CN105699515B - The assay method of the agricultural chemicals such as Rogor in a kind of Xinhui tangerine peel and product - Google Patents
The assay method of the agricultural chemicals such as Rogor in a kind of Xinhui tangerine peel and product Download PDFInfo
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- 239000003905 agrochemical Substances 0.000 title claims abstract description 15
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000003556 assay Methods 0.000 title claims abstract description 6
- 241000675108 Citrus tangerina Species 0.000 title abstract 3
- 238000000605 extraction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000000746 purification Methods 0.000 claims abstract description 13
- -1 chlopyrifos Chemical compound 0.000 claims abstract description 9
- 239000005949 Malathion Substances 0.000 claims abstract description 5
- YASYVMFAVPKPKE-UHFFFAOYSA-N acephate Chemical compound COP(=O)(SC)NC(C)=O YASYVMFAVPKPKE-UHFFFAOYSA-N 0.000 claims abstract description 5
- OEBRKCOSUFCWJD-UHFFFAOYSA-N dichlorvos Chemical compound COP(=O)(OC)OC=C(Cl)Cl OEBRKCOSUFCWJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- JXSJBGJIGXNWCI-UHFFFAOYSA-N diethyl 2-[(dimethoxyphosphorothioyl)thio]succinate Chemical compound CCOC(=O)CC(SP(=S)(OC)OC)C(=O)OCC JXSJBGJIGXNWCI-UHFFFAOYSA-N 0.000 claims abstract description 5
- RIZMRRKBZQXFOY-UHFFFAOYSA-N ethion Chemical compound CCOP(=S)(OCC)SCSP(=S)(OCC)OCC RIZMRRKBZQXFOY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229960000453 malathion Drugs 0.000 claims abstract description 5
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- BULVZWIRKLYCBC-UHFFFAOYSA-N phorate Chemical compound CCOP(=S)(OCC)SCSCC BULVZWIRKLYCBC-UHFFFAOYSA-N 0.000 claims abstract description 5
- PZXOQEXFMJCDPG-UHFFFAOYSA-N omethoate Chemical compound CNC(=O)CSP(=O)(OC)OC PZXOQEXFMJCDPG-UHFFFAOYSA-N 0.000 claims abstract description 4
- JYQUHIFYBATCCY-UHFFFAOYSA-N quinalphos Chemical compound C1=CC=CC2=NC(OP(=S)(OCC)OCC)=CN=C21 JYQUHIFYBATCCY-UHFFFAOYSA-N 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 84
- 239000000945 filler Substances 0.000 claims description 43
- 239000000523 sample Substances 0.000 claims description 43
- 241001672694 Citrus reticulata Species 0.000 claims description 33
- 239000002048 multi walled nanotube Substances 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000006228 supernatant Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000000575 pesticide Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 238000002955 isolation Methods 0.000 claims description 12
- 239000012224 working solution Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 8
- 238000004817 gas chromatography Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000012488 sample solution Substances 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000004364 calculation method Methods 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000000567 combustion gas Substances 0.000 claims description 2
- 238000010812 external standard method Methods 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 238000005374 membrane filtration Methods 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 241001122767 Theaceae Species 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical group CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000011068 loading method Methods 0.000 claims 1
- NNKVPIKMPCQWCG-UHFFFAOYSA-N methamidophos Chemical compound COP(N)(=O)SC NNKVPIKMPCQWCG-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000447 pesticide residue Substances 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 2
- 238000004445 quantitative analysis Methods 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 238000004451 qualitative analysis Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 12
- 238000001514 detection method Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 244000269722 Thea sinensis Species 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ACBXSZJPFWBZDR-UHFFFAOYSA-N [P].[S].N1=CC=CC2=CC=CC=C12 Chemical compound [P].[S].N1=CC=CC2=CC=CC=C12 ACBXSZJPFWBZDR-UHFFFAOYSA-N 0.000 description 2
- 229930013930 alkaloid Natural products 0.000 description 2
- 150000003797 alkaloid derivatives Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000003993 organochlorine pesticide Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 101100478118 Caenorhabditis elegans spe-4 gene Proteins 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- 244000273928 Zingiber officinale Species 0.000 description 1
- 235000006886 Zingiber officinale Nutrition 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229930003944 flavone Natural products 0.000 description 1
- 150000002213 flavones Chemical class 0.000 description 1
- 235000011949 flavones Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000008397 ginger Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000008216 herbs Nutrition 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YTJSFYQNRXLOIC-UHFFFAOYSA-N octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[SiH3] YTJSFYQNRXLOIC-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
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
- G01N30/14—Preparation by elimination of some components
-
- 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
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas 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
- G01N2030/062—Preparation extracting sample from raw material
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The assay method of the agricultural chemicals such as Rogor in a kind of Xinhui tangerine peel and product, the agricultural chemicals are DDVP, acephatemet, orthene, thimet, omethoate, Rogor, chlopyrifos, malathion, parathion, quinalphos, Ethodan, and methods described includes：The making of standard curve, sample extraction, sample purification and sample measure, the present invention has the advantages of quick, high sensitivity, strong anti-matrix interference ability simple to operate, suitable for Xinhui tangerine peel and its qualitative and quantitative analysis of product Pesticide Residues.
