CN101813677B - Method for analyzing and determining organics persistently containing chlorine in aquatic product - Google Patents
Method for analyzing and determining organics persistently containing chlorine in aquatic product Download PDFInfo
- Publication number
- CN101813677B CN101813677B CN 201010162673 CN201010162673A CN101813677B CN 101813677 B CN101813677 B CN 101813677B CN 201010162673 CN201010162673 CN 201010162673 CN 201010162673 A CN201010162673 A CN 201010162673A CN 101813677 B CN101813677 B CN 101813677B
- Authority
- CN
- China
- Prior art keywords
- aquatic products
- normal hexane
- concentrated
- chlorinated organics
- persistence
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Sampling And Sample Adjustment (AREA)
Abstract
本发明公开了一种水产品中持久性含氯有机物的分析测定方法，包括如下步骤：A)将水产品的肌肉组织进行干燥并研磨；B)索氏萃取；C)凝胶色谱净化；D)浓硫酸脱脂；E)弗罗里硅层析柱进行层析；以及F)气相色谱法测定持久性含氯有机物。本发明的方法中，样品提取及净化操作简单，溶剂耗量少，分析速度快，对40种持久性含氯有机物不仅可以准确定性还可以精确定量，检测限底，灵敏度高，检出限均低于4ng/g-lw。
The invention discloses a method for analyzing and measuring persistent chlorine-containing organic substances in aquatic products, which comprises the following steps: A) drying and grinding muscle tissue of aquatic products; B) Soxhlet extraction; C) gel chromatography purification; D ) Degreasing with concentrated sulfuric acid; E) Chromatography on a Florisil column; and F) Determination of persistent chlorine-containing organic compounds by gas chromatography. In the method of the present invention, the sample extraction and purification operations are simple, the solvent consumption is small, and the analysis speed is fast. The 40 kinds of persistent chlorine-containing organic compounds can not only be accurately qualitative but also accurately quantitative, with low detection limit, high sensitivity, and uniform detection limit. Less than 4ng/g-lw.
Description
Technical field
The invention belongs to chemical analysis field, include the analysis determining method of organic pollutants, especially the analysis determining method of persistence chlorinated organics in aquatic products.
Background technology
The persistence chlorinated organics mainly includes machine chloro pesticide (OCPs) and polychlorinated biphenyl (PCBs), and wherein benzene hexachloride (HCHs), D.D.T. (dichloro-diphenyl-trichloroethane) (DDTs), Niran, drinox, dieldrite, endrin, hexachloro-benzene (HCB), polychlorinated biphenyl (PCBs) etc. have been put into about the Convention of Stockholm of persistence organic pollutant (POPs) and the priority pollutants blacklist of countries in the world.Organo-chlorine pesticide is mainly used in preventing and treating the harmful organism in agricultural production, and polychlorinated biphenyl is widely used in the fields such as power industry, Plastics Processing Industry, chemical industry and printing because of its good chemical inertness.Organo-chlorine pesticide in use, polychlorinated biphenyl is accompanied by the use of household electrical appliances, discarded and removal process all is discharged in surrounding environment in a large number, and the ecosystem and human health are formed potential hazard.They have been used as the persistence poisonous and harmful substance of a quasi-representative at present, receive people's concern.
Along with the raising of China's living standards of the people, fish aquatic products shared ratio in eating patterns is more and more higher.Because China's Inland Water and immediate offshore area are generally polluted, so the safety problem of edible fishes aquatic products can not be ignored.In recent years, quality testing department is mainly microbiotic and heavy metal higher around content, that easily detect for the detection of fish aquatic products chemical pollutant, seldom carries out system for persistence organic pollutant and detects.Complicated due to the pollutant component in the fish aquatic products, the chlorinated organics kind many and many places in the trace level, so the efficient extraction of fish aquatic products is the difficult point that in the fish aquatic products, the persistence chlorinated organics is analyzed with effectively separate and the Accurate Determining of purification, multiple trace chlorinated organics always.
