CN101782558A - Method for detecting organophosphorus multi-pesticide residue in tea based on matrix effect compensation - Google Patents
Method for detecting organophosphorus multi-pesticide residue in tea based on matrix effect compensation Download PDFInfo
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Abstract
The invention relates to a method for detecting an organophosphorus multi-pesticide residue in tea based on matrix effect compensation, which belongs to the technical field of safety detection of foods. The method comprises the following steps of: (1) mixing a pesticide standard solution; (2) preparing a sample solution; (3) detecting a sample to be detected by a gas chromatogram and mixing the standard solution. The method is rapid, simple and economic, has high sensitivity, effectively reduces or eliminates the interference of a complex matrix derived from the tea on the detection of organophosphorus pesticide residues and provides a scientific basis for further improving an evaluation system of the quality safety of the tea.
Description
Technical field
The invention belongs to the food safety detection technical field, be specifically related to a kind of based on method for detecting organophosphorus multi-pesticide residue in the tealeaves of matrix effect compensation.
Background technology
It is the analysis of trace components in the complex mixture that the residues of pesticides chromatogram detects, and the influence of matrix effect problem is remarkable unusually.Matrix effect in the pesticide residue analysis process, be that the matrix components of other except that analyte causes the determinand measured value to depart from true value in the sample, influence the quantitative precision and the precision of determinand, and influence factor be changeable, very difficult quilt is eliminated fully, has a strong impact on the accuracy of testing result.Most of agricultural chemicals in gas chromatographic analysis, show matrix enhancement effect in various degree, especially the matrix effect of organophosphorus insecticide is very obvious, detection as organophosphorus pesticide in the high fat content sample, the agricultural chemicals recovery that majority contains the P=0 group can surpass 130%, and this phenomenon is called the response enhancement effect that matrix causes.
Tealeaves is because of its complicated as perennial woody plant and following process process, and the sample substrate background is abundant unusually, and this is just more complex than general fruit and vegetable in the influence of sample substrate, and the influence of matrix effect is suitable complexity especially.Matrix effect increases stochastic error and systematic error, and the accuracy of impact analysis and sensitivity have a strong impact on accurately quantitative and positive determinacy of agricultural residual mensuration.
What now, be used for remedying matrix effect abroad more commonly has a correction method of matrix match-on criterion.As the gas chromatography matrix enhancement effect research to organophosphorus pesticide such as Erney D R in 1993; Kocourek V in 1998 etc. are to the stability study of agricultural chemicals in plant extract matrix; Martinez.Vidal J L in 2004 etc. measure the research that agricultural defective goods are estimated to gas chromatography mass spectrometry in 6 kinds of food.The exploitation of external at present multi-pesticide residue method perhaps all uses the matrix match-on criterion to calibrate, so that identical in the matrix environment in the standard specimen and the sample, but obtain and the strict matrix of mating of each sample, this a large amount of routine work for Routine Test Lab is unpractical.Remedy matrix effect and also have several different methods such as standard addition method, multiple purifying method, correction factor calibration method in addition.Measure the residual research of organophosphorus farming in the typical fruits and vegetables matrix as gas such as calendar year 2001 Podhomiak L V spectrum pfpd; Calendar year 2001 Schenck F J even depth purifies and reduces the research of gas spectrum to the matrix effect of the residual mensuration of food middle peasant; Gas such as Gonz-lez spectrum ecd measured the systematic error with the quantitative measurement of pyrethro ids in the typical curve relative correction vegetables such as the matrix effect research of pesticide multi-residues in the typical vegetables, Martinez-Galera M in 2003 in 2002; Gas chromatography mass spectrometries such as Ferndndez Gonzdl ez C in 2003 are measured the research of the fungicide in the white grape; Spe such as Albero B, gas chromatography mass spectrometry were measured the residual mensuration research of honey middle peasant in 2004; Consuelo S in 2005 etc. offset the mensuration research of matrix effect method to the coupling of agricultural residual gas matter with the matrix protection agent.
Domestic research to this problem at present is less, and the exploitation of at present domestic many pesticide residue analysis method does not also attach great importance to the influence that matrix effect produced mostly, does not take the corresponding compensation measure yet.Zhao Haifeng in 2006 is only arranged with the agricultural residual research in the gas chromatography mass spectrometry mensuration vegetables, proofread and correct the matrix enhancement effect with the matrix match-on criterion; Yellow treasured in 2006 is bravely measured pesticide multi-residues research in the fruits and vegetables with gas chromatography mass spectrometry, has carried out several pieces of researchs such as the matrix effect research of agricultural chemicals list concentration and matrix protection agent exploration and has reported.