Description
Technical field
The present invention relates to the Detection Technologies of Pesticide Residues field, the agricultural chemicals such as Rogor in more particularly to a kind of Xinhui tangerine peel and product
Assay method.
Background technology
Xinhui tangerine peel is all good famous local speciality of rare integration of drinking and medicinal herbs, nourishment maintenance, be Guangdong ten it is big it is genuine in
One of medicinal material, it is the first precious and clear front yard tribute of " Guangdong Triratna " (dried orange peel, old ginger, straw grass).But Xinhui tangerine peel and its product
The food safety risk very severe faced, once occurred the residual pollution report of Xinhui tangerine peel agriculture in recent years, and not only influenceed health, damage
Evil consumer's interests, can also influence Xinhui tangerine peel and its product export competitiveness and product reputation.
In the existing Pesticides Testing standard in China, a large amount of use steams acetone, liver of the acetone to people again in sample pre-treatments
Kidney and pancreatic damage are very big.And dichloromethane and acetone steam again and it is certain using having to residue detection operator's health
Risk.Therefore, establish that cost is cheap, green, quickly and accurately Xinhui tangerine peel and its product Pesticide Residues analysis side
Method is very important.
The content of the invention
For above-mentioned technical problem, the present invention provides the assay method of the agricultural chemicals such as Rogor in a kind of Xinhui tangerine peel and product.
Agricultural chemicals is stated as DDVP, acephatemet, orthene, thimet, omethoate, Rogor, chlopyrifos, malathion, parathion, quinoline
Sulphur phosphorus, Ethodan, the described method comprises the following steps：
(1) making of standard curves：Above-mentioned 11 kinds of pesticide standard sample solution 1.000ml are pipetted respectively to 25mL browns appearance
In measuring bottle, diluted with chromatogram pure ethyl acetate and be settled to scale, be configured to the standard inventory that mass concentration is 4.000 μ g/mL
Liquid；Standard reserving solution 0.0050mL, 0.0125mL, 0.050mL, 0.50mL, 5.0mL are drawn, is respectively placed in 10mL brown capacity
Bottle in, diluted with chromatogram pure ethyl acetate and be settled to scale, shaken up, obtained mass concentration be respectively 0.0020 μ g/mL,
0.0050 μ g/mL, 0.020 μ g/mL, 0.20 μ g/mL, 2.0 μ g/mL standard working solution；1 μ L standard working solutions are taken to inject respectively
In gas chromatograph, using mass concentration as abscissa, component peak area is ordinate, draws standard curve；
(2) sample extractions：Extracted after sample is soaked with organic solvent；
(3) sample purifications：By extract solution obtained by step (2) after extracting column purification, it is blown to nitrogen and is closely done, addition has
Solvent dissolved residue, through membrane filtration；
(4) samples determine：With gas chromatograph detect sample, with retention time it is qualitative, with calculated by peak area testing sample
Described in 11 kinds of agricultural chemicals residual quantity, with external standard method result of calculation；Chromatographic condition is as follows：
Chromatographic column：Capillary column using (14%- cyanogen propvl-phenvl)-methyl polysiloxane as fixer；Carrier gas：Purity
＞ 99.999% helium；Flow velocity：1.0mL/min；Sample size：1.0 μ L, Splitless injecting samples；Column temperature：Initial 100 DEG C, keep
1min, with 20 DEG C/min temperature programmings to 220 DEG C, 2min is kept, then with 5 DEG C/min temperature programmings to 250 DEG C, keep 10min；
Injector temperature：250℃；Detector temperature：250℃；Detector：Flame photometric detector；Phosphorus optical filter：526nm；Burning
Gas：Purity ＞ 99.999% hydrogen, flow velocity：62.5mL/min；Combustion-supporting gas：Air, flow velocity：90.0mL/min.