The abstraction technique of solid sample mainly contains at present: soxhlet extraction, microwave auxiliary extraction, ultrasonic extraction, accelerated solvent extraction, pressurized liquid extraction and supercritical fluid extraction.Wherein soxhlet extraction is the most classical, and the scope of application is wider, and the recovery is higher, and reappearance is stable.But extraction time is longer, and the use amount of solvent is larger.With respect to soxhlet extraction, other extracting process is improving to some extent aspect extraction time and solvent use amount, but have deficiency separately, for example low pole or nonpolar organic matter all nonpolar extractants when extraction are not high to the microwave energy utilization factor during microwave auxiliary extraction yet; Ultrasonic extraction easily makes organic substance decomposing of less stable etc.Sample purification aspect after extraction mainly contains aluminium oxide purification, Fu Luoli silica purge, silica gel purification, gel infiltration purification etc.For purifying good analytic sample, the method for the outer main employing gas chromatography/electron capture detector (GC/ECD) of Present Domestic coupling is carried out separation and the mensuration of chlorinated organics.
Yet there are no the report of measuring for chlorinated organics analysis in the fish aquatic products.The difficulty of carrying out the existence of described analysis mensuration comprises: 1, the content of chlorinated organics in the fish aquatic products is trace, and the detectability of instrument does not reach usually; 2, in whole flow process, can the recovery of chlorine-containing compound desirable, and namely the reliability of method can not guarantee; 3, the background of chlorine-containing compound complicated (being that the interference of a lot of compounds is arranged in the biosome such as fish), can not effectively remove the impurity chaff interference).
Summary of the invention
The present invention is directed to the analysis determining method that persistence chlorinated organics in aquatic products is not also arranged in prior art, and the analysis determining method of persistence chlorinated organics in a kind of aquatic products is provided.Because organic interference in aquatic products especially fish aquatic products is more, impurity is thoroughly purified have higher requirement.Gel chromatography and Fu Luoli silicon layer are analysed column purification aquatic products sample organic extract liquid, the polarity and the nonpolar chaff interference that bring when extracting to remove, have many advantages: gel chromatography is removed aquatic products, and especially large molecule interfering material is effective in the fish aquatic products, automaticity is high, and the batch self-purging that is fit to a plurality of samples is processed; The Fu Luoli silicon layer analyses that column purification efficient is high, the pillar commercialized degree is high, technology maturation, be easy to get, and both coupling adds that the sulfuric acid degreasing can realize aquatic products especially thorough degreasing and the purification of fish aquatic products sample extraction liquid.
In aquatic products of the present invention, the analysis determining method of persistence chlorinated organics comprises the steps:
A) musculature of aquatic products is carried out drying and grinding;
B) soxhlet extraction;
C) GPC cleanup system;
D) concentrated sulphuric acid degreasing;
E) Fu Luoli silicon chromatographic column carries out chromatography; And
F) gas chromatography determination persistence chlorinated organics.
Wherein, in steps A) in, the musculature of aquatic products is carried out freeze drying and is ground with agate mortar.
At step B) in, after soxhlet extraction after filtering with the absorbent cotton that undertakes anhydrous sodium sulfate, to remove a small amount of moisture and solid impurity; Wherein, soxhlet extraction adopt volume ratio be 1～1.5: 1 normal hexane with acetone mixed solvent as extractant, Soxhlet extraction apparatus temperature of heating plate is 60～70 ℃, automatic extraction time is 960～1440min.
At step C) in, GPC cleanup system comprises that single concentration process and two connects the machine process, two processes can be completed with two log on procedures automatically by the list in gel permeation chrommatograph is concentrated, and then nitrogen blows concentrated.
Step D) concentrated sulphuric acid degreasing in is specially: to step C) add normal hexane in the scavenging solution that makes, and process further removal lipid with the concentrated sulphuric acid, and centrifuging, water extracts 2 times with normal hexane again, merges organic phase, and nitrogen blows concentrated.
Step e) chromatography in is specially: add the skim anhydrous sodium sulfate on Fu Luoli silicon chromatographic column, successively clean the activation chromatographic column with acetone and normal hexane; Loading is the normal hexane of 9: 1 and the mixed liquor wash-out of acetone with volume ratio, collects eluent; The wash-out liquid nitrogen blows, then adds normal hexane continuation nitrogen to blow, triplicate, last constant volume.
Step F) in, gas chromatography determination persistence chlorinated organics carries out qualitative and quantitative detection with the gas chromatograph that is equipped with electron capture detector, is specially: separate on (5% phenyl) methyl polysiloxane HP-5 45m * 300um * nonpolar chromatographic column of 0.22um; Carrier gas is high-purity helium, constant voltage 10psi; 260 ℃ of injector temperatures; 310 ℃ of detector temperatures; Column temperature is initially 80 ℃ and keep 2min, then the speed with 20 ℃/min rises to 150 ℃, continuation rises to 190 ℃ with the speed of 4 ℃/min, then the speed with 1 ℃/min is warming up to 210 ℃, the speed of 2 ℃/min rises to 230 ℃, speed with 30 ℃/min rises to 300 ℃ at last, and keeps 4min at 300 ℃; Without shunting auto injection 1 μ L; Calculate the concentration of persistence chlorinated organics in aquatic products with chromatographic peak area under each compound retention time.
