CN105699515A - Determination method of pesticides including dimethoate in Xinhui tangerine peels and products of Xinhui tangerine peels - Google Patents
Determination method of pesticides including dimethoate in Xinhui tangerine peels and products of Xinhui tangerine peels Download PDFInfo
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- CN105699515A CN105699515A CN201610057106.4A CN201610057106A CN105699515A CN 105699515 A CN105699515 A CN 105699515A CN 201610057106 A CN201610057106 A CN 201610057106A CN 105699515 A CN105699515 A CN 105699515A
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- 239000000575 pesticide Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 21
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 241000675108 Citrus tangerina Species 0.000 title abstract 6
- 239000005947 Dimethoate Substances 0.000 title abstract 3
- 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
- 229950001327 dichlorvos Drugs 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
- PZXOQEXFMJCDPG-UHFFFAOYSA-N omethoate Chemical compound CNC(=O)CSP(=O)(OC)OC PZXOQEXFMJCDPG-UHFFFAOYSA-N 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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 88
- 239000000945 filler Substances 0.000 claims description 43
- 241001672694 Citrus reticulata Species 0.000 claims description 34
- 238000000605 extraction Methods 0.000 claims description 27
- 239000002048 multi walled nanotube Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000006228 supernatant Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000002955 isolation Methods 0.000 claims description 14
- 239000012224 working solution Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- -1 chlopyrifos Chemical compound 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000003556 assay Methods 0.000 claims description 4
- OYFLKNAULOKYRI-UHFFFAOYSA-N ethoxy-phenyl-quinolin-8-yloxy-sulfanylidene-$l^{5}-phosphane Chemical compound C=1C=CC2=CC=CN=C2C=1OP(=S)(OCC)C1=CC=CC=C1 OYFLKNAULOKYRI-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 238000004817 gas chromatography Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229950010630 quintiofos Drugs 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 238000004364 calculation method Methods 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 239000000567 combustion gas Substances 0.000 claims description 3
- 239000012467 final product 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
- 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
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 238000010812 external standard method Methods 0.000 claims description 2
- 239000000834 fixative Substances 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
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 241001122767 Theaceae Species 0.000 claims 1
- 239000000447 pesticide residue Substances 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 2
- 238000004451 qualitative analysis Methods 0.000 abstract description 2
- 238000004445 quantitative analysis Methods 0.000 abstract description 2
- 239000005944 Chlorpyrifos Substances 0.000 abstract 1
- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical compound CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- NNKVPIKMPCQWCG-UHFFFAOYSA-N methamidophos Chemical compound COP(N)(=O)SC NNKVPIKMPCQWCG-UHFFFAOYSA-N 0.000 abstract 1
- JYQUHIFYBATCCY-UHFFFAOYSA-N quinalphos Chemical compound C1=CC=CC2=NC(OP(=S)(OCC)OCC)=CN=C21 JYQUHIFYBATCCY-UHFFFAOYSA-N 0.000 abstract 1
- 230000035945 sensitivity Effects 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 42
- 238000001514 detection method Methods 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 6
- 244000269722 Thea sinensis Species 0.000 description 5
- 239000012086 standard solution Substances 0.000 description 4
- 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
- 238000005516 engineering process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 229930013930 alkaloid Natural products 0.000 description 2
- 150000003797 alkaloid derivatives Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 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
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- GAMYVSCDDLXAQW-AOIWZFSPSA-N Thermopsosid Natural products O(C)c1c(O)ccc(C=2Oc3c(c(O)cc(O[C@H]4[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O4)c3)C(=O)C=2)c1 GAMYVSCDDLXAQW-AOIWZFSPSA-N 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
- 238000005349 anion exchange Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000000378 dietary effect Effects 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229930003944 flavone Natural products 0.000 description 1
- 150000002212 flavone derivatives 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
- 230000010354 integration Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 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
- 239000002245 particle Substances 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- VHBFFQKBGNRLFZ-UHFFFAOYSA-N vitamin p Natural products O1C2=CC=CC=C2C(=O)C=C1C1=CC=CC=C1 VHBFFQKBGNRLFZ-UHFFFAOYSA-N 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
Abstract
The invention provides a determination method of pesticides including dimethoate and the like in Xinhui tangerine peels and products of the Xinhui tangerine peels. The pesticides comprise dichlorvos, methamidophos, acephate, phorate, omethoate, dimethoate, chlorpyrifos, malathion, parathion, quinalphos and ethion. The method comprises the following steps: manufacturing a standard curve, extracting a sample, purifying the sample and determining the sample. The determination method has the advantages of simplicity and rapidness in operation, high sensitivity and strong matrix interference resistance capability, and is suitable for qualitative and quantitative analysis of pesticide residues in the Xinhui tangerine peels and the products of the Xinhui tangerine peels.