Further, the sample is Xinhui citrus reticulata, jam of dried orange peel, dried orange peel pattern cake, preserved prune, and step (2) sample carries
The method taken is：Weigh 2.00g samples to be placed in 50mL centrifuge tubes, add 2mL water, vibrate 1min, ultrasonic 10min, add 5mL
Ethyl acetate, ultrasonic 10min, 5min is centrifuged, draw supernatant liquor, added 3mL ethyl acetate and repeat to extract, merge supernatant
Liquid, mix.
Further, the sample is Xinhui tangerine peel, the general tea of mandarin orange, and the method for step (2) the sample extractions is：Weigh
2.00g samples are placed in 50mL centrifuge tubes, add 4mL water, vibrate 1min, ultrasonic 10min, add 5mL ethyl acetate, ultrasound
10min, 5min is centrifuged, draw supernatant liquor, added 5mL ethyl acetate and repeat to extract, merge supernatant, mix.
Specifically, organic solvent is 1mL ethyl acetate in the step (3).
Specifically, the centrifugal speed is 3000r/min.
Specifically, the pesticide standard sample solution concentration is 100 μ g/mL, and solvent is acetone.
Specifically, the aperture of the filter membrane is 0.22 μm.
Specifically, the extraction column includes column jecket, lower sieve plate, lower floor's filler, isolation sieve plate, upper strata filler and upper sieve plate；
The lower sieve plate, lower floor's filler, isolation sieve plate, upper strata filler and upper sieve plate are distributed in the column jecket from the bottom to top successively；Its
Described in lower floor's filler be modified multiwalled carbon nanotube, dosage 0.5g；The upper strata filler is N- propyl group ethylenediamine fillers, is used
Measure as 0.5g；The thickness of the upper sieve plate is more than the lower sieve plate.Because upper sieve plate bears bigger pressure.
Specifically, the preparation method of the extraction column is：Column jecket described in 10mL is taken, the lower sieve plate is laid in bottom, loads
0.5g modified multiwalled carbon nanotubes, gently beaing makes uniformly to fill, and loads after being flattened with isolation sieve plate on isolation sieve plate top
0.5g N- propyl group ethylenediamine fillers, gently beat, and are flattened with the upper sieve plate, are lived successively with 6mL methanol, 6mL ethyl acetate
Change, produce.
Compared with prior art, for the present invention using ethyl acetate as Extraction solvent, dosage is few but recovery of standard addition is high, should
Reagent is low to human health damage, and the present invention is environmentally friendly；The present invention is low using self-control solid phase extraction column, testing cost；
Sample size has a good linear response in the range of 0.001~1mg/kg, and in 0.001mg/kg, 0.005mg/kg and
Mark-on reclaims experiment under tri- kinds of pitch-based spheres of 0.01mg/kg is respectively provided with the higher rate of recovery.The present invention also has simple to operate
Quickly, high sensitivity, the advantages of anti-matrix interference ability is strong, suitable for the qualitative of Xinhui tangerine peel and its product Pesticide Residues and
Quantitative analysis.
In order to more fully understand and implement, the invention will now be described in detail with reference to the accompanying drawings.
Brief description of the drawings
Fig. 1 is 11 kinds of pestsides synthesis standard liquid gas chromatograms (2.0 μ g/mL) of the invention, by peak sequence from 1 to 11
It is followed successively by：DDVP, acephatemet, orthene, thimet, omethoate, Rogor, chlopyrifos, malathion, parathion, quinoline
Sulphur phosphorus, Ethodan；
Fig. 2 is that Xinhui tangerine peel blank adds mixed standard specimen product to pass through the chromatogram after SPE pillars (PSA+C18) purification；
Fig. 3 is that Xinhui tangerine peel blank adds mixed standard specimen product to pass through the chromatogram after SPE pillars (C18+MWNTs) purification；
Fig. 4 is that Xinhui tangerine peel blank adds mixed standard specimen product to pass through the chromatogram after SPE pillars (PSA+MWNTs) purification；
Fig. 5 is extraction column profile of the present invention；
Fig. 6 is the gas chromatogram that Xinhui tangerine peel adds mixed target standard curve qualitative, quantitative；
Fig. 7 is the gas chromatogram that the general tea of mandarin orange adds mixed target standard curve qualitative, quantitative.
