post.40~80mL n-hexanes and dichloro are added when liquid level is down to anhydrous sodium sulfate layer
Methane is according to 97:1~97:The 4 mixed solution of volume ratio is eluted, and eluent is concentrated into 0.5~1.0mL.
The extract solution that chromatogram column purification is purified through compound silica gel is injected into alkali alumina purification chromatographic column, will be through multiple
Close silica gel purification chromatogram column purification after concentrate eluant be fully transferred to alkali alumina purification chromatographic column on, with 3~6mL just oneself
Alkane rinses eggplant-shape bottle 3 times~4 times, and washing lotion is transferred on post.When liquid level is down to anhydrous sodium sulfate layer add 20~50mL just oneself
Alkane elution alkali alumina purification chromatographic column, adds the mixing of dichloromethane and n-hexane when liquid level is down to anhydrous sodium sulfate layer
Solution is eluted, then eluent is concentrated into near do.
Above-mentioned concentrate eluant is analyzed using gas chromatography-mass spectrometry, samples (5%- phenyl)-methyl polysilicon oxygen
The capillary chromatographic column of alkane filler, a small amount of mineral wool is filled with the dottle pin and graphite grazing pad of high temperature resistant low-bleed, deactivation processing
Shunt and regardless of the universal bushing pipe of stream；The program of column oven is：Maintained 2 minutes at 100 DEG C first, then with 15 DEG C of min-1Heating
Speed is raised to 180 DEG C from 100 DEG C；Then with 3 DEG C of min-1Heating rate be raised to 240 DEG C from 180 DEG C；Finally with 10 DEG C of min-1
Heating rate be raised to 285 DEG C from 240 DEG C, and maintain 10min at 285 DEG C.Total run time is 42min.Carrier gas uses high
Pure helium (purity>99.999%), constant flow rate is 1mL min-1.Sample and the sample size of standard liquid are 2.0 μ L, using not shunting
Sample introduction pattern, injector temperature are 300 DEG C.Make polychlorinated biphenyl all in matrix completely separable.Mass spectrometry parameters are：
Ionization pattern, electron bombardment ionization source (EI), energy 70eV.Ion source temperature is 230 DEG C, 150 DEG C of level Four bar temperature, transmission line temperature
Spend for 300 DEG C, solvent delay 4min.
Quantitative analysis is finally carried out, using double internal standard quanitations, 8 kinds of Polychlorinated biphenyls Isotopic Internal Standards (13C12-labelled
PCBs 28,52,118,153,180,202,206 and 209) and 2 kinds of Polychlorinated biphenyls isotopes reclaim internal standards (13C12-PCB101
、13C12- PCB194) quantify, Isotopic Internal Standard is used for calibrating the determinands of 33 kinds of Polychlorinated biphenyls.After being computed in the present embodiment
Testing result is as follows：The rate of recovery of the polychlorinated diphenyl ether (33 kinds) under 20 μ g/kg mark-on level is in dairy products：88%~
105%.
The result of the above-mentioned rate of recovery meets in european union directive (European Union document 2002/657/EC)
Related request.The rate of recovery need to be in the range of 80%~110% during 10 μ g/kg≤P 100 μ g/kg of ＜, and P refers to the concentration of determinand.
The rate of recovery that each persistent organism is can be seen that according to the result of example detection all meets european union directive
Related request in (European Union document 2002/657/EC), illustrate using multilayer silicon provided by the invention
Multilayer silica gel chromatographic column prepared by the preparation of glue purification chromatographic column and fill method, which can be used to detecting persistence in environmental sample, to be had
The content of machine thing, and high sensitivity, degree of accuracy height, favorable reproducibility and the rate of recovery are high.
Claims (2)
1. the method for Polychlorinated biphenyls, the silica gel chromatographic column are purified by acidic silica gel in a kind of post detection dairy products using silica gel chromatograph
Chromatographic column, compound silica gel purification chromatographic column and alkali alumina purification chromatographic column composition, the preparation method of each chromatographic column are as follows：
(1), each filler component is weighed according to following mass parts：
A acidic silica gels purify chromatographic column：1. 2~4 parts of activated silica gel；2. 4~6 parts of acidic silica gel；3. 1~2 part of activated silica gel；④
2~4 parts of anhydrous sodium sulfate；
B compound silica gels purify chromatographic column：1. 1~3 part of silver nitrate silica gel；2. 1~2 part of activated silica gel；3. 2~4 parts of alkaline silica gel；
4. 1~2 part of activated silica gel；5. 3~6 parts of acidic silica gel；6. 2~4 parts of activated silica gel；7. 2~4 parts of anhydrous sodium sulfate；
C alkali aluminas purify chromatographic column：1. 1~3 part of alkali alumina；2. 2~4 parts of anhydrous sodium sulfate；
(2) chromatographic column of three dried and cleans, is taken, chromatogram column internal diameter is 1 with length ratio:8~10, according to each in step (1)
The order of component successively pours into each filler from the upper port of chromatographic column successively, and tri- kinds of proportionings of A, B and C correspond to a color respectively
Post is composed, every kind of filler allows the filler that pours into tile uniform after the upper port of chromatographic column pours into, and chromatogram column wall is without filling out
Thing attachment is filled, after the completion of all fillers are filling, opens the rotary-piston of chromatographic column lower end, it is true in the lower port access of chromatographic column
Empty pump, then opens vavuum pump, and the outer wall of chromatographic column is beaten when vacuumizing, when the height of chromatographic column inner stuffing no longer declines
