CN102636593A - Dispersion solid-phase extraction method for measuring 20 pesticide residues in tea - Google Patents
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Abstract
The invention provides a dispersion solid-phase extraction method for measuring 20 pesticide residues in tea. The dispersion solid-phase extraction method serves as a pretreatment method of a tea sample and comprises the following operation steps of: weighing 1 gram of the tea sample with the quantity being accurate to 0.01 gram, putting the tea sample in a polypropylene centrifugal tube of 10 milliliter with a plug, adding 3 milliliters of acetonitrile into the sample, oscillating the sample for 3 minutes, centrifuging the tea sample for 3 minutes at the rate of 4000 rpm, moving supernate into another centrifugal tube, adding 3 milliliters of acetonitrile into residues, and combining two extracting solutions after the steps are repeated; and blowing the extracting solutions to be dry by virtue of nitrogen at 40 DEG C, accurately moving 1.00 milliliter of acetonitrile for dissolving the solutions again, adding 150 milligrams of ODS reagent and 50 milligrams of PSA reagent into the solutions, performing vortex on the solutions and the reagents on a vortex mixer for 90 seconds, centrifuging the solutions and the reagents for 3 minutes at the rate of 4000 rpm, and passing obtained supernate through a filter membrane of 0.22 micrometer, thus obtaining the residues to be measured by a liquid chromatography-mass spectrometer. According to the method, the pretreatment time is shortened greatly, the reagent consumption quantity is reduced, the analysis cost is reduced, and the analysis sensitivity is improved, so that the method can be applied to measuring the pesticide residues in the tea.
Description
Technical field
The present invention relates to the pre-treating method of tealeaves pesticide residue analysis sample, is a kind of dispersion SPE method, is applied in the tealeaves pesticide residue analysis.
Background technology
Tealeaves is the important industrial crops of China, also is national people's daily necessities.Along with people's improves the food security quality requirements day by day, and the safe mass problem of tealeaves is more and more paid attention to by people.Particularly in recent years, developed country serves as reasons to protect the health with the area, continues to increase the detection kind of residues of pesticides in the tealeaves, and constantly reduces the detectability of detection material.This has become the topmost TBT (Technical Barriers to Trade) of current China tea export.China is tealeaves consumption big country, also is simultaneously pesticide producing and use big country, and pesticide dosage occupies first place in the world, because of drinking existing generation of incident that the agricultural chemicals acute poisoning is taken place by the tealeaves of pollution by pesticides.Therefore, correctly the detecting of residues of pesticides in the tealeaves is to guarantee pressing for of agricultural products in China international trade and food security, also is simultaneously the needs of realizing agricultural power and emerging in large numbers the agricultural product of a collection of world star level.
Tealeaves is made up of many different attribute materials; In the analysis the residues of pesticides component that will detect often in sample content extremely low; Possibly also have the various ingredients coexistence, so, how to carry out effective sample pre-treatments; Can the enriched with trace target components often become the key that effectively detect tea-leaf safety property from tealeaves, and it also is the bottleneck of present analytical test work and the weak link of research both at home and abroad.Therefore, need to carry out tackling key problem, the particularly extraction in the ultramicron pesticide residue analysis, purification, extraction, purifying or pre-separation in the tealeaves to this restriction difficult problem of sample pre-treatments.
In the tealeaves pesticide residue analysis, classical sample-pretreating method such as Suo Shi extract and all there is certain deficiency in liquid-liquid extraction.These method steps are loaded down with trivial details, not only spend the plenty of time, and consumption of organic solvent is big, and extraction efficiency is lower.Same, the tealeaves extraction and cleaning process in the existing national standard method has been used the method for SPE, and also there are some problems in this method, as: 1, pre-treatment process is complicated, grow (1.5-2 hour) consuming time; 2, the employed solid-phase extraction column of purification process costs an arm and a leg (120-150 unit/prop up), and disposable use, causes analysis cost significantly to improve; 3, solvent-oil ratio big (40-50 milliliter) works the mischief to environment and analysis operation person in the pre-treatment process.
The present invention adopts the pre-treatment that disperses solid phase extraction to be used for tealeaves trace residues of pesticides.The method principle be the solvent selecting different types of agricultural chemicals is had the excellent dissolution performance as extraction agent, purifying adsorbent directly is scattered in the extract to be clean, the interference component in the adsorbing base.The advantage of this method is the cleaning activation balance that needn't carry out solid phase extraction column, and the transfer of sample and rotary evaporation step such as concentrate, and is easy and simple to handle; Extraction efficiency is high, and the recovery is high, and solvent-oil ratio is little; Analysis cost is low, is a kind of sample-pretreating method of environmental protection.The present invention is applied to this pre-treating method and liquid chromatograph mass spectrography in the tealeaves pesticide residue analysis.The high score of both having brought into play chromatogram has been brought into play mass spectral high distinguishing ability again from ability, is highly suitable for the qualitative and quantitative analysis of multicomponent mixture.
Summary of the invention
The object of the invention is exactly to the tealeaves sample pre-treatments, has proposed a kind of simple, easy to operate, reappearance is better, sensitivity is higher dispersion SPE method, is used for the fast detecting of 20 kinds of persticide residues of tealeaves.