Because the generation of matrix effect has considerable influence for the accurate qualitative and quantitative of compound, so matrix effect is investigated assessment and adopted an effective measure that to eliminate or compensate be to carry out an indispensable important step in pesticide residue analysis method exploitation or the method validation process, be to obtain more accurate and a basic prerequisite must considering of result accurately.
Summary of the invention
Problem at the prior art existence, the objective of the invention is to design provide a kind of fast, simple, economical, highly sensitive, and can reduce effectively or eliminate the interference measured to organophosphorus pesticide from the complex matrices of tealeaves based on method for detecting organophosphorus multi-pesticide residue in the tealeaves of matrix effect compensation.
Described based on method for detecting organophosphorus multi-pesticide residue in the tealeaves of matrix effect compensation, it is characterized in that may further comprise the steps:
1) pesticide standard solution preparation
A. agricultural chemicals hybrid standard stock solution preparation: take by weighing various organophosphorus insecticide standard items, use acetone diluted, be mixed with the single pesticide standard storing solution of 1000mg/L one by one,, be mixed with the hybrid standard stock solution with acetone according to the instrument response of each agricultural chemicals;
B. the matrix protection agent solution is prepared: after fructose is dissolved in water, use the acetone constant volume, being mixed with concentration is the matrix protection agent A of 35-45mg/mL, after the L-glonate-gamma-lactonic is dissolved in water, use the acetone constant volume, being mixed with concentration is the matrix protection agent B of 15-25mg/mL;
C. agricultural chemicals hybrid standard working fluid preparation: get 1.0mL agricultural chemicals hybrid standard stock solution, add matrix protection agent A 0.05-0.15mL and B 0.05-0.15mL and be mixed with agricultural chemicals hybrid standard working fluid, standby;
2) sample solution preparation
A. test portion preparation: get the tealeaves sample, after comminutor is pulverized, make and treat test sample, standby;
B. testing sample extracts: get and treat test sample 4g, add 10-15ml acetone, in oscillator quick oscillation 5-15 minute, centrifugal 10-15min under centrifuge speed 3500-5000rpm condition got supernatant then;
C. purify: get the 5ml supernatant, the rotation vacuum concentrates after supernatant is closely done, be settled to 2.0ml with acetone solution, transfer in the centrifuge tube, and in centrifuge tube, add (C18) 80-120mg, mixing 2-4min on vortex mixer, centrifugal 5-10min under centrifuge speed 3500-5000rpm condition then, get supernatant 1ml after centrifugal, add matrix protection agent A 0.05-0.15mL and B 0.05-0.15mL at last, for chromatographic determination;
3) treat test sample and mixed standard solution by gas Chromatographic Determination
A. measure: draw 1.0 μ L agricultural chemicals hybrid standard working fluids and treating in the test sample injecting chromatograph after purifying by automatic sampler, qualitative with the twin columns retention time, with the sample solution peak area and the standard solution peak area quantification of analytical column A acquisition;
B. interpretation of result: the retention time of unknown component is compared with the retention time of standard specimen on same chromatographic column respectively in the sample that twin columns record, if in the sample in two of certain component groups of retention times and the standard two groups of retention times of a certain agricultural chemicals differ all this agricultural chemicals of regarding as in ± 0.05min;
Tested persticide residue is in massfraction ω in the sample, and computing formula is as follows:
In the formula:
The content of agricultural chemicals in Ψ-standard solution, unit are mg/litre (mg/L);
The peak area of tested agricultural chemicals in the A-sample;
A
sThe peak area of tested agricultural chemicals in the-pesticide standard solution;
V
1-extraction solvent cumulative volume;
V
2-draw out the volume of the extraction solution that is used to detect;
V
3-sample constant volume;
The quality of m-sample.
Described based on method for detecting organophosphorus multi-pesticide residue in the tealeaves of matrix effect compensation, it is characterized in that taking by weighing metrifonate in the described step 1), DDVP, acephatemet, Menite, orthene, ethoprop, thimet, omethoate, Carbicron, disulfoton, propetamphos, iprobenfos, dichlofenthion, Azodrin, Rogor, phosphamidon, Nankor, methylpyrimidine sulphur phosphorus, chlopyrifos, parathion-methyl, Diothyl, the malathion, fenifrothion, parathion, Rilariol, isocarbophos, phenthoate dimephenthoate cidial, Ravap, Plondrel, phosfolan_methyl, Ethodan, Hostathion, famphur, EPN, phosmet, Phosalone, azinphos-methyl, pyrazophos, azinphos ethyl, Resistox, 2-dichloroethylk dimethyl phosphate, sulfotep, basudin, Fonofos, the malicious phosphorus in ground, Entex, bromophos, paraoxon, isofenphos, Profenofos and phosfolan standard sample of pesticide, use acetone diluted one by one, be mixed with the single pesticide standard storing solution of 51 kinds of agricultural chemicals 1000mg/L, and be mixed with the hybrid standard stock solution with acetone; When treating chromatographic determination, get 1.0mL agricultural chemicals hybrid standard stock solution, add matrix protection agent A 0.1mL and B 0.1mL and be mixed with agricultural chemicals hybrid standard working fluid.