In the present invention, described aquatic products are fish, shrimps or shellfish aquatic products.
Positive progressive effect of the present invention is:
1, aquatic products sample pretreating method of the present invention can not only effectively extract the target chlorinated organics, and the recovery is high, up to 68.9%-79.1%, and can thoroughly remove the polarity of the complexity that coextraction brings and the impact of nonpolar organic impurities;
2, gas chromatography of the present invention both can carry out qualitative examination to the chlorinated organics in aquatic products, can carry out quantitative test again.Especially to the multiple isomers in 40 kinds of chlorinated organics, but accurate qualitative accurate quantification again not only;
3, treatment scheme automaticity of the present invention is high, and analysis speed is fast, and manual labor is saved, and is fit to the batch processing of a plurality of samples, and the sample collimation is good, and reappearance is high, and analysis determining method is reliable;
4, the present invention is suitable for the analysis mensuration of trace persistence chlorinated organics in aquatic products, detectability is low, highly sensitive, the detection limit of 40 kinds of chlorinated organics is all lower than 4ng/g-lw (ng/g-fat is heavy, i.e. the aquatic products nanogram number of contained chlorinated organics in every gram fat in the fish aquatic products especially).
Description of drawings
Fig. 1 is schematic flow sheet of the present invention
Fig. 2 A is that in the wild silverfish body in lake, Huzhou City of Zhejiang Province South Pacific, the chlorinated organics chromatogram is always schemed;
Fig. 2 B is that in Fig. 2 A, retention time is the chromatogram enlarged drawing at 13 ~ 19min section place;
Fig. 2 C is that in Fig. 2 A, retention time is the chromatogram enlarged drawing at 26 ~ 38min section place;
Fig. 3 A is that in the wild whitefish body in lake, Huzhou City of Zhejiang Province South Pacific, the chlorinated organics chromatogram is always schemed;
Fig. 3 B is that in Fig. 3 A, retention time is the chromatogram enlarged drawing at 14.5～18min section place;
Fig. 3 C is that in Fig. 3 A, retention time is the chromatogram enlarged drawing at 22～27min section place;
Fig. 3 D is that in Fig. 3 A, retention time is the chromatogram enlarged drawing at 30～36min section place;
Fig. 4 A is that in certain fish musculature of providing of UNEP (United Nations Environment Program) (UNEP), the chlorinated organics chromatogram is always schemed;
Fig. 4 B is that in Fig. 4 A, retention time is the chromatogram enlarged drawing at 14.5～16.25min section place;
Fig. 4 C is that in Fig. 4 A, retention time is the chromatogram enlarged drawing at 17～22min section place;
Fig. 4 D is that in Fig. 4 A, retention time is the chromatogram enlarged drawing at 26～36min section place; And
Fig. 4 E is that in Fig. 4 A, retention time is the chromatogram enlarged drawing at 38 ~ 50min section place.
Embodiment
Embodiment 1
Use the present invention that the wild silverfish in lake, Huzhou City of Zhejiang Province South Pacific is analyzed, measure the wherein contamination of chlorinated organics.
Take out the silverfish sample of-20 ℃ of preservations from refrigerator, thaw under normal temperature.Full fish freeze drying 48h, dry rear sample grinds with agate mortar.
Electronic balance accurately takes two parts, 3.0g sample, with the continuous soxhlet extraction of the mixed liquor (volume ratio is 1: 1) of 100mL normal hexane and acetone.Soxhlet extraction apparatus temperature of heating plate is 63 ℃, and extraction time is 960min automatically.A extract adopts gravimetric determination silverfish fat content, and the absorbent cotton that another part use undertakes anhydrous sodium sulfate filters, and removes a small amount of moisture and solid impurity.
Then extract advances gel permeation chrommatograph and purifies, and to remove the macromolecule material, solvent is concentrated into 8mL in single concentrated program process, replaces and concentrate with normal hexane at two log on procedure Solvents to be settled to 4mL; Then scavenging solution again nitrogen blow and be concentrated into approximately 1mL.