Description
Technical field
The present invention relates to the Detection Technologies of Pesticide Residues field, particularly to the assay method of the pesticide such as Rogor in a kind of Xinhui tangerine peel and goods。
Background technology
Xinhui tangerine peel is the famous local speciality that rare integration of edible and medicinal herbs, dietetic therapy are all good, for one of big genuine Chinese crude drug in Guangdong ten, is the first precious and clear front yard tribute of " Guangdong three essentials-essence " (Pericarpium Citri Reticulatae, old ginger, straw grass)。But the food safety risk that Xinhui tangerine peel and goods thereof face is very severe, in recent years once occurred that Xinhui tangerine peel agriculture was residual and polluted report, and not only affected health, damage consumer's interests, also can affect Xinhui tangerine peel and goods export competitiveness thereof and product reputation。
In the existing Pesticides Testing standard of China, in sample pre-treatments, acetone is heavily steamed in a large amount of uses, and acetone is very big to Liver and kidney and the pancreatic damage of people。And residue detection operator ' s health is had certain risk by the heavily steaming of dichloromethane and acetone and use。Therefore, set up with low cost, environmental protection, quickly and accurately Xinhui tangerine peel and goods Pesticide Residues component analysis method is very important。
Summary of the invention
For above-mentioned technical problem, the present invention provides the assay method of the pesticide such as Rogor in a kind of Xinhui tangerine peel and goods。Stating pesticide is dichlorvos, Bayer 71628, orthene, thimet, omethoate, Rogor, chlopyrifos, Malathion, parathion, quintiofos, Ethodan, said method comprising the steps of:
(1). the making of standard curve: pipette in above-mentioned 11 kinds of standard sample of pesticide brown volumetric flasks of solution 1.000ml to 25mL respectively, with chromatographically pure diluted ethyl acetate and be settled to scale, it is configured to the standard reserving solution that mass concentration is 4.000 μ g/mL；Draw standard reserving solution 0.0050mL, 0.0125mL, 0.050mL, 0.50mL, 5.0mL, it is respectively placed in the brown volumetric flask of 10mL, with chromatographically pure diluted ethyl acetate and be settled to scale, shake up, prepared mass concentration 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；Taking respectively in 1 μ L standard working solution injection gas chromatography instrument, with mass concentration for abscissa, component peaks area is vertical coordinate, drawing standard curve；
(2). sample extraction: use organic solvent extraction after being soaked by sample；
(3). sample purification: by step (2) gained extracting solution after extraction column purifies, it is blown to nitrogen near dry, adds organic solvent dissolved residue, through membrane filtration；
(4). sample determination: detect sample with gas chromatograph, qualitative with retention time, with the residual quantity of 11 kinds of pesticide described in calculated by peak area testing sample, with external standard method result of calculation；Chromatographic condition is as follows:
Chromatographic column: the capillary column being fixative with (14%-cyanogen propvl-phenvl)-methyl polysiloxane；The helium of carrier gas: purity > 99.999%；Flow velocity: 1.0mL/min；Sample size: 1.0 μ L, Splitless injecting samples；Column temperature: initial 100 DEG C, keeps 1min, with 20 DEG C/min temperature programming to 220 DEG C, keeps 2min, then with 5 DEG C/min temperature programming to 250 DEG C, keeps 10min；Injector temperature: 250 DEG C；Detector temperature: 250 DEG C；Detector: flame photometric detector；Phosphorus optical filter: 526nm；The hydrogen of combustion gas: purity > 99.999%, flow velocity: 62.5mL/min；Combustion-supporting gas: air, flow velocity: 90.0mL/min。