Described based on method for detecting organophosphorus multi-pesticide residue in the tealeaves of matrix effect compensation, it is characterized in that step b adds water 8.5mL dissolving in the described step 1) in fructose 1.75-2.25g, be settled to 50mL with acetone again, making concentration is the matrix protection agent A of 35-45mg/mL; Add water 10mL dissolving in L-glonate-gamma-lactonic 0.75-1.25g, be settled to 50mL with acetone again, making concentration is the matrix protection agent B of 15-25mg/mL.
Described based on method for detecting organophosphorus multi-pesticide residue in the tealeaves of matrix effect compensation, it is characterized in that described step 2) in centrifugal 10min under the centrifugal employing of the step b 4000rpm condition.
Described based on method for detecting organophosphorus multi-pesticide residue in the tealeaves of matrix effect compensation, it is characterized in that described step 2) in centrifugal 5min under the centrifugal employing of the step c 4000rpm condition.
Described based on method for detecting organophosphorus multi-pesticide residue in the tealeaves of matrix effect compensation, it is characterized in that described step 2) in step c get supernatant 1ml after centrifugal, add matrix protection agent A 0.1mL and B 0.1mL at last, for chromatographic determination; Treat that test sample is too muddy after the purification, with carrying out chromatographic determination again behind the 0.2 μ m membrane filtration.
Described based on method for detecting organophosphorus multi-pesticide residue in the tealeaves of matrix effect compensation, it is characterized in that GC conditions is in the described step 3):
Chromatographic column: pre-column, 1.0m, the 0.32mm internal diameter takes off quartz capillary column alive, adopts two root chromatogram columns, is respectively: the A post: 50% polyphenyl methyl siloxane post, 30m * 0.32mm * 0.25 μ m,
B post: 100% polymethyl siloxane post, 30m * 0.32mm * 0.25 μ m; Temperature: injector temperature is 220 ℃, and detector temperature is 250 ℃; Heating schedule: be initially 80 ℃, behind the maintenance 1min, be raised to 220 ℃, keep 1min with 15 ℃/min programming rate; Be raised to 250 ℃ with 20 ℃/min programming rate then, keep 7min;
Gas and flow:
Carrier gas: nitrogen, purity 〉=99.999%, flow velocity are 10mL/min,
Combustion gas: hydrogen, purity 〉=99.999%, flow velocity are 75mL/min,
Combustion-supporting gas: air, flow velocity are 100mL/min;
Input mode: split sampling not.
Described based on method for detecting organophosphorus multi-pesticide residue in the tealeaves of matrix effect compensation, the purity that it is characterized in that described various agricultural chemicals is more than or equal to 96%.
Principle of the present invention: organophosphorus insecticide is through acetone extraction in the sample; extract solution after the matrix dispersion extraction purifies, concentrates; add the matrix protection agent; two injection ports with double tower automatic sampler while injection gas chromatography; component is separated through two capillary posts of opposed polarity in the sample, and flame photometric detector (FPD) (FPD) detects.External standard method is qualitative, quantitative.
Behind the organophosphorus pesticide, disperse Solid-Phase Extraction to purify in the present invention's usefulness acetone reagent extraction tealeaves with C18; The mixture that adds matrix protection agent-fructose and gulonolactone in preceding extraction purified solution is with the compensation matrix effect; Measure with gas chromatography-flame photometric detector (FPD), improved 51 kinds of residual detection correctness of organophosphorus farming, minimum detectability is reduced to 0.005mg/L-0.02mg/L; And prolonged the instrument maintenance cycle to a certain extent, reduced the instrument maintenance cost.This method fast, simple, economical, highly sensitive, reduce effectively or eliminated the interference of measuring to organophosphorus pesticide from the complex matrices of tealeaves, for the appraisement system that further improves quality and safety of tea provides scientific basis.
The advantage that the present invention compared with prior art exists is:
(1) the present invention proposes a kind of the matrix protection agent (fructose and gulonolactone) that can replace the matrix match-on criterion to proofread and correct; to substitute the method for the compensation matrix effect that loaded down with trivial details matrix match-on criterion proofreaies and correct; fast, economical easy and simple to handle; grasp easily; method recovery of standard addition 80-110%; RSD 0.98～6.6%, is enough to satisfy daily Detecting Pesticide requirement.