Add the 3mL normal hexane, then process further degreasing with the 3mL concentrated sulphuric acid, centrifuging, water continues to extract twice with the 3mL normal hexane, merges organic phase, and nitrogen blows and is concentrated into approximately 1mL.
First clean the commercial Fu Luoli silicon pillar of activation with 5mL acetone, then clean activation with the 5mL normal hexane, discard cleaning fluid; Then the extract of the concentrated sulphuric acid being processed is crossed pillar, and sample bottle is crossed post after cleaning with a small amount of normal hexane; Then use mixed liquor (volume ratio is 9: 1) the drip washing pillar of 5mL normal hexane and acetone, collect three parts and cross post efflux and soft nitrogen and blow and be concentrated into approximately 1mL.Add the 5mL normal hexane again nitrogen blow and be concentrated into approximately 1mL, this step triplicate, concentrated constant volume is 100 μ L at last.
Adopt Agilent7890 type gas chromatography and this sample of electron capture detector (ECD) (ECD) quantitative measurement.Testing sample separates on the nonpolar chromatographic column of (5% phenyl) methyl polysiloxane Agilent HP-5; Carrier gas is high-purity helium, constant voltage 10psi; 260 ℃ of injector temperatures; 310 ℃ of detector temperatures; Column temperature is initially 80 ℃, keeps 2min, rises to 150 ℃ with the speed of 20 ℃/min, continuation rises to 190 ℃ with the speed of 4 ℃/min, and then the speed with 1 ℃/min is warming up to 210 ℃, and the speed of 2 ℃/min rises to 230 ℃, speed with 30 ℃/min rises to 300 ℃ at last, keeps 4min; Without shunting auto injection 1 μ L.On the basis of each chlorinated organics chromatographic retention, be analyzed according to the chromatographic peak data that obtain and the standard colour chart peak data of each chlorinated organics, judge whether to contain this kind chlorinated organics.Press the content of each chlorinated organics of chromatogram peak height quantitative test under each retention time.Chromatogram the results are shown in Figure 2.Measurement result is: detect HCB at 15.568min, concentration is 8.00ng/g-lw; 15.728min detect PCA (pentachlorobenzene methyl ether), concentration is 5.47ng/g-lw; 17.643min detect δ-HCH, concentration is 3.63ng/g-lw; 27.453min detect o, p '-DDE, concentration is 11.0ng/g-lw; 30.314min detect p, p '-DDE, concentration is 186ng/g-lw; 34.457min detect p, p '-DDD, concentration is 18.9ng/g-lw; 34.729min detect o, p '-DDT, concentration is 14.3ng/g-lw; 35.819min detect CB153, concentration is 6.78ng/g-lw; 38.382min detect p, p '-DDT, concentration is 18.3ng/g-lw.
Use the present invention that the wild whitefish in lake, Huzhou City of Zhejiang Province South Pacific is analyzed, measure the wherein contamination of chlorinated organics.
Take out the whitefish sample of-20 ℃ of preservations from refrigerator, thaw under normal temperature.Get the whitefish muscle of back, freeze drying 48h.After dry, sample grinds with agate mortar.
Electronic balance accurately takes two parts, 3.0g sample, with the continuous soxhlet extraction of the mixed liquor (volume ratio is 1: 1) of 100mL normal hexane and acetone.Soxhlet extraction apparatus temperature of heating plate is 63 ℃, and extraction time is 960min automatically.A extract adopts gravimetric determination whitefish fat content, and the absorbent cotton that another part use undertakes anhydrous sodium sulfate filters, and removes a small amount of moisture and solid impurity.
Then extract advances gel permeation chrommatograph and purifies, and to remove the macromolecule material, solvent is concentrated into 8mL in single concentrated program process, replaces and concentrate with normal hexane at two log on procedure Solvents to be settled to 4mL; Then scavenging solution again nitrogen blow and be concentrated into approximately 1mL.
Add the 3mL normal hexane, then process further degreasing with the 3mL concentrated sulphuric acid, centrifuging, water continues to extract twice with the 3mL normal hexane, merges organic phase, and nitrogen blows and is concentrated into approximately 1mL.
First clean activation Fu Luoli silicon pillar with 5mL acetone, then clean activation with the 5mL normal hexane, discard cleaning fluid; Then the extract of the concentrated sulphuric acid being processed is crossed pillar, and sample bottle is crossed post after cleaning with a small amount of normal hexane; Then use mixed liquor (volume ratio is 9: 1) the drip washing pillar of 5mL normal hexane and acetone, collect three parts and cross post efflux and soft nitrogen and blow and be concentrated into approximately 1mL.Add the 5mL normal hexane again nitrogen blow and be concentrated into approximately 1mL, this step triplicate, concentrated constant volume is 100 μ L at last.