Technical scheme of the present invention is following:
The pre-treating method of the agricultural chemicals determination of residual amount in a kind of tealeaves is characterized in that disperseing solid phase extraction, and method step comprises:
1), fine ground tealeaves sample is placed the polypropylene centrifuge tube of 10 milliliters of tool plugs, add acetonitrile and extract, vibration is also centrifugal, pipettes supernatant to another centrifuge tube, repeats above extraction step, merges extracted twice liquid, and 40 degrees centigrade of nitrogen blow to doing;
2), in centrifuge tube, add acetonitrile and redissolve, add ODS reagent and PSA reagent, vortex is also centrifugal, the collection supernatant;
3), get supernatant and cross 0.22 micron filter membrane after, feed flow phase chromatograph-mas spectrometer is measured.
The advantage of this method:
1, processing procedure is fairly simple, has shortened extraction analysis time (2 minutes) greatly;
2, adsorbent has only used a spot of ODS and PSA, and is better to the clean-up effect of object, and analysis cost low (5-10 unit/inferior) is economic, practical;
3, with respect to national standard method, the quantity of solvent that this method consumed reduces (7-10 milliliter) greatly, and is friendly more to environment;
4, the extraction efficiency of method is high, and the recovery is high, has reduced the loss of target compound.
Therefore, this method is simple, quick, greatly reduces experimental cost, is suitable for the mensuration of trace components in the tealeaves sample substrate, has stronger using value.
Description of drawings:
The multiple-reaction monitoring of 20 kinds of pesticide standard solution (MRM) chromatogram (10 microgram/kilogram) is like Fig. 1-Figure 20:
Fig. 1. the multiple-reaction monitoring chromatogram of Simanex standard solution
Fig. 2. the multiple-reaction monitoring chromatogram of Atrazine standard solution
Fig. 3. the multiple-reaction monitoring chromatogram of ametryn standard solution
Fig. 4. the multiple-reaction monitoring chromatogram of Garagard standard solution
Fig. 5. the multiple-reaction monitoring chromatogram of propazine standard solution
Fig. 6. the multiple-reaction monitoring chromatogram of eyeball bacterium azoles standard solution
Fig. 7. the multiple-reaction monitoring chromatogram of triazolone standard solution
Fig. 8. the multiple-reaction monitoring chromatogram of Tebuconazole standard solution
Fig. 9. the multiple-reaction monitoring chromatogram of Hostathion standard solution
Figure 10. the multiple-reaction monitoring chromatogram of propiconazole standard solution
Figure 11. the multiple-reaction monitoring chromatogram of Difenoconazole standard solution
Figure 12. the multiple-reaction monitoring chromatogram of Methomyl standard solution
Figure 13. the multiple-reaction monitoring chromatogram of Mobucin standard solution
Figure 14. the multiple-reaction monitoring chromatogram of sevin standard solution
Figure 15. the multiple-reaction monitoring chromatogram of carbofuran standard solution
Figure 16. the multiple-reaction monitoring chromatogram of Menite standard solution
Figure 17. the multiple-reaction monitoring chromatogram of methiocarb standard solution
Figure 18. the multiple-reaction monitoring chromatogram of Carbicron standard solution
Figure 19. the multiple-reaction monitoring chromatogram of Aphox standard solution
Figure 20. the multiple-reaction monitoring chromatogram of metrifonate standard solution.
Embodiment
Utilize this method to measure 20 kinds of pesticide residues in the tealeaves.
Take by weighing the fine ground tealeaves sample of 1 gram, be accurate to 0.01 gram, in the polypropylene centrifuge tube as for 10 milliliters of tool plugs; Add 3 milliliters of acetonitriles, vibrated 3 minutes, centrifugal 3 minutes with 4000 rev/mins; Pipette supernatant to another centrifuge tube; In residue, add 3 milliliters of acetonitriles again, repeat above extraction step, merge extracted twice liquid; 40 degrees centigrade of nitrogen blow to doing, and accurately pipette 1 milliliter of acetonitrile and redissolve, and add 150 milligrams of ODS reagent and 50 milligrams of PSA reagent; Vortex is 90 seconds on turbine mixer; 4000 rev/mins centrifugal 3 minutes, after getting supernatant and crossing 0.22 micron filter membrane, feed flow phase chromatograph-mas spectrometer is measured.