Embodiment
Instrument and reagent：The Ultar of GCMS-QP 2010 (Japanese Shimadzu Corporation)：It is automatic with FPD detectors, AOC-20si
Sampling system, the high-purity hydrogen generators of SGH-300 (Beijing Orient elite garden company), (Kunshan surpasses KQ 2200DB types ultrasonator
Sound Instrument Ltd.), 2-16 type common bench supercentrifuge (German Sigma companies), IKA turbine mixers, DN-12W
Nitrogen evaporator (Shanghai is than youth company), SPE devices (Supelco companies of the U.S.), SPE void columns pipe (Shanghai De Lian companies).
11 kinds of standard sample of pesticide：Specification is 100 μ g/mL, and peace a word used in place name bottle is sealed, and is purchased from Ministry of Agriculture's environmental protection scientific research
Detection institute.
Methanol, acetonitrile, ethyl acetate are chromatographically pure, purchased from Merck KGaA company, and n-hexane is that analysis is pure, rich purchased from Tianjin
Space company, octadecyl silane (hereinafter referred to as C18) solid phase extraction filler is purchased from Suzhou match branch company, N- propyl group second two
Amine filler (hereinafter referred to as PSA) is purchased from Shandong secret company, and multi-walled carbon nanotube (hereinafter referred to as MWNTs) is purchased from Shenzhen's nanometer
Port Co., Ltd, experimental water are deionized-distilled water.The preparation method of modified multiwalled carbon nanotube exists《Modified multi-wall carbon nano-tube
4 kinds of organo-chlorine pesticides of trace residue in pipe Solid Phase Extraction-high Performance Liquid Chromatography agricultural product》(《Chromatogram》Magazine,
Vol.30, No.9,966~970) in have it is disclosed.
Following examples specimen in use is purchased from local supermarket.
Embodiment 1：Sample determines
The preparation of 1.1 standard reserving solutions：It is accurate respectively to draw DDVP, acephatemet, orthene, thimet, oxygen pleasure
Fruit, Rogor, chlopyrifos, malathion, parathion, quinalphos, the μ g/mL standard solutions 1.000mL to 25mL of Ethodan 100.0
Brown volumetric flask, diluted with chromatogram pure ethyl acetate and be settled to scale, it is 4.000 μ g/mL's to be configured to mass concentration respectively
Standard reserving solution, 4 DEG C of preservations are standby.
The preparation of 1.2 standard working solutions：Respectively it is accurate draw standard reserving solution 0.0050mL, 0.0125mL, 0.050mL,
0.50mL, 5.0mL, it is respectively placed in 10mL brown volumetric flasks, is diluted with chromatogram pure ethyl acetate and be settled to scale, shaken up,
Obtained mass concentration is respectively 0.0020 μ g/mL, 0.0050 μ g/mL, 0.020 μ g/mL, 0.20 μ g/mL, 2.0 μ g/mL standard
Working solution, 4 DEG C of preservations are standby.
1.3 draw standard curve：Take respectively in 1 μ L standard working solutions injection gas chromatograph, using mass concentration as horizontal seat
Mark, component peak area is ordinate, draws standard curve.
The extraction of 1.4 samples：Weigh 2.00g preserved prune samples to be placed in 50mL centrifuge tubes, add 2mL water, vibrate 1min,
Ultrasonic 10min, 5mL ethyl acetate is added, ultrasonic 10min, 5min is centrifuged with 3000r/min, supernatant liquor is drawn, adds
3mL ethyl acetate repeats to extract, and merges supernatant, mixes.
The purification of 1.5 samples：10mL SPE void column pipes are taken, the lower sieve plate of bottom paving, loads the more wall carbon of 0.5g modifications and receives
Mitron, gently beaing makes uniformly to fill, and adds 0.5g N- propyl group ethylenediamine fillers after being flattened with isolation sieve plate, gently beats,
Upper sieve plate is pressed, produces self-control solid phase extraction column.Activated successively with 6mL methanol, 6mL ethyl acetate using preceding.Sample is taken to carry
Take supernatant to cross self-control solid phase extraction column, collect efflux, nitrogen, which is blown to, closely to be done, and adds the dissolving of 1mL chromatograms pure ethyl acetate residual
Slag, vibrates 1min, and solution is crossed machine in 0.22 μm of organic phase filter membrane and determined.