Adopt Agilent7890 type gas chromatography and this sample of ECD electron capture detector (ECD) quantitative measurement.Testing sample separates on the nonpolar chromatographic column of (5% phenyl) methyl polysiloxane Agilent HP-5; Carrier gas is high-purity helium, constant voltage 10psi; 260 ℃ of injector temperatures; 310 ℃ of detector temperatures; Column temperature is initially 80 ℃ (keeping 2min), speed with 20 ℃/min rises to 150 ℃, continuation rises to 190 ℃ with the speed of 4 ℃/min, then the speed with 1 ℃/min is warming up to 210 ℃, the speed of 2 ℃/min rises to 230 ℃, speed with 30 ℃/min rises to 300 ℃ at last, (keeping 4min); Without shunting auto injection 1 μ L.On the basis of each chlorinated organics chromatographic retention, be analyzed according to the chromatographic peak data that obtain and the standard colour chart peak data of each chlorinated organics, judge whether to contain this kind chlorinated organics.Press the content of each chlorinated organics of chromatogram peak height quantitative test under each retention time.Chromatogram the results are shown in Figure 3.Measurement result is: detect HCB (hexachloro-benzene) at 15.561min, concentration is 23.3ng/g-lw; Detect PCA (pentachlorobenzene methyl ether) at 15.729min, concentration is 20.2ng/g-lw; 16.557min detect γ-HCH, concentration is 16.6ng/g-lw; 17.645min detect δ-HCH, concentration is 60.3ng/g-lw; 22.575min detect CB44, concentration is 299ng/g-lw; 27.391min detect o, p '-DDE, concentration is 23.7ng/g-lw; 30.241min detect p, p '-DDE, concentration is 681ng/g-lw; 30.987min detect o, p '-DDD, concentration is 108ng/g-lw; 34.373min detect p, p '-DDD, concentration is 63.6ng/g-lw; 35.815min detect CB153, concentration is 44.7ng/g-lw.
Use the present invention that certain fish musculature that UNEP (United Nations Environment Program) (UNEP) provides is analyzed, measure the wherein contamination of chlorinated organics.
Electronic balance accurately takes the 2.5g sample after drying and grinding, with the mixed liquor (volume ratio is 1: 1) of 100mL normal hexane and acetone soxhlet extraction continuously.Soxhlet extraction apparatus temperature of heating plate is 63 ℃, and extraction time is 960min automatically.Extract filters with the absorbent cotton that undertakes anhydrous sodium sulfate, removes a small amount of moisture and solid impurity.
Then extract advances gel permeation chrommatograph and purifies, and to remove the macromolecule material, solvent is concentrated into 8mL in single concentrated program process, replaces and concentrate with normal hexane at two log on procedure Solvents to be settled to 4mL; Then scavenging solution again nitrogen blow and be concentrated into approximately 1mL.
Add the 3mL normal hexane, then process further degreasing with the 3mL concentrated sulphuric acid, centrifuging, water continues to extract twice with the 3mL normal hexane, merges organic phase, and nitrogen blows and is concentrated into approximately 1mL.
First clean activation Fu Luoli silicon pillar with 5mL acetone, then clean activation with the 5mL normal hexane, discard cleaning fluid; Then the extract of the concentrated sulphuric acid being processed is crossed pillar, and sample bottle is crossed post after cleaning with a small amount of normal hexane; Then use mixed liquor (volume ratio is 9: 1) the drip washing pillar of 5mL normal hexane and acetone, collect three parts and cross post efflux and soft nitrogen and blow and be concentrated into approximately 1mL.Add the 5mL normal hexane again nitrogen blow and be concentrated into approximately 1mL, this step triplicate, concentrated constant volume is 100 μ L at last.