Further, described sample is Xinhui citrus reticulata, jam of dried orange peel, Pericarpium Citri Reticulatae pattern cake, preserved prune, and the method for described step (2) sample extraction is: weighs 2.00g sample and is placed in 50mL centrifuge tube, add 2mL water, vibration 1min, ultrasonic 10min, add 5mL ethyl acetate, ultrasonic 10min, centrifugal 5min, draws the supernatant, adds 3mL ethyl acetate and repeats to extract, merge supernatant, mixing。
Further, described sample is Xinhui tangerine peel, the general tea of Citrus chachiensis Hort., described step (2). the method for sample extraction is: weighs 2.00g sample and is placed in 50mL centrifuge tube, add 4mL water, vibration 1min, ultrasonic 10min, add 5mL ethyl acetate, ultrasonic 10min, centrifugal 5min, draws the supernatant, adds 5mL ethyl acetate and repeats to extract, merge supernatant, mixing。
Specifically, in described step (3), organic solvent is 1mL ethyl acetate。
Specifically, described centrifugal speed is 3000r/min。
Specifically, described standard sample of pesticide solution concentration is 100 μ g/mL, and solvent is acetone。
Specifically, the aperture of described filter membrane is 0.22 μm。
Specifically, described extraction column includes column jecket, lower sieve plate, lower floor's filler, isolation sieve plate, upper strata filler and upper sieve plate；Described lower sieve plate, lower floor's filler, isolation sieve plate, upper strata filler and upper sieve plate are distributed in described column jecket successively from the bottom to top；Wherein said lower floor filler is modified multiwalled carbon nanotube, and consumption is 0.5g；Described upper strata filler is N-propyl group ethylenediamine filler, and consumption is 0.5g；The thickness of described upper sieve plate is more than described lower sieve plate。Because upper sieve plate bears bigger pressure。
Specifically, the preparation method of described extraction column is: take column jecket described in 10mL, described lower sieve plate is laid in bottom, load 0.5g modified multiwalled carbon nanotube, beat gently and make uniform filling, after flattening with isolation sieve plate, load 0.5gN-propyl group ethylenediamine filler on isolation sieve plate top, beat gently, flatten with described upper sieve plate, successively with 6mL methanol, the activation of 6mL ethyl acetate, to obtain final product。
Compared with prior art, the present invention adopts ethyl acetate as Extraction solvent, and consumption is few but recovery of standard addition high, and this reagent is low to human health damage, and the present invention is environmentally friendly；The present invention uses self-control solid phase extraction column, and testing cost is low；Sample size has good linear response within the scope of 0.001～1mg/kg, and the mark-on recovery test under three kinds of pitch-based sphere of 0.001mg/kg, 0.005mg/kg and 0.01mg/kg is respectively provided with the higher response rate。The present invention also has the advantage that matrix interference ability quick, highly sensitive, anti-simple to operate is strong, it is adaptable to the qualitative and quantitative analysis of Xinhui tangerine peel and goods Pesticide Residues thereof。
In order to be more fully understood that and implement, describe the present invention in detail below in conjunction with accompanying drawing。
Accompanying drawing explanation
Fig. 1 is 11 kinds of pestsides synthesis standard solution gas chromatograms of the present invention (2.0 μ g/mL), is followed successively by from 1 to 11 by peak sequence: dichlorvos, Bayer 71628, orthene, thimet, omethoate, Rogor, chlopyrifos, Malathion, parathion, quintiofos, Ethodan；
Fig. 2 is that Xinhui tangerine peel blank adds the chromatogram after mixed standard specimen product are purified by SPE pillar (PSA+C18)；
Fig. 3 is that Xinhui tangerine peel blank adds the chromatogram after mixed standard specimen product are purified by SPE pillar (C18+MWNTs)；
Fig. 4 is that Xinhui tangerine peel blank adds the chromatogram after mixed standard specimen product are purified by SPE pillar (PSA+MWNTs)；