1.6 GC detection：Test solution is detected using gas-chromatography (GC).GC conditions：Chromatographic column：
Agilent RTX-1701(30m×0.32mm×0.25μm)；Carrier gas：High-purity helium (percent by volume ＞ 99.999%)；Stream
Speed：1.0mL/min；Sample size：1.0μL；Input mode：Temperature programming Splitless injecting samples；Heating schedule：Initial 100 DEG C, keep
1min, 220 DEG C are warming up to 20 DEG C/min, keep 2min, then 250 DEG C are warming up to 5 DEG C/min, keep 10min；Injection port temperature
Degree：250℃；Detector temperature：250℃；Detector：Flame photometric detector (FPD)；Phosphorus optical filter：526nm；Combustion gas：Hydrogen
Gas (percent by volume ＞ 99.999%), flow velocity：62.5mL/min；Combustion-supporting gas：Air, flow velocity：90.0mL/min.
Wherein, 11 kinds of residues of pesticides gas chromatograms are as shown in Figure 1.Residues of pesticides result is calculated as follows：Result of calculation
Blank value need to be deducted.
In formula：X --- for the residual quantity for sample Pesticides of having a try, unit mg/kg；
C --- the concentration of sample solution Pesticides, unit are μ g/mL；
V --- the constant volume of final sample liquid, unit mL；
M --- for the quality for sample of having a try, unit g；
Embodiment 2：The selection of Extraction solvent
The present embodiment Plays storing solution, the preparation of standard working solution, the purification of sample and chromatographic condition and embodiment 1
Identical, the extracting method of sample is as follows：Weigh negative Xinhui tangerine peel powder 2.00g samples to be placed in 50mL centrifuge tubes, add
0.20 μ g/mL standard solutions, 2mL water is added, vibrate and ultrasonic, carry out 2 with 5mL petroleum ethers, methanol and ethyl acetate respectively
Secondary extraction.Experimental result is shown in Table 1.
<The recovery of standard addition of the different organic solvents of table 1 extraction>
It was found from the recovery of standard addition comparative analysis of the different organic solvents of table 1 extraction, ethyl acetate obtains as Extraction solvent
The rate of recovery arrived is relatively high and stable, and optimum is used to extract the residues of pesticides in Xinhui tangerine peel and its product of the present invention.
Embodiment 3：The selection of solid phase extraction column stuffing type
Due to the chemical compositions such as the distinctive some volatile oil of Xinhui tangerine peel, chromocor compound, alkaloid with conventional method not
Easily remove, also the component such as protein, fat, sugar and organic acid, these impurity understand the survey of severe jamming target analytes in addition
It is fixed, while can also greatly shorten the service life of chromatographic column, it is therefore desirable to purification pre-treatment is carried out to sample.From single filler
SPE pillars, remove deimpurity DeGrain.
C18 fillers have higher adsorbance to impurity such as protein, fat, vitamins, but also can firm adsorbed target
Compound, it have impact on recovery of standard addition.PSA fillers can effectively adsorb flavones, alkaloid, carbohydrate, phenols, aliphatic acid, organic acid
Water solubility and oil-soluble impurities in sample can be effectively removed with impurity, MWNTs such as pigments.The present embodiment is by 3 kinds of SPE fillers
(PSA, C18, MWNTs) combination of two uses contrast collection of illustrative plates effect.The present embodiment Plays storing solutions, standard working solution are matched somebody with somebody
System, the extraction of sample and chromatographic condition are same as Example 1, as a result see Fig. 2~4.
PSA+MWNTs filler extraction posts：Referring to Fig. 5, it is profile.Including column jecket 1, lower sieve plate 2, lower floor's filler 3,
Isolate sieve plate 4, upper strata filler 5 and upper sieve plate 6.The lower sieve plate 2, lower floor's filler 3, isolation sieve plate 4, upper strata filler 5 and upper sieve
Plate 6 is distributed in the column jecket 1 from the bottom to top successively.The thickness of wherein described upper sieve plate 6 is greater than the lower sieve plate 2.