(2) the present invention adds 51 kinds of residual detection correctness of organophosphorus farming such as organophosphorus pesticide-acephatemet, orthene, chlopyrifos, Rogor, isocarbophos, malathion, iprobenfos that the matrix protection agent has improved the commonly used and normal inspection of tea export in the tea place; strong as 8.31 multiplications of (with concentration sample/standard specimen) acephatemet; the strong organophosphorus pesticide that waits of orthene 4.90 multiplication is all proofreaied and correct to about 1, reduces effectively or has eliminated the interference of measuring to organophosphorus pesticide from the complex matrices of tealeaves.
(3) the present invention adds the peak shape that the matrix protection agent can also improve the target organophosphorus pesticide, and its signal to noise ratio (S/N ratio) is significantly improved, and reduces the agricultural residual detectability of 51 kinds of organophosphoruss to 0.005-0.02mg/kg, has improved the sensitivity that organophosphorus pesticide detects in the tealeaves.
(4) the present invention has prolonged the instrument maintenance cycle to a certain extent, making daily per 100 samples of gas chromatograph must carry out 1 daily maintenance increases to every 150-200 sample and carries out 1 daily maintenance, reduce the instrument maintenance cost, improved detection efficiency.
Description of drawings
Fig. 1 carries out the chromatogram that the organophosphorus pesticide detection obtains for using method of the present invention to the blank tealeaves sample that has added 13 kinds of organophosphorus pesticides.
Among the figure: 1-acephatemet, 2-orthene, 3-thimet, 4-omethoate, 5-Rogor, 6-parathion-methyl, 7-fenifrothion, 8-parathion, 9-isocarbophos, 10-methidathion, 11-Ethodan, 12-carbophenothion, 13-Hostathion.
Embodiment
Below further specify the present invention by specific embodiment.
Embodiment:
1. pesticide standard solution preparation
Single pesticide standard storing solution: accurately take by weighing a certain amount of certain standard sample of pesticide, use acetone diluted, be mixed with the single pesticide standard storing solution of 51 kinds of agricultural chemicals 1000mg/L one by one, be stored in below-18 ℃ in the refrigerator.
Agricultural chemicals hybrid standard stock solution and agricultural chemicals hybrid standard working fluid: 51 kinds of agricultural chemicals are divided into 2 groups, according to group in the table 1, according to separation efficiency 51 kinds of organophosphorus pesticides are divided into 2 groups, instrument response according to each agricultural chemicals, other single agricultural chemicals storing solution on the same group of drawing certain volume one by one injects same volumetric flask respectively,, adopt and be mixed with 2 groups of agricultural chemicals hybrid standard stock solutions to scale with acetone diluted with quadrat method.When treating chromatographic determination; get 1.0mL agricultural chemicals hybrid standard stock solution; add matrix protection agent A 0.1mL and B 0.1mL and be configured to agricultural chemicals hybrid standard working fluid; or adding matrix protection agent A 0.05mL and B 0.1mL; or matrix protection agent A 0.1mL and B 0.15mL, or matrix protection agent A 0.15mL and B 0.15mL.