Adopt Agilent7890 type gas chromatography and this sample of ECD electron capture detector (ECD) quantitative measurement.Testing sample separates on the nonpolar chromatographic column of (5% phenyl) methyl polysiloxane Agilent HP-5; Carrier gas is high-purity helium, constant voltage 10psi; 260 ℃ of injector temperatures; 310 ℃ of detector temperatures; Column temperature is initially 80 ℃ (keeping 2min), speed with 20 ℃/min rises to 150 ℃, continuation rises to 190 ℃ with the speed of 4 ℃/min, then the speed with 1 ℃/min is warming up to 210 ℃, the speed of 2 ℃/min rises to 230 ℃, speed with 30 ℃/min rises to 300 ℃ at last, (keeping 4min); Without shunting auto injection 1 μ L.On the basis of each chlorinated organics chromatographic retention, be analyzed according to the chromatographic peak data that obtain and the standard colour chart peak data of each chlorinated organics, judge whether to contain this kind chlorinated organics.Press the content of each chlorinated organics of chromatogram peak height quantitative test under each retention time.Chromatogram the results are shown in Figure 4.Measurement result is: detect HCB (hexachloro-benzene) at 15.568min, concentration is 2.99ng/g-dw; 19.271min detect CB28, concentration is 4.22ng/g-dw; 21.258min detect CB52, concentration is 13.8ng/g-dw; 22.576min detect CB44, concentration is 9.6ng/g-dw; 27.432min detect o, p '-DDE, concentration is 26.2ng/g-dw; 30.291min detect p, p '-DDE, concentration is 61.5ng/g-dw; 32.101min detect endrin, concentration is 27.0ng/g-dw; 33.005min detect 5a,6,9,9a-hexahydro-6,9-methano-2,4 II, concentration is 13.8ng/g-dw; 33.291min detect CB149, concentration is 80.9ng/g-dw; 33.481min detect CB118, concentration is 105ng/g-dw; 34.438min detect p, p '-DDD, concentration is 85.0ng/g-dw; 35.248min detect CB146, concentration is 34.6ng/g-dw; 35.887min detect CB153, concentration is 195ng/g-dw; 38.331min detect p, p '-DDT, concentration is 125ng/g-dw; 38.698min detect CB138, concentration is 174ng/g-dw; 40.950min detect CB183, concentration is 38.4ng/g-dw; 45.532min detect CB180, concentration is 136ng/g-dw; 46.934min detect CB170, concentration is 37.6ng/g-dw; 50.184min detect CB209, concentration is 8.56ng/g-dw.
The present invention is on the basis that has overcome described 3 difficulties of background technology, and nearly 40 kinds of the chlorinated organics kinds that can detect comprise organo-chlorine pesticide and the large class of polychlorinated biphenyl two, and it is separately a great problem on chromatogram.In order to solve the qualitative question of 40 kinds of compounds, this research connects HP-5 post (30 meters long) and HT-5 post (15 meters long), both effectively separates just reached object, also all can go out the effect at peak.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and in the General Principle of this explanation is applied to other embodiment and needn't pass through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not breaking away from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (3)
1. the analysis determining method of persistence chlorinated organics in aquatic products, is characterized in that: comprise the steps:
A) musculature of aquatic products is carried out drying and grinding;
B) soxhlet extraction; Filter with the absorbent cotton that undertakes anhydrous sodium sulfate again after soxhlet extraction; Wherein, soxhlet extraction adopt volume ratio be 1～1.5: 1 normal hexane with acetone mixed solvent as extractant, Soxhlet extraction apparatus temperature of heating plate is 60～70 ℃, automatic extraction time is 960～1440min;
C) GPC cleanup system; Then extract advances gel permeation chrommatograph and purifies, and to remove the macromolecule material, solvent is concentrated in single concentrated program process, replaces and concentrates with normal hexane at two log on procedure Solvents; Then scavenging solution again nitrogen blow concentrated;
D) concentrated sulphuric acid degreasing;
E) Fu Luoli silicon chromatographic column carries out chromatography; Add the skim anhydrous sodium sulfate on Fu Luoli silicon chromatographic column, successively clean the activation chromatographic column with acetone and normal hexane; Loading is the normal hexane of 9: 1 and the mixed liquor wash-out of acetone with volume ratio, collects eluent; The wash-out liquid nitrogen blows, then adds normal hexane continuation nitrogen to blow, triplicate, last constant volume; And
F) gas chromatography determination persistence chlorinated organics; Gas chromatography determination persistence chlorinated organics carries out qualitative and quantitative detection with the gas chromatograph that is equipped with electron capture detector: separate on (5% phenyl) methyl polysiloxane HP-5 45m * 300um * nonpolar chromatographic column of 0.22um; Carrier gas is high-purity helium, constant voltage 10psi; 260 ℃ of injector temperatures; 310 ℃ of detector temperatures; Column temperature is initially 80 ℃ and keep 2min, then the speed with 20 ℃/min rises to 150 ℃, continuation rises to 190 ℃ with the speed of 4 ℃/min, then the speed with 1 ℃/min is warming up to 210 ℃, the speed of 2 ℃/min rises to 230 ℃, speed with 30 ℃/min rises to 300 ℃ at last, and keeps 4min at 300 ℃; Without shunting auto injection 1 μ L; Calculate the concentration of persistence chlorinated organics in aquatic products with chromatographic peak area under each compound retention time;
Described aquatic products are fish, shrimps or shellfish aquatic products.