The capacity of the column jecket 1 is 10ml, can be bought by commercial channel.The aperture of the lower sieve plate 2 be 5~100 μm,
Thickness is 3~5mm.The aperture of the isolation sieve plate 4 is 5~100 μm, and thickness is 2~5mm.The aperture of the upper sieve plate 6 is 5
~100 μm, thickness is 6~10mm.
Lower floor's filler 3 is modified multiwalled carbon nanotube, dosage 0.5g, the purity of the modified multiwalled carbon nanotube
＞ 95%, a diameter of 10~20nm, length are 300~800nm.Its preparation method exists《Modified multiwalled carbon nanotube SPE-
4 kinds of organo-chlorine pesticides of trace residue in high effective liquid chromatography for measuring agricultural product》(《Chromatogram》Magazine, Vol.30, No.9,966
~970) have in disclosed.The upper strata filler 5 is N- propyl group ethylenediamine fillers, dosage 0.5g, the N- propyl group ethylenediamine
45 μm of the particle mean size of filler, specific surface area 480m2/g。
The preparation method of the PSA+MWNTs filler extraction posts of the present invention is as follows：Column jecket 1 is taken, the lower sieve plate 2 of bottom laying, is claimed
0.5g modified multiwalled carbon nanotube is taken, is placed on the lower sieve plate 2, gently beaing fills uniform filling, with isolation sieve plate 4
Flatten, then weigh 0.5g N- propyl group ethylenediamine fillers, be placed on the isolation sieve plate 4, gently beat, flattened with upper sieve plate 6,
Produce.
PSA+C18 filler extraction posts：The preparation method of the extraction column and the preparation method base of PSA+MWNTs filler extraction posts
This is identical, its distinctive points be upper strata filler be 0.5g PSA, lower floor's filler be 0.5g C18.
C18+MWNTs filler extraction posts：The preparation method of the extraction column and the preparation method of PSA+MWNTs filler extraction posts
It is essentially identical, its distinctive points be upper strata filler be 0.5g C18, lower floor's filler be 0.5g MWNTs.
From Fig. 2, Fig. 3, using the SPE posts of other two kinds of combined stuffings, impurity peaks quantity is more, can disturb result point
Analysis, some target compound rate of recovery are low.From fig. 4, it can be seen that the SPE posts filled using PSA+MWNTs fillers, impurity peaks are to each agriculture
Medicine target peak does not interfere with, and separating degree is good between each peak, and separating degree is shown in Table 2, and each target compound rate of recovery is high.Use self-control
Mixed type SPE posts (PSA+MWNTs) carry out pre-treatment, and the post has used the activity that can keep stable in extensive pH value range
Functional group and anion exchange absorbing agent, the optimization and high selectivity of purification can be ensured, obtain good using effect.
Therefore, finally from adsorption stuffings of the PSA+MWNTs as self-control SPE posts.
<The separating degree of 2 11 kinds of standard sample of pesticide of table>
Embodiment 4：Linear relationship is tested
The present embodiment Plays storing solution, the preparation of standard working solution and chromatographic condition are same as Example 1, take a system
The standard work of row different quality concentration (0.0020 μ g/mL, 0.0050 μ g/mL, 0.020 μ g/mL, 0.20 μ g/mL, 2.0 μ g/mL)
Make liquid, linear regression is carried out to the concentration of each target compound with instrument response peak area, draws standard curve, experimental result is shown in
Table 3.
<The linear relationship of 3 11 kinds of agricultural chemicals of table>
As seen from the results in Table 2, the concentration (x) of 11 kinds of agricultural chemicals in the range of 0.0020~2.0 μ g/mL with respond peak area
(y) it is linear.
Embodiment 5：Precision, detection limit and quantitative limit
Under the chromatographic condition of embodiment 1,0.020 μ g/mL of measure mixed standard solution 6 times, it is (relative to calculate precision
Standard deviation, RSD).It is detection limit (LOD) according to 11 kinds of compounds contents corresponding to 3 times of signal to noise ratio peak areas, 10 times of signal to noise ratio
Compounds content corresponding to peak area is quantitative limit (LOQ), is computed, the results are shown in Table 4.