51 kinds of organophosphorus pesticide tabulations of table 1 and grouping
| Sequence number | Chinese name | English name | Purity | Solvent | Group |
| ??1 | DDVP | ??Dichiorvos | ??≥96％ | Acetone | ??I |
| ??2 | 2-dichloroethylk dimethyl phosphate | ??Naled | ??≥96％ | Acetone | ??II |
| ??3 | Metrifonate | ??Trichlorfon | ??≥96％ | Acetone | ??I |
| ??4 | Acephatemet | ??Methami?daphos | ??≥96％ | Acetone | ??I |
| ??5 | Menite | ??Mevinphos | ??≥96％ | Acetone | ??I |
| ??6 | Orthene | ??Acephate | ??≥96％ | Acetone | ??I |
| ??7 | Ethoprop | ??Ethoprophos | ??≥96％ | Acetone | ??I |
| ??8 | Thimet | ??Phorate | ??≥96％ | Acetone | ??I |
| ??9 | Sulfotep | ??Sulfotep | ??≥96％ | Acetone | ??II |
| ??10 | Flolimat | ??Omethoate | ??≥96％ | Acetone | ??I |
| ??11 | Diazinon | ??Diazinon | ??≥96％ | Acetone | ??II |
| ??12 | Carbicron | ??Dicrotophos | ??≥96％ | Acetone | ??I |
| ??13 | Fonofos | ??Fonofos | ??≥96％ | Acetone | ??II |
| ??14 | Disulfoton | ??Disulfoton | ??≥96％ | Acetone | ??I |
| ??15 | Propetamphos | ??propetamphos | ??≥96％ | Acetone | ??I |
| ??16 | Dichlofenthion | ??Dichlofenthion | ??≥96％ | Acetone | ??I |
| ??17 | Azodrin | ??Monocrotophos | ??≥96％ | Acetone | ??I |
| Sequence number | Chinese name | English name | Purity | Solvent | Group |
| ??18 | Rogor | ??Dimethoate | ??≥96％ | Acetone | ??I |
| ??19 | Phosphamidon | ??Phosphamidon | ??≥96％ | Acetone | ??I |
| ??20 | Chlorpyrifos-methyl | ??Chlorpyrifos-methyl | ??≥96％ | Acetone | ??I |
| ??21 | Nankor | ??Fenchlorphos | ??≥96％ | Acetone | ??I |
| ??22 | Pirimiphos-methyl | ??Pirimiphos-methyl | ??≥96％ | Acetone | ??I |
| ??23 | Chlopyrifos | ??Chlorpyrifos | ??≥96％ | Acetone | ??I |
| ??24 | Parathion-methyl | ??Parathion-methyl | ??≥96％ | Acetone | ??I |
| ??25 | The malicious phosphorus in ground | ??Trichloronate | ??≥96％ | Acetone | ??II |
| ??26 | Diothyl | ??Primiphos-rthyl | ??≥96％ | Acetone | ??II |
| ??27 | Entex | ??Fenthion | ??≥96％ | Acetone | ??II |
| ??28 | Paraoxon | ??Paraoxon | ??≥96％ | Acetone | ??II |
| ??29 | Bromophos | ??Bromophos | ??≥96％ | Acetone | ??II |
| ??30 | The malathion | ??Malathion | ??≥96％ | Acetone | ??I |
| ??31 | Fenifrothion | ??Fenitrothion | ??≥96％ | Acetone | ??I |
| ??32 | Parathion | ??Parathion | ??≥96％ | Acetone | ??I |
| ??33 | Isofenphos | ??Isofenphos | ??≥96％ | Acetone | ??II |
| ??34 | Rilariol | ??Bromophos-ethyl | ??≥96％ | Acetone | ??I |
| ??35 | Isocarbophos | ??isocarbophos | ??≥96％ | Acetone | ??I |
| ??36 | Quinalphos | ??Quinalphos | ??≥96％ | Acetone | ??I |
| ??37 | Phenthoate dimephenthoate cidial | ??Phenthoate | ??≥96％ | Acetone | ??I |
| Sequence number | Chinese name | English name | Purity | Solvent | Group |
| ??38 | Ravap | ??Tetrachlorvinphos | ??≥96％ | Acetone | ??I |
| ??39 | Profenofos | ??Profenofos | ??≥96％ | Acetone | ??II |
| ??40 | Plondrel | ??Ditalimfos | ??≥96％ | Acetone | ??I |
| ??41 | Phosfolan_methyl | ??Phosfolan-methyl | ??≥96％ | Acetone | ??I |
| ??42 | Azinphos-methyl | ??Azinphos-methyl | ??≥96％ | Acetone | ??I |
| ??43 | Phosfolan | ??Phosfolan | ??≥96％ | Acetone | ??II |
| ??44 | Ethodan | ??Ethion | ??≥96％ | Acetone | ??I |
| ??45 | Hostathion | ??Triazophos | ??≥96％ | Acetone | ??I |
| ??46 | Famphur | ??Famphur | ??≥96％ | Acetone | ??I |
| ??47 | EPN | ??EPN | ??≥96％ | Acetone | ??I |
| ??48 | Phosmet | ??Phosmet | ??≥96％ | Acetone | ??I |
| ??49 | Phosalone | ??Phosalone | ??≥96％ | Acetone | ??I |
| ??50 | Azinphos ethyl | ??Azinphos-ethyl | ??≥96％ | Acetone | ??I |
| ??51 | Resistox | ??Coumaphos | ??≥96％ | Acetone | ??I |
2. matrix protection agent solution preparation
Take by weighing fructose 2g and add water 8.5mL dissolving, be settled to 50mL, be designated as matrix protection agent A with acetone; Take by weighing L-glonate-gamma-lactonic 1g and add water 10mL dissolving, be settled to 50mL, be designated as matrix protection agent B with acetone.Be stored in 4 ℃ of left and right sides refrigerators stand-by.Also can be mixed with 35,40 or the matrix protection agent A and 15 of 45mg/mL, 20 or the matrix protection agent B of 25mg/mL
3. analytical procedure
3.1 test portion preparation
Get and be no less than 100g tealeaves sample, put into comminutor and pulverize, make and treat test sample, put into the packing containers for future use.