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 Citrus chachiensis Hort. adds mixed target standard curve qualitative, quantitative。
Detailed description of the invention
Instrument and reagent: GCMS-QP2010Ultar (Shimadzu Corporation of Japan): join FPD detector, AOC-20si automatic sample handling system, SGH-300 High Purity Hydrogen generator (Beijing Orient elite garden company), KQ2200DB type ultrasonator (Kunshan ultrasonic instrument company limited), 2-16 type common bench high speed centrifuge (Sigma company of Germany), IKA turbine mixer, DN-12W Nitrogen evaporator (Shanghai is than youth company), SPE device (Supelco company of the U.S.), SPE void column pipe (Shanghai De Lian company)。
11 kinds of standard sample of pesticide: specification is 100 μ g/mL, peace a word used in place name bottle seals and preserves, all purchased from environmental conservation scientific research detection institute of the Ministry of Agriculture。
Methanol, acetonitrile, ethyl acetate be chromatographically pure, purchased from Merck KGaA company, normal hexane is analytical pure, purchased from Tianjin Fu Yu company, octadecyl silane (hereinafter referred to as C18) solid phase extraction filler matches branch company purchased from Suzhou, N-propyl group ethylenediamine filler (hereinafter referred to as PSA) is purchased from Shandong secret company, multi-walled carbon nano-tubes (hereinafter referred to as MWNTs) is purchased from Nanometer Port Co., Ltd., Shenzhen, and experimental water is deionized-distilled water。The preparation method of modified multiwalled carbon nanotube is at " in modified multiwalled carbon nanotube Solid Phase Extraction-high Performance Liquid Chromatography agricultural product 4 kinds of organochlorine pesticides of trace residue " (" chromatograph " magazine, Vol.30, No.9,966～970) disclosed in having in。
Following example specimen in use is all purchased from local supermarket。
Embodiment 1: sample determination
The preparation of 1.1 standard reserving solutions: accurately draw dichlorvos, Bayer 71628, orthene, thimet, omethoate, Rogor, chlopyrifos, Malathion, parathion, quintiofos, the Ethodan 100.0 μ g/mL brown volumetric flask of standard solution 1.000mL to 25mL respectively, with chromatographically pure diluted ethyl acetate and be settled to scale, it is configured to the standard reserving solution that mass concentration is 4.000 μ g/mL respectively, 4 DEG C of preservations, standby。
The preparation of 1.2 standard working solution: accurately draw standard reserving solution 0.0050mL, 0.0125mL, 0.050mL, 0.50mL, 5.0mL respectively, it is respectively placed in the brown volumetric flask of 10mL, with chromatographically pure diluted ethyl acetate and be settled to scale, shake up, prepared mass concentration 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, standby。
1.3 drawing standard curves: taking respectively in 1 μ L standard working solution injection gas chromatography instrument, with mass concentration for abscissa, component peaks area is vertical coordinate, drawing standard curve。
The extraction of 1.4 samples: weigh 2.00g preserved prune sample and be placed in 50mL centrifuge tube, add 2mL water, vibration 1min, ultrasonic 10min, add 5mL ethyl acetate, ultrasonic 10min, with the centrifugal 5min of 3000r/min, draw the supernatant, add 3mL ethyl acetate and repeat to extract, merge supernatant, mixing。
The purification of 1.5 samples: take 10mL Solid-Phase Extraction void column pipe, the lower sieve plate of bottom paving, load 0.5g modified multiwalled carbon nanotube, beat gently and make uniform filling, add 0.5gN-propyl group ethylenediamine filler after flattening with isolation sieve plate, beat gently, press upper sieve plate, obtain self-control solid phase extraction column。Successively with 6mL methanol, the activation of 6mL ethyl acetate before using。Taking sample extraction supernatant and cross self-control solid phase extraction column, collect effluent, nitrogen is blown near dry, adds 1mL chromatographically pure acetic acid ethyl dissolution residue, and vibrate 1min, and solution is crossed machine on 0.22 μm of organic facies filter membrane and measured。