<Precision, detection limit and the quantitative limit of 4 11 kinds of agricultural chemicals of table>
Embodiment 6：Actual sample determines
The present embodiment Plays storing solution, the preparation of standard working solution, the purification of sample and chromatographic condition and embodiment 1
It is identical, the sample such as detection in the market Xinhui citrus reticulata, Xinhui tangerine peel, the general tea of mandarin orange, jam of dried orange peel, dried orange peel pattern cake and preserved prune on sale,
When sample is Xinhui citrus reticulata, jam of dried orange peel, dried orange peel pattern cake, preserved prune, the extracting method of sample is：2.00g samples are weighed to be placed in
In 50mL centrifuge tubes, 2mL water is added, vibrates 1min, ultrasonic 10min, adds 5mL ethyl acetate, ultrasonic 10min, with 3000r/
Min centrifuges 5min, draws supernatant liquor, adds 3mL ethyl acetate and repeats to extract, merges supernatant, mix.When sample is new
Meeting dried orange peel, the extracting method of the general tea time sample of mandarin orange are：Weigh 2.00g samples to be placed in 50mL centrifuge tubes, add 4mL water, vibration
1min, ultrasonic 10min, 5mL ethyl acetate is added, ultrasonic 10min, 5min is centrifuged with 3000r/min, draws supernatant liquor, then
Add 5mL ethyl acetate to repeat to extract, merge supernatant, mix.
Its 11 kinds of residues of pesticides are analyzed, and add 1.0 μ g/kg, 5.0 μ g/kg and 10 μ in each sample respectively
The hybrid standard product of tri- kinds of concentration levels of g/kg determine its rate of recovery, the results are shown in Table 5~7 and Fig. 6~7.
<The Xinhui citrus reticulata of table 5 and Xinhui tangerine peel measurement result and recovery of standard addition>
<The general tea of the mandarin orange of table 6 and jam of dried orange peel measurement result and recovery of standard addition>
<The dried orange peel pattern cake of table 7 and preserved prune measurement result and recovery of standard addition>
"-" represents not detect in table 5~7, and result of the test explanation, the present invention use GC methods, can accurately, quickly, it is square
Just the residual quantity of 11 kinds of agricultural chemicals in Xinhui tangerine peel and its product is detected.
The invention is not limited in above-mentioned embodiment, if the various changes or deformation to the present invention do not depart from the present invention
Spirit and scope, if these changes and deformation belong within the scope of the claim and equivalent technologies of the present invention, then this hair
It is bright to be also intended to comprising these changes and deformation.
Claims (8)
- A kind of 1. assay method of the agricultural chemicals such as Rogor in Xinhui tangerine peel and product, it is characterised in that：The agricultural chemicals is DDVP, first Amine phosphorus, orthene, thimet, omethoate, Rogor, chlopyrifos, malathion, parathion, quinalphos, Ethodan, it is described Method comprises the following steps：(1) making of standard curves：11 kinds of pesticide standard sample solution 1.000ml are pipetted respectively to 25mL brown volumetric flasks In, diluted with chromatogram pure ethyl acetate and be settled to scale, be configured to the standard reserving solution that mass concentration is 4.000 μ g/mL；Inhale Standard reserving solution 0.0050mL, 0.0125mL, 0.050mL, 0.50mL, 5.0mL are taken, is respectively placed in 10mL brown volumetric flasks, Diluted with chromatogram pure ethyl acetate and be settled to scale, shaken up, obtained mass concentration is respectively 0.0020 μ g/mL, 0.0050 μ g/ ML, 0.020 μ g/mL, 0.20 μ g/mL, 2.0 μ g/mL standard working solution；1 μ L standard working solutions are taken to inject gas-chromatography respectively In instrument, using mass concentration as abscissa, component peak area is ordinate, draws standard curve；(2) sample extractions：Extracted after sample is soaked with organic solvent；(3) sample purifications：By extract solution obtained by step (2) after extracting column purification, it is blown to nitrogen and is closely done, is added organic molten Agent dissolved residue, 1min is vibrated, through membrane filtration；The extraction column include column jecket, lower sieve plate, lower floor's filler, isolation sieve plate, on Layer filler and upper sieve plate；The lower sieve plate, lower floor's filler, isolation sieve plate, upper strata filler and upper sieve plate are distributed from the bottom to top successively In the column jecket；Wherein described lower floor's filler is modified multiwalled carbon nanotube, dosage 0.5g；The upper strata filler is N- third Base ethylenediamine filler, dosage 0.5g；The thickness of the upper sieve plate is more than the lower sieve plate；(4) samples determine：With gas chromatograph detect sample, with retention time it is qualitative, with institute in calculated by peak area testing sample The residual quantity of 11 kinds of agricultural chemicals is stated, with external standard method result of calculation；Chromatographic condition is as follows：Chromatographic column：Capillary column using (14%- cyanogen propvl-phenvl)-methyl polysiloxane as fixer；Carrier gas：Volume basis Than>99.999% helium；Flow velocity：1.0mL/min；Sample size：1.0 μ L, Splitless injecting samples；Column temperature：Initial 100 DEG C, keep 1min, 220 DEG C are warming up to 20 DEG C/min, keep 2min, then 250 DEG C are warming up to 5 DEG C/min, keep 10min；Injection port temperature Degree：250℃；Detector temperature：250℃；Detector：Flame photometric detector；Phosphorus optical filter：526nm；Combustion gas：Volume hundred Divide ratio>99.999% hydrogen, flow velocity：62.5mL/min；Combustion-supporting gas：Air, flow velocity：90.0mL/min.