2. the analysis determining method of persistence chlorinated organics in aquatic products as claimed in claim 1, is characterized in that: in steps A) in, the musculature of aquatic products is carried out freeze drying and is ground with agate mortar.
3. the analysis determining method of persistence chlorinated organics in aquatic products as claimed in claim 1, it is characterized in that: the concentrated sulphuric acid defatting step step D) is: to step C) add normal hexane in the scavenging solution that makes, and process further removal lipid with the concentrated sulphuric acid, centrifuging, water extracts 2 times with normal hexane again, merge organic phase, nitrogen blows concentrated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010162673 CN101813677B (en) | 2010-04-29 | 2010-04-29 | Method for analyzing and determining organics persistently containing chlorine in aquatic product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010162673 CN101813677B (en) | 2010-04-29 | 2010-04-29 | Method for analyzing and determining organics persistently containing chlorine in aquatic product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101813677A CN101813677A (en) | 2010-08-25 |
| CN101813677B true CN101813677B (en) | 2013-06-05 |
Family
ID=42620988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010162673 Expired - Fee Related CN101813677B (en) | 2010-04-29 | 2010-04-29 | Method for analyzing and determining organics persistently containing chlorine in aquatic product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101813677B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103331038B (en) * | 2013-07-03 | 2015-04-15 | 大连海事大学 | Separation column packing for separating PCBs or OCPs and separation method |
| CN105572280B (en) * | 2015-12-14 | 2022-06-14 | 中国环境科学研究院 | Method for fractionating fat from animal samples |
| CN106323689B (en) * | 2016-08-22 | 2020-02-21 | 中国食品发酵工业研究院有限公司 | A Water Quality Monitoring-Oriented Trap for Trace Polar Organic Pollutants |
| CN106840806B (en) * | 2017-03-28 | 2023-07-14 | 山东省分析测试中心 | System and method for preparing adsorbable organic halide sample |
| CN107328906A (en) * | 2017-08-24 | 2017-11-07 | 山东省城市供排水水质监测中心 | The assay method of total organic content in a kind of water |
| CN108196020A (en) * | 2017-12-19 | 2018-06-22 | 浙江省海洋水产研究所 | The separation method of persistence organic pollutant in a kind of aquatic products |
| CN110161144A (en) * | 2019-06-13 | 2019-08-23 | 中国水产科学研究院黄海水产研究所 | Method for detecting residual quantity of organochlorine and pyrethroid pesticides in food |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6133740A (en) * | 1996-01-30 | 2000-10-17 | Valco Instrument Co., Inc | Chlorine specific gas chromatographic detector |
| JP2001004611A (en) * | 1999-06-25 | 2001-01-12 | Toyo Ink Mfg Co Ltd | Selective solid phase extraction method |
| JP2001296291A (en) * | 2000-02-09 | 2001-10-26 | Tosoh Corp | Measurement method of dioxin concentration in fly ash |
| JP3255957B2 (en) * | 1992-02-20 | 2002-02-12 | 株式会社デンソー | Automotive electronic control unit |
| CN1341855A (en) * | 2001-08-23 | 2002-03-27 | 中国科学院南京土壤研究所 | Determination method of trace organic chlorine pesticide and polychlorobiphenyl residual amount |
| CN1563976A (en) * | 2004-03-24 | 2005-01-12 | 南京大学 | Synchronous purifying and extracting process for analysis of organic chlorine and organic phosphorus pesticide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03255957A (en) * | 1990-03-06 | 1991-11-14 | Tokico Ltd | Chlorine amount measuring device |
-
2010
- 2010-04-29 CN CN 201010162673 patent/CN101813677B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3255957B2 (en) * | 1992-02-20 | 2002-02-12 | 株式会社デンソー | Automotive electronic control unit |
| US6133740A (en) * | 1996-01-30 | 2000-10-17 | Valco Instrument Co., Inc | Chlorine specific gas chromatographic detector |
| JP2001004611A (en) * | 1999-06-25 | 2001-01-12 | Toyo Ink Mfg Co Ltd | Selective solid phase extraction method |
| JP2001296291A (en) * | 2000-02-09 | 2001-10-26 | Tosoh Corp | Measurement method of dioxin concentration in fly ash |