3.2 extract
Accurately take by weighing the 4.0g test portion and put in the people 15mL centrifuge tube, add 10mL or 12ml acetone, in oscillator on quick oscillation 10 or 15min, the back is with hydro-extractor 4000 or 5000rpm centrifugal 10 or 15min, it is to be clean to get supernatant.
3.3 purify
Get 5.0mL supernatant rotation vacuum and concentrate near doing; accurately be settled to 2.0mL with acetone solution; and be transferred in the 5mL centrifuge tube, add C1880,100 or 120mg, on the vortex mixer behind the mixing 2min; on hydro-extractor 4000 or 5000rpm centrifugal 5 or 10min; get supernatant 1.0mL, add matrix protection agent A 0.1mL and B 0.1mL, or add matrix protection agent A 0.05mL and B 0.1mL; or matrix protection agent A 0.1mL and B 0.15mL, or matrix protection agent A 0.15mL and B 0.15mL.
For chromatographic determination.Too muddy as sample, measure again after using 0.2 μ m membrane filtration.
3.4 measure
3.4.1 chromatogram reference conditions
3.4.1.1 chromatographic column
Pre-column, 1.0m, the 0.32mm internal diameter takes off quartz capillary column alive.
Adopt two root chromatogram columns, be respectively:
A post: 50% polyphenyl methyl siloxane (DB-1701) post, 30m * 0.32mm * 0.25 μ m;
B post: 100% polymethyl siloxane (DB-1) post, 30m * 0.32mm * 0.25 μ m.
3.4.1.2 temperature
Injector temperature, 220 ℃.
Detector temperature, 250 ℃;
Heating schedule: be initially 80 ℃ (maintenance 1min) and be raised to 220 ℃ (keeping 1min) with 15 ℃/min programming rate; Be raised to 250 ℃ (keeping 7min) with 20 ℃/min programming rate then.
3.4.1.3 gas and flow
Carrier gas: nitrogen, purity 〉=99.999%, flow velocity are 10mL/min.
Combustion gas: hydrogen, purity 〉=99.999%, flow velocity are 75mL/min.
Combustion-supporting gas: air, flow velocity are 100mL/min.
3.4.1.4 input mode
Split sampling not.Sample is duplicate, by double tower automatic sampler while sample introduction.
3.4.2 stratographic analysis
Draw in 1.0 μ L standard mixed solutions (or the sample after the purifying) injecting chromatograph by automatic sampler, qualitative with the twin columns retention time, more quantitative with sample solution peak area and standard solution peak area ratio that analytical column A obtains.
4. expression of results
4.1 it is qualitative
The retention time of unknown component (RT) is compared with the retention time (RT) of standard specimen on same chromatographic column respectively in the sample that twin columns record, if in the sample in two of certain component groups of retention times and the standard two groups of retention times of a certain agricultural chemicals differ all this agricultural chemicals of regarding as in ± 0.05min.
4.2 calculate
Tested persticide residue is in massfraction ω in the sample, and numerical value is with every kilogram of milligram (mg/kg) expression, and by formula calculate (1).
In the formula:
The content of agricultural chemicals in Ψ-standard solution, unit are mg/litre (mg/L);
The peak area of tested agricultural chemicals in the A-sample;
A
sThe peak area of tested agricultural chemicals in the-pesticide standard solution;
V
1-extraction solvent cumulative volume;
V
2-draw out the volume of the extraction solution that is used to detect;
V
3-sample constant volume;
The quality of m-sample.
Result of calculation keeps three significant figures.
(1) use above-mentioned method the blank tealeaves sample that has added 13 kinds of organophosphorus pesticides is carried out the organophosphorus pesticide detection, chromatogram is seen Fig. 1, and testing result sees Table 2.