The detection of 1.6GC: adopt gas chromatogram (GC) that test solution is detected。GC conditions: chromatographic column: AgilentRTX-1701 (30m × 0.32mm × 0.25 μm)；Carrier gas: high-purity helium (percent by volume > 99.999%)；Flow velocity: 1.0mL/min；Sample size: 1.0 μ L；Input mode: temperature programming Splitless injecting samples；Heating schedule: initial 100 DEG C, keeps 1min, is warming up to 220 DEG C with 20 DEG C/min, keeps 2min, then is warming up to 250 DEG C with 5 DEG C/min, keeps 10min；Injector temperature: 250 DEG C；Detector temperature: 250 DEG C；Detector: flame photometric detector (FPD)；Phosphorus optical filter: 526nm；Combustion gas: hydrogen (percent by volume > 99.999%), flow velocity: 62.5mL/min；Combustion-supporting gas: air, flow velocity: 90.0mL/min。
Wherein, 11 kinds of pesticide residues gas chromatograms are as shown in Figure 1。Pesticide residues result is calculated as follows: result of calculation need to deduct blank value。
In formula: X is for the residual quantity of sample Pesticides of having a try, and unit is mg/kg；
The concentration of c sample solution Pesticides, unit is μ g/mL；
The constant volume of the final sample liquid of V, unit is mL；
M is for the quality of sample of having a try, and unit is 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 are identical, the extracting method of sample is as follows: weighs negative Xinhui tangerine peel powder 2.00g sample and is placed in 50mL centrifuge tube, add 0.20 μ g/mL standard solution, add 2mL water, vibration is also ultrasonic, is undertaken 2 times by 5mL petroleum ether, methanol and ethyl acetate respectively and extracts。Experimental result is in Table 1。
<recovery of standard addition that table 1 different organic solvents is extracted>
The recovery of standard addition relative analysis extracted from table 1 different organic solvents is it can be seen that the response rate that obtains as Extraction solvent of ethyl acetate is relatively high and stable, and optimum is for extracting the pesticide residues in Xinhui tangerine peel of the present invention and goods thereof。
Embodiment 3: the selection of solid phase extraction column stuffing type
Owing to the chemical composition conventional methods such as Xinhui tangerine peel some volatile oil distinctive, chromocor compound, alkaloid not easily remove, in addition also have the components such as protein, fat, sugar and organic acid, the mensuration of these impurity meeting severe jamming target analytes, also can be greatly shortened the service life of chromatographic column, it is therefore desirable to carry out sample purifying pre-treatment simultaneously。Select the SPE pillar of single filler, remove deimpurity DeGrain。
The impurity such as protein, fat, vitamin are had a higher adsorbance by C18 filler, but also can firm adsorbed target compound, have impact on recovery of standard addition。The impurity such as PSA filler energy active adsorption flavone, alkaloid, saccharide, phenols, fatty acid, organic acid and pigment, MWNTs can effectively remove the water solublity in sample and oil-soluble impurities。3 kinds of SPE filler (PSA, C18, MWNTs) combination of two are used contrast collection of illustrative plates effect by the present embodiment。The present embodiment Plays storing solution, the preparation of standard working solution, the extraction of sample and chromatographic condition and embodiment 1 are identical, and result is shown in Fig. 2～4。
PSA+MWNTs filler extraction post: refer to Fig. 5, it is profile。Including column jecket 1, lower sieve plate 2, lower floor's filler 3, isolation sieve plate 4, upper strata filler 5 and upper sieve plate 6。Described lower sieve plate 2, lower floor's filler 3, isolation sieve plate 4, upper strata filler 5 and upper sieve plate 6 are distributed in described column jecket 1 successively from the bottom to top。The thickness of wherein said upper sieve plate 6 is greater than described lower sieve plate 2。