- 2. according to the method for claim 1, it is characterised in that：The sample be Xinhui citrus reticulata, jam of dried orange peel, dried orange peel pattern cake, Preserved prune, the method for step (2) sample extraction are：Weigh 2.00g samples to be placed in 50mL centrifuge tubes, add 2mL water, shake 1min, ultrasonic 10min are swung, 5mL ethyl acetate is added, ultrasonic 10min, centrifuges 5min, draw supernatant liquor, add 3mL second Acetoacetic ester repeats to extract, and merges supernatant, mixes.
- 3. according to the method for claim 1, it is characterised in that：The sample is Xinhui tangerine peel, the general tea of mandarin orange, the step (2) method of sample extractions is：Weigh 2.00g samples to be placed in 50mL centrifuge tubes, add 4mL water, vibrate 1min, ultrasound 10min, 5mL ethyl acetate is added, ultrasonic 10min, centrifuges 5min, draws supernatant liquor, added 5mL ethyl acetate and repeat to carry Take, merge supernatant, mix.
- 4. according to the method in claim 2 or 3, it is characterised in that organic solvent is 1mL acetic acid second in the step (3) Ester.
- 5. according to the method in claim 2 or 3, it is characterised in that：The centrifugal speed is 3000r/min.
- 6. according to the method in claim 2 or 3, it is characterised in that：The pesticide standard sample solution concentration is 100 μ g/mL, Solvent is acetone.
- 7. according to the method in claim 2 or 3, it is characterised in that：The aperture of the filter membrane is 0.22 μm.
- 8. according to the method in claim 2 or 3, it is characterised in that the preparation method of the extraction column is：Take described in 10mL The lower sieve plate is laid in column jecket, bottom, loads 0.5g modified multiwalled carbon nanotubes, and gently beaing makes uniformly to fill, and is sieved with isolation Plate is isolating sieve plate top loading 0.5g N- propyl group ethylenediamine fillers after flattening, and gently beats, is flattened with the upper sieve plate, according to It is secondary to be activated with 6mL methanol, 6mL ethyl acetate, produce.
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| CN101241113A (en) * | 2007-02-07 | 2008-08-13 | 劲牌有限公司 | Chinese herbal medicine residual organophosphorus pesticide detection method |
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| CN103399099A (en) * | 2013-08-14 | 2013-11-20 | 山东农业大学 | Method for detecting nine organophosphorus pesticides simultaneously |
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| CN101241113A (en) * | 2007-02-07 | 2008-08-13 | 劲牌有限公司 | Chinese herbal medicine residual organophosphorus pesticide detection method |
| RU2408010C2 (en) * | 2008-09-01 | 2010-12-27 | Федеральное государственное образовательное учреждение высшего профессионального образования Саратовский военный институт биологической и химической безопасности Министерства обороны Российской Федерации (СВИ БХБ) | Gas chromatographic method for quantitative determnation of organophosphorus toxic substances using dialkyl esters of methyl-phosphoric acid as internal standard |
| CN103399099A (en) * | 2013-08-14 | 2013-11-20 | 山东农业大学 | Method for detecting nine organophosphorus pesticides simultaneously |
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