Table 2 adds the sample detection result
| Mark-on concentration | Detectable concentration | Recovery % | |
| Acephatemet | ??0.1 | ??0.084 | ??84 |
| Orthene | ??0.1 | ??0.092 | ??92 |
| Thimet | ??0.1 | ??0.100 | ??100 |
| Omethoate | ??0.1 | ??0.080 | ??80 |
| Rogor | ??0.1 | ??0.096 | ??96 |
| Parathion-methyl | ??0.1 | ??0.093 | ??93 |
| Fenifrothion | ??0.1 | ??0.102 | ??102 |
| Parathion | ??0.1 | ??0.095 | ??95 |
| Isocarbophos | ??0.1 | ??0.094 | ??94 |
| Methidathion | ??0.1 | ??0.093 | ??93 |
| Ethodan | ??0.1 | ??0.090 | ??90 |
| Carbophenothion | ??0.1 | ??0.082 | ??82 |
| Hostathion | ??0.1 | ??0.082 | ??82 |
(2) use above-mentioned method 53 on the market different tealeaves samples (scope covers green tea, black tea, oolong, Pu'er etc.) have been carried out the organophosphorus pesticide detection, the result detects 11 kinds of organophosphorus pesticides in 15 samples, concrete outcome sees Table 3.
Organophosphorus pesticide testing result in table 3 actual sample
| Acephatemet | Rogor | Omethoate | Menite | Orthene | Isocarbophos | Fenifrothion | Quinalphos | Chlopyrifos | Carbophenothion | Methidathion | |
| Dragon Well tea 1 | ??0.05 | ||||||||||
| Dragon Well tea 2 | ??0.01 | ||||||||||
| Long Ding becomes civilized | ??0.2 | ||||||||||
| Hair peak 1 | ??0.1 | ||||||||||
| Hair peak 2 | ??0.02 | ||||||||||
| Pilochun (a green tea) | ??0.01 | ||||||||||
| High-quality green tea | ??0.1 | ||||||||||
| Red fannings 1 | ??0.03 | ||||||||||
| Red fannings 2 | ??0.02 | ||||||||||
| Iron Guanyin 1 | ??0.02 | ||||||||||
| Iron Guanyin 2 | ??0.2 | ||||||||||
| Clovershrub 1 | ??0.01 | ||||||||||
| Clovershrub 2 | ??0.01 | ||||||||||
| Pu'er tea 1 | ??0.05 | ||||||||||
| Pu'er tea 2 | ??0.05 |
Claims (8)
1. based on method for detecting organophosphorus multi-pesticide residue in the tealeaves of matrix effect compensation, it is characterized in that may further comprise the steps:
1) pesticide standard solution preparation
A. agricultural chemicals hybrid standard stock solution preparation: take by weighing various organophosphorus insecticide standard items, use acetone diluted, be mixed with the single pesticide standard storing solution of 1000mg/L one by one,, be mixed with the hybrid standard stock solution with acetone according to the instrument response of each agricultural chemicals;
B. the matrix protection agent solution is prepared: after fructose is dissolved in water, use the acetone constant volume, being mixed with concentration is the matrix protection agent A of 35-45mg/mL, after the L-glonate-gamma-lactonic is dissolved in water, use the acetone constant volume, being mixed with concentration is the matrix protection agent B of 15-25mg/mL;
C. agricultural chemicals hybrid standard working fluid preparation: get 1.0mL agricultural chemicals hybrid standard stock solution, add matrix protection agent A 0.05-0.15mL and B 0.05-0.15mL and be mixed with agricultural chemicals hybrid standard working fluid, standby;
2) sample solution preparation
A. test portion preparation: get the tealeaves sample, after comminutor is pulverized, make and treat test sample, standby;
B. testing sample extracts: get and treat test sample 4g, add 10-15ml acetone, in oscillator quick oscillation 10-15 minute, centrifugal 10-15min under centrifuge speed 3500-5000rpm condition got supernatant then;
C. purify: get the 5ml supernatant, the rotation vacuum concentrates after supernatant is closely done, be settled to 2.0ml with acetone solution, transfer in the centrifuge tube, and in centrifuge tube, add (C18) 80-120mg, mixing 2-4min on vortex mixer, centrifugal 5-10min under centrifuge speed 3500-5000rpm condition then, get supernatant 1ml after centrifugal, add matrix protection agent A 0.05-0.15mL and B 0.05-0.15mL at last, for chromatographic determination;
3) treat test sample and mixed standard solution by gas Chromatographic Determination
A. measure: draw 1.0 μ L agricultural chemicals hybrid standard working fluids and treating in the test sample injecting chromatograph after purifying by automatic sampler, qualitative with the twin columns retention time, with the sample solution peak area and the standard solution peak area quantification of analytical column A acquisition;
B. interpretation of result: the retention time of unknown component is compared with the retention time of standard specimen on same chromatographic column respectively in the sample that twin columns record, if in the sample in two of certain component groups of retention times and the standard two groups of retention times of a certain agricultural chemicals differ all this agricultural chemicals of regarding as in ± 0.05min;
Tested persticide residue is in massfraction ω in the sample, and computing formula is as follows:
In the formula:
The content of agricultural chemicals in Ψ-standard solution, unit are mg/litre (mg/L);
The peak area of tested agricultural chemicals in the A-sample;
A
sThe peak area of tested agricultural chemicals in the-pesticide standard solution;
V
1-extraction solvent cumulative volume;
V
2-draw out the volume of the extraction solution that is used to detect;
V
3-sample constant volume;
The quality of m-sample.