The capacity of described column jecket 1 is 10ml, can be buied by commercial channel。The aperture of described lower sieve plate 2 is 5～100 μm, thickness is 3～5mm。The aperture of described isolation sieve plate 4 is 5～100 μm, and thickness is 2～5mm。The aperture of described upper sieve plate 6 is 5～100 μm, and thickness is 6～10mm。
Described lower floor filler 3 is modified multiwalled carbon nanotube, and consumption is 0.5g, the purity > 95% of described modified multiwalled carbon nanotube, and diameter is 10～20nm, and length is 300～800nm。Disclosed in its preparation method has in " in modified multiwalled carbon nanotube Solid Phase Extraction-high Performance Liquid Chromatography agricultural product 4 kinds of organochlorine pesticides of trace residue " (" chromatograph " magazine, Vol.30, No.9,966～970)。Described upper strata filler 5 is N-propyl group ethylenediamine filler, and consumption is 0.5g, the particle mean size 45 μm of described N-propyl group ethylenediamine filler, specific surface area 480m2/g。
The preparation method of the PSA+MWNTs filler extraction post of the present invention is as follows: take column jecket 1, lower sieve plate 2 is laid in bottom, weigh the modified multiwalled carbon nanotube of 0.5g, be placed on described lower sieve plate 2, beat gently and make uniform filling fill, flatten with isolation sieve plate 4, weigh the N-propyl group ethylenediamine filler of 0.5g again, be placed on described isolation sieve plate 4, beat gently, flatten with upper sieve plate 6, to obtain final product。
PSA+C18 filler extraction post: the preparation method of the preparation method of this extraction column and PSA+MWNTs filler extraction post is essentially identical, its distinctive points is in that upper strata filler be 0.5gPSA, lower floor's filler is 0.5gC18。
C18+MWNTs filler extraction post: the preparation method of the preparation method of this extraction column and PSA+MWNTs filler extraction post is essentially identical, its distinctive points is in that upper strata filler be 0.5gC18, lower floor's filler is 0.5gMWNTs。
From Fig. 2, Fig. 3, using the SPE post of other two kinds of combined stuffings, impurity peaks quantity is many, can disturb interpretation of result, and some target compound response rate is low。From fig. 4, it can be seen that use the SPE post that PSA+MWNTs filler is filled, each pesticide target peak is not interfered with by impurity peaks, and between each peak, separating degree is good, and separating degree is in Table 2, and each target compound response rate is high。Self-control mixed type SPE post (PSA+MWNTs) is used to carry out pre-treatment, this post employs the activity functional groups and anion exchange absorbing agent that can remain stable in pH value range widely, ensure that the optimization of purification and high selectivity, it is thus achieved that well result of use。Therefore, finally select PSA+MWNTs as the adsorption stuffing of self-control SPE post。
<separating degrees of 211 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 and embodiment 1 are identical, take the standard working solution of a series of 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), with instrument response peak area, the concentration of each target compound is carried out linear regression, drawing standard curve, experimental result is in Table 3。
<linear relationships of 311 kinds of pesticide of table>
As seen from the results in Table 2, the concentration (x) of 11 kinds of pesticide is linear with response peak area (y) within the scope of 0.0020～2.0 μ g/mL。
Embodiment 5: precision, detection limit and quantitative limit
Under the chromatographic condition of embodiment 1, measure the mixed standard solution 6 times of 0.020 μ g/mL, calculate precision (relative standard deviation, RSD)。The 11 kind compounds contents corresponding according to 3 times of signal to noise ratio peak areas are detection limit (LOD), and the compounds content that 10 times of signal to noise ratio peak areas are corresponding is quantitative limit (LOQ), is computed, and result is in Table 4。