When, after continuing to vacuumize at least 3 minutes, screw chromatographic column lower end piston；
(3) dichloromethane slowly, is injected into chromatographic column from chromatographic column upper port along chromatogram column wall, opens the work of chromatographic column lower end
Plug, make the flow velocity of the liquid of inflow chromatographic column maximum, make all fillers all wetted and bubble-free, when respectively being filled out in chromatographic column
Fill thing clear layer, form for the moment, stop injection dichloromethane, finally with enough n-hexane elution chromatography posts, eluted
The piston of chromatographic column lower end is closed after finishing；
It is characterized in that the detection method comprises the following steps：
(1), dairy products sample, which is put into refrigerator, freezes, it is to be frozen completely after, frozen dairy product is put into freeze drier, freeze
- 20 DEG C~-40 DEG C of drying machine precooling temperature, -30 DEG C~-40 DEG C of temperature is freeze-dried, the sample after freezing loads Soxhlet
Extraction filter cylinder simultaneously places soxhlet type apparatus, and water-bath extraction 5h~8h, siphonage time is 3~4 times/h, and the sample that concentration is made carries
Take liquid；
(2) acid silica gel purification chromatographic column, compound silica gel purification chromatogram, are rinsed respectively with the mixed liquor of n-hexane and dichloromethane
Post and alkali alumina purification chromatographic column, the flow velocity of flushing is maximum, makes liquid level equal with silica gel；
(3), the sample extracting solution of concentration is injected into acidic silica gel purification chromatographic column, is eluted with n-hexane, controls gel column
Flow velocity be 1.0~3.0mL/min, eluent is concentrated into 0.5~1.5mL；
Extract solution after acidic silica gel purifies chromatogram column purification is injected into compound silica gel purification chromatographic column, with n-hexane and
Dichloromethane is according to 97:1~97:The 4 mixed solution of volume ratio elutes in advance；It is net that acidic silica gel purification chromatographic column will be passed through again
Concentrate eluant is fully transferred in compound silica gel purification chromatographic column after change；When liquid level is down to anhydrous sodium sulfate layer add just oneself
Alkane and dichloromethane are according to 97:1~97:The 4 mixed solution of volume ratio is eluted, eluent is concentrated into 0.5~
1.0mL；
The extract solution that chromatogram column purification is purified through compound silica gel is injected into alkali alumina purification chromatographic column, will be through comprehensive silicon
Concentrate eluant is fully transferred in alkali alumina purification chromatographic column after glue purification chromatogram column purification, when liquid level is down to anhydrous sulphur
N-hexane elution alkali alumina purification chromatographic column is added during sour sodium layer, dichloromethane is added when liquid level is down to anhydrous sodium sulfate layer
The mixed solution of alkane and n-hexane is eluted, then eluent is concentrated into near do；
(4), the concentrate eluant in step (3) is analyzed using gas chromatography-mass spectrometry；
(5), quantitative analysis, using double internal standard quanitations, 8 kinds of Polychlorinated biphenyls Isotopic Internal Standards：13C12-labelled PCBs 28、
52nd, 118,153,180,202,206 and 209, and 2 kinds of Polychlorinated biphenyls isotope recovery internal standards：13C12-PCB101、13C12-
PCB194's quantifies, and Isotopic Internal Standard is used for calibrating the determinand of 33 kinds of Polychlorinated biphenyls.
2. the method for Polychlorinated biphenyls in detection dairy products according to claim 1, it is characterised in that：Gas phase in step (4)
The operating parameter of chromatograph-mass spectrometer is：Sample the capillary chromatographic column of (5%- phenyl)-methyl polysiloxane filler, resistance to height
The dottle pin and graphite grazing pad of warm low-bleed, deactivation are filled with mineral wool shunting and regardless of the universal bushing pipe of stream in handling；Column oven
Program be：Maintained 2 minutes at 100 DEG C first, then 180 DEG C are raised to from 100 DEG C with 15 DEG C/min heating rate；Then with 3
DEG C/min heating rate is raised to 240 DEG C from 180 DEG C；Finally 285 DEG C are raised to from 240 DEG C with 10 DEG C/min heating rate, and
10min is maintained at 285 DEG C；Total run time is 42min；Carrier gas uses purity>99.999% high-purity helium, constant flow rate
For 1mL/min；Sample and the sample size of standard liquid are 2.0 μ L, and using Splitless injecting samples pattern, injector temperature is 300 DEG C；Mass spectrum
Instrument parameter is：Ionization pattern, electron bombardment ionization source EI, energy 70eV；Ion source temperature is 230 DEG C, 150 DEG C of level Four bar temperature,
Transmission line temperature is 300 DEG C, solvent delay 4min.
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| CN112946152B (en) * | 2019-12-11 | 2024-02-02 | 中国科学院大连化学物理研究所 | HRGC-HRMS detection method for 209 polychlorinated biphenyl homologs in animal-derived food |
| CN111089922A (en) * | 2019-12-31 | 2020-05-01 | 江苏微谱检测技术有限公司 | Sample purification method for gel permeation chromatography detection |
| CN112444576B (en) * | 2020-11-04 | 2021-12-28 | 中山大学 | Method for improving detection precision of polychlorinated biphenyl in whale fish fat and application thereof |
| CN115524428A (en) * | 2022-01-07 | 2022-12-27 | 江苏微谱检测技术有限公司 | Method for measuring indicative polychlorinated biphenyl in food |
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