2. as claimed in claim 1 based on method for detecting organophosphorus multi-pesticide residue in the tealeaves of matrix effect compensation, it is characterized in that taking by weighing metrifonate in the described step 1), DDVP, acephatemet, Menite, orthene, ethoprop, thimet, omethoate, Carbicron, disulfoton, propetamphos, iprobenfos, dichlofenthion, Azodrin, Rogor, phosphamidon, Nankor, methylpyrimidine sulphur phosphorus, chlopyrifos, parathion-methyl, Diothyl, the malathion, fenifrothion, parathion, Rilariol, isocarbophos, phenthoate dimephenthoate cidial, Ravap, Plondrel, phosfolan_methyl, Ethodan, Hostathion, famphur, EPN, phosmet, Phosalone, azinphos-methyl, pyrazophos, azinphos ethyl, Resistox, 2-dichloroethylk dimethyl phosphate, sulfotep, basudin, Fonofos, the malicious phosphorus in ground, Entex, bromophos, paraoxon, isofenphos, Profenofos and phosfolan standard sample of pesticide, use acetone diluted one by one, be mixed with the single pesticide standard storing solution of 51 kinds of agricultural chemicals 1000mg/L, and be mixed with the hybrid standard stock solution with acetone; When treating chromatographic determination, get 1.0mL agricultural chemicals hybrid standard stock solution, add matrix protection agent A 0.1mL and B 0.1mL and be mixed with agricultural chemicals hybrid standard working fluid.
3. as claimed in claim 1 based on method for detecting organophosphorus multi-pesticide residue in the tealeaves of matrix effect compensation, it is characterized in that step b adds water 8.5mL dissolving in the described step 1) in fructose 1.75-2.25g, be settled to 50mL with acetone again, making concentration is the matrix protection agent A of 35-45mg/mL; Add water 10mL dissolving in L-glonate-gamma-lactonic 0.75-1.25g, be settled to 50mL with acetone again, making concentration is the matrix protection agent B of 15-25mg/mL.
4. as claimed in claim 1 based on method for detecting organophosphorus multi-pesticide residue in the tealeaves of matrix effect compensation, it is characterized in that described step 2) in centrifugal 10min under the centrifugal employing of the step b 4000rpm condition.
5. as claimed in claim 1 based on method for detecting organophosphorus multi-pesticide residue in the tealeaves of matrix effect compensation, it is characterized in that described step 2) in centrifugal 5min under the centrifugal employing of the step c 4000rpm condition.
6. as claimed in claim 1 based on method for detecting organophosphorus multi-pesticide residue in the tealeaves of matrix effect compensation, it is characterized in that described step 2) in step c get supernatant 1ml after centrifugal, add matrix protection agent A 0.1mL and B 0.1mL at last, for chromatographic determination; Treat that test sample is too muddy after the purification, with carrying out chromatographic determination again behind the 0.2 μ m membrane filtration.
7. as claimed in claim 1 based on method for detecting organophosphorus multi-pesticide residue in the tealeaves of matrix effect compensation, it is characterized in that GC conditions is in the described step 3):
Chromatographic column: pre-column, 1.0m, the 0.32mm internal diameter takes off quartz capillary column alive, adopts two root chromatogram columns, is respectively: the A post: 50% polyphenyl methyl siloxane post, 30m * 0.32mm * 0.25 μ m,
B post: 100% polymethyl siloxane post, 30m * 0.32mm * 0.25 μ m;
Temperature: injector temperature is 220 ℃, and detector temperature is 250 ℃;
Heating schedule: be initially 80 ℃, behind the maintenance 1min, be raised to 220 ℃, keep 1min with 15 ℃/min programming rate; Be raised to 250 ℃ with 20 ℃/min programming rate then, keep 7min;
Gas and flow:
Carrier gas: nitrogen, purity 〉=99.999%, flow velocity are 10mL/min,
Combustion gas: hydrogen, purity 〉=99.999%, flow velocity are 75mL/min,
Combustion-supporting gas: air, flow velocity are 100mL/min;
Input mode: split sampling not.
8. as claimed in claim 2 based on method for detecting organophosphorus multi-pesticide residue in the tealeaves of matrix effect compensation, the purity that it is characterized in that described various agricultural chemicals is more than or equal to 96%.
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