<precision of 411 kinds of pesticide of table, detection limit and quantitative limit>
Embodiment 6: actual sample measures
The present embodiment Plays storing solution, the preparation of standard working solution, the purification of sample and chromatographic condition and embodiment 1 are identical, Xinhui citrus reticulata on sale on detection market, Xinhui tangerine peel, the general tea of Citrus chachiensis Hort., jam of dried orange peel, the samples such as Pericarpium Citri Reticulatae pattern cake and preserved prune, when sample is Xinhui citrus reticulata, jam of dried orange peel, Pericarpium Citri Reticulatae pattern cake, during preserved prune, the extracting method of sample is: weighs 2.00g sample and is placed in 50mL centrifuge tube, add 2mL water, vibration 1min, ultrasonic 10min, add 5mL ethyl acetate, ultrasonic 10min, with the centrifugal 5min of 3000r/min, draw the supernatant, add 3mL ethyl acetate to repeat to extract, merge supernatant, mixing。When sample be Xinhui tangerine peel, the general tea time sample of Citrus chachiensis Hort. extracting method be: weigh 2.00g sample and be placed in 50mL centrifuge tube, add 4mL water, vibration 1min, ultrasonic 10min, add 5mL ethyl acetate, ultrasonic 10min, with the centrifugal 5min of 3000r/min, draw the supernatant, add 5mL ethyl acetate and repeat to extract, merge supernatant, mixing。
Its 11 kinds of pesticide residues being analyzed, and the hybrid standard product adding 1.0 μ g/kg, 5.0 μ g/kg and 10 tri-kinds of concentration levels of μ g/kg respectively in each sample measure its response rate, result is in Table 5～7 and Fig. 6～7。
<table 5 Xinhui citrus reticulata and Xinhui tangerine peel measurement result and recovery of standard addition>
<the general tea of table 6 Citrus chachiensis Hort. and jam of dried orange peel measurement result and recovery of standard addition>
<table 7 Pericarpium Citri Reticulatae pattern cake and preserved prune measurement result and recovery of standard addition>
In table 5～7, "-" represents and does not detect, and result of the test illustrates, the present invention adopts GC method, it is possible to detect the residual quantity of 11 kinds of pesticide in Xinhui tangerine peel and goods thereof accurately, quickly and easily。
The invention is not limited in above-mentioned embodiment, if to the various changes of the present invention or deformation without departing from the spirit and scope of the present invention, if these are changed and deform within the claim and the equivalent technologies scope that belong to the present invention, then the present invention is also intended to comprise these changes and deformation。
Claims (9)
1. the assay method of the pesticide such as Rogor in an Xinhui tangerine peel and goods, it is characterized in that: described pesticide is dichlorvos, Bayer 71628, orthene, thimet, omethoate, Rogor, chlopyrifos, Malathion, parathion, quintiofos, Ethodan, said method comprising the steps of:
(1). the making of standard curve: pipette in described 11 kinds of standard sample of pesticide brown volumetric flasks of solution 1.000ml to 25mL respectively, with chromatographically pure diluted ethyl acetate and be settled to scale, it is configured to the standard reserving solution that mass concentration is 4.000 μ g/mL；Draw standard reserving solution 0.0050mL, 0.0125mL, 0.050mL, 0.50mL, 5.0mL, it is respectively placed in the brown volumetric flask of 10mL, with chromatographically pure diluted ethyl acetate and be settled to scale, shake up, prepared mass concentration 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；Taking respectively in 1 μ L standard working solution injection gas chromatography instrument, with mass concentration for abscissa, component peaks area is vertical coordinate, drawing standard curve；
(2). sample extraction: use organic solvent extraction after being soaked by sample；