| CN1341855A (en) * | 2001-08-23 | 2002-03-27 | 中国科学院南京土壤研究所 | Determination method of trace organic chlorine pesticide and polychlorobiphenyl residual amount |
| CN1563976A (en) * | 2004-03-24 | 2005-01-12 | 南京大学 | Synchronous purifying and extracting process for analysis of organic chlorine and organic phosphorus pesticide |
Non-Patent Citations (4)
| Title |
|---|
| 孔祥盈.气相色谱测定水产品中六六六和滴滴涕的残留.《食品研究与开发》.2005,第26卷(第2期), |
| 微波萃取气相色谱法测定鱼肉中有机氯残留;郑林 等;《四川理工学院学报(自然科学版)》;20100228;第23卷(第1期);62-65 * |
| 气相色谱测定水产品中六六六和滴滴涕的残留;孔祥盈;《食品研究与开发》;20050430;第26卷(第2期);138-141 * |
| 郑林 等.微波萃取气相色谱法测定鱼肉中有机氯残留.《四川理工学院学报(自然科学版)》.2010,第23卷(第1期), |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101813677A (en) | 2010-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101813677B (en) | Method for analyzing and determining organics persistently containing chlorine in aquatic product | |
| Jen et al. | Determination of phthalate esters from food-contacted materials by on-line microdialysis and liquid chromatography | |
| CN102980961B (en) | Pretreatment method of detection on malachite green, crystal violet and residues of malachite green and crystal violet in eels | |
| CN102841161B (en) | Gas chromatography-mass spectrometric detection method for octyl phenol and nonyl phenol in aquatic products | |
| CN104076109B (en) | The Simultaneously test method of seven kinds of indicative polychlorinated biphenyl in high fat content food | |
| RO129027B1 (en) | Method of multi-residual determination of phthalates in food milk samples by ultrasonic extraction, micro-extraction in solid phase in headspace and gas chromatography coupled with mass spctrometry () | |
| CN109521160A (en) | Heavy metal quick screening method in a kind of solid waste Leaching | |
| CN105203654A (en) | Method for measuring content of 11 illegally added medicaments in veterinary drug powder | |
| CN108680687A (en) | The detection method of Polychlorinated biphenyls in a kind of marine product | |
| CN114002362B (en) | Pretreatment device and pretreatment method applied to food polyphenol detection | |
| Demirhan et al. | Overview of green sample preparation techniques in food analysis | |
| Zhang et al. | Determination of chloramphenicol residues in aquatic products using immunoaffinity column cleanup and high performance liquid chromatography with ultraviolet detection | |
| CN102955008B (en) | A method for the detection of sulfa drug residues in eels by pressurized capillary electrochromatography | |
| CN108459112B (en) | Method for detecting content of organochlorine pesticide in crab cream of Eriocheir sinensis | |
| Schenck et al. | Determination of organochlorine pesticide and polychlorinated biphenyl residues in fatty fish by tandem solid-phase extraction cleanup | |
| CN104713974A (en) | Method for determining 55 kinds of pesticide residues in vegetable | |
| CN104880522A (en) | Method for determining residual quantity of chloramphenicol in bee wax by n-hexane pre-treatment-high performance liquid chromatography-tandem mass spectrometry | |
| Mohammad et al. | Simultaneous extraction of polycyclic aromatic hydrocarbons through the complete dissolution of solid biological samples in sodium hydroxide/urea/thiourea aqueous solution | |
| CN106770725B (en) | A kind of method of dinocap residual quantity in quick measurement vegetable and fruit | |
| CN102507802B (en) | A method for extracting residual pyrethroid pesticides in water environment | |
| Chau et al. | Column Chromatographic Determination of Mirex, Photomirex, and Poly chlorinated Biphenyls in Lake Sediments | |
| Thibaud et al. | An international intercalibration for methylmercury in biological tissue | |
| CN108107119A (en) | A kind of method for detecting Determination of Chloramphenicol Residues In Aquatic Products By Charm Ii | |
| Ji et al. | Determination of berberine in Rhizoma coptidis and its preparations by non‐aqueous capillary electrophoresis | |
| CN108872139A (en) | Organophosphorus pesticide detection method in a kind of vegetable and fruit |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130605 Termination date: 20160429 |