(3). sample purification: by step (2) gained extracting solution after extraction column purifies, it is blown to nitrogen near dry, adds organic solvent dissolved residue, vibrate 1min, through membrane filtration；
(4). sample determination: detect sample with gas chromatograph, qualitative with retention time, with the residual quantity of 11 kinds of pesticide described in calculated by peak area testing sample, with external standard method result of calculation；Chromatographic condition is as follows:
Chromatographic column: the capillary column being fixative with (14%-cyanogen propvl-phenvl)-methyl polysiloxane；The helium of carrier gas: percent by volume > 99.999%；Flow velocity: 1.0mL/min；Sample size: 1.0 μ L, Splitless injecting samples；Column temperature: initial 100 DEG C, keeps 1min, is warming up to 220 DEG C with 20 DEG C/min, keeps 2min, then is warming up to 250 DEG C with 5 DEG C/min, keeps 10min；Injector temperature: 250 DEG C；Detector temperature: 250 DEG C；Detector: flame photometric detector；Phosphorus optical filter: 526nm；The hydrogen of combustion gas: percent by volume > 99.999%, flow velocity: 62.5mL/min；Combustion-supporting gas: air, flow velocity: 90.0mL/min。
2. method according to claim 1, it is characterised in that: described sample is Xinhui citrus reticulata, jam of dried orange peel, Pericarpium Citri Reticulatae pattern cake, preserved prune, and the method for described step (2) sample extraction is: weighs 2.00g sample and is placed in 50mL centrifuge tube, add 2mL water, vibration 1min, ultrasonic 10min, add 5mL ethyl acetate, ultrasonic 10min, centrifugal 5min, draws the supernatant, adds 3mL ethyl acetate and repeats to extract, merge supernatant, mixing。
3. method according to claim 1, it is characterised in that: described sample is Xinhui tangerine peel, the general tea of Citrus chachiensis Hort., described step (2). the method for sample extraction is: weighs 2.00g sample and is placed in 50mL centrifuge tube, add 4mL water, vibration 1min, ultrasonic 10min, add 5mL ethyl acetate, ultrasonic 10min, centrifugal 5min, draws the supernatant, adds 5mL ethyl acetate and repeats to extract, merge supernatant, mixing。
4. according to the method in claim 2 or 3, it is characterised in that in described step (3), organic solvent is 1mL ethyl acetate。
5. according to the method in claim 2 or 3, it is characterised in that: described centrifugal speed is 3000r/min。
6. according to the method in claim 2 or 3, it is characterised in that: described standard sample of pesticide solution concentration is 100 μ g/mL, and solvent is acetone。
7. according to the method in claim 2 or 3, it is characterised in that: the aperture of described filter membrane is 0.22 μm。
8. according to the method in claim 2 or 3, it is characterised in that: described extraction column includes column jecket, lower sieve plate, lower floor's filler, isolation sieve plate, upper strata filler and upper sieve plate；Described lower sieve plate, lower floor's filler, isolation sieve plate, upper strata filler and upper sieve plate are distributed in described column jecket successively from the bottom to top；Wherein said lower floor filler is modified multiwalled carbon nanotube, and consumption is 0.5g；Described upper strata filler is N-propyl group ethylenediamine filler, and consumption is 0.5g；The thickness of described upper sieve plate is more than described lower sieve plate。
9. method according to claim 8, it is characterized in that the preparation method of described extraction column is: take column jecket described in 10mL, described lower sieve plate is laid in bottom, load 0.5g modified multiwalled carbon nanotube, beat gently and make uniform filling, after flattening with isolation sieve plate, load 0.5gN-propyl group ethylenediamine filler on isolation sieve plate top, beat gently, flatten with described upper sieve plate, successively with 6mL methanol, the activation of 6mL ethyl acetate, to obtain final product。
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