Chromatographic condition: chromatographic column: Waters symmetry C8 column (150 * 2.1 millimeters); Column temperature: 40 degrees centigrade; Flow velocity: 0.2 ml/min; Sample size: 10 microlitres; Moving phase: A phase: water (containing 0.1% formic acid); B phase: methyl alcohol (containing 0.1% formic acid).Condition of gradient elution is seen table 1:
Table 1 liquid chromatography condition of gradient elution
| Time (min) | A phase (%) | B phase (%) | ? |
| 0.00 | 95 | 5 | ? |
| 15.00 | 0 | 100 | ? |
| 22.00 | 95 | 5 | ? |
Mass spectrum condition: ion gun: electric spray ion source; Scan pattern: positive ion mode; Capillary voltage: 3 kilovolts; Extraction voltage: 20 volts; Ion source temperature: 120 degrees centigrade; The temperature of desolvating: 350 degrees centigrade; The airshed of desolvating: 600 liters/hour; Taper hole airshed: 600 liters/hour; Detection mode: multiple-reaction monitoring (MRM); Select ion detection: every kind of compound is selected a quota ion respectively, 2 qualitative ions.Qualitative ion pair, quota ion are to, collision gas energy and go bunch voltage referring to table 2:
The qualitative, quantitative ion pair of 20 kinds of agricultural chemicals of table 2, collision gas energy and taper hole voltage
Adopt this method and national standard method (GB/T23204-2008) to carry out the contrast experiment, measure 1 μ g/kg standard solution in the tealeaves matrix, replicate determination three times, calculating mean value.Wherein national standard method adopts Clearnert TPT SPE column purification tea extract, rotary evaporation method enrichment method target analytes.This method directly adopts the method purification enrichment that disperses SPE, has omitted concentration step.The sensitivity of 20 kinds of agricultural chemicals and relevant chemicals is higher in this method; Response signal is apparently higher than National Standard Method; Same concentrations adds target analysis result (seeing table 3) demonstration in the tealeaves: have the response signal of 18 kinds of materials stronger than the response signal of National Standard Method in this law; The signal that has only 2 kinds of materials than National Standard Method a little less than, this shows that the sensitivity of this method is higher.In addition; In this method purifying step, disperse the solvent-oil ratio of SPE little (only needing the 1-2 milliliter), the extraction time short (only needing 90 seconds); And conventional SPE solvent-oil ratio be 46 milliliters, required time is 1-2 hour, and the cost of solid phase extraction column is higher.Above experimental result shows that this method has shortened the pre-treatment time greatly, has reduced reagent consumption, has reduced analysis cost, has improved sensitivity for analysis, is a kind of sample-pretreating method of environmental protection.
Be applied to actual tealeaves and measure, the recovery (is seen table 4) between 78% ~ 138%, and the detectability scope obviously increases, and linearly dependent coefficient reaches more than 0.997 (sees table 5).Dispersion SPE method of the present invention, easy to operate, method is sensitive, and accuracy is high, in the tealeaves persticide residue detects, has important use and is worth.
The result that two kinds of methods of table 3 are measured the matrix standard solution compares
The test figure that 20 kinds of agricultural chemicals of table 4 add concentration and average recovery rate thereof
| Sequence number | The compound title | Add concentration/(μ g/kg) | Average recovery rate/(%) | Add concentration/(μ g/kg) | Average recovery rate/(%) |
| 1 | Simanex | 5 | 117 | 50 | 112 |
| 2 | Atrazine | 5 | 110 | 50 | 107 |
| 3 | Ametryn | 1 | 78 | 10 | 108 |
| 4 | Garagard | 1 | 91 | 10 | 120 |
| 5 | Propazine | 5 | 97 | 50 | 115 |
| 6 | Eyeball bacterium azoles | 2.5 | 95 | 25 | 120 |
| 7 | Triazolone | 5 | 111 | 50 | 114 |
| 8 | Tebuconazole | 5 | 117 | 50 | 111 |
| 9 | Hostathion | 2.5 | 104 | 25 | 131 |
| 10 | Propiconazole | 5 | 117 | 50 | 115 |
| 11 | Difenoconazole | 5 | 125 | 50 | 107 |
| 12 | Methomyl | 20 | 121 | 200 | 116 |
| 13 | Mobucin | 5 | 117 | 50 | 131 |
| 14 | Sevin | 5 | 138 | 50 | 128 |
| 15 | Carbofuran | 5 | 125 | 50 | 128 |
| 16 | Menite | 10 | 120 | 100 | 120 |
| 17 | Methiocarb | 5 | 112 | 50 | 132 |
| 18 | Carbicron | 5 | 131 | 50 | 121 |
| 19 | Aphox | 0.5 | 144 | 5 | 119 |
| 20 | Metrifonate | 10 | 135 | 100 | 133 |
Linear equation, related coefficient and the range of linearity of 20 kinds of agricultural chemicals of table 5
| Sequence number | The compound title | Linear equation | Coefficient R | The range of linearity (μ g/kg) |
| 1 | Simanex | Y=-4634.94+5890.93X | 0.9999 | 5-100 |
| 2 | Atrazine | Y=-3773.81+12633.39X | 0.9999 | 1-100 |
| 3 | Ametryn | Y=7902.87+21226.81X | 0.9997 | 1-20 |
| 4 | Garagard | Y=16804.64+47320.20X | 0.9994 | 1-20 |
| 5 | Propazine | Y=2812.47+14601.53X | 0.9999 | 0.5-100 |
| 6 | Nitrile bacterium azoles | Y=14128.05+12429.56X | 0.9989 | 2.5-50 |
| 7 | Triazolone | Y=6585.10+8371.74X | 0.9998 | 5-100 |
| 8 | Tebuconazole | Y=2254.21+17134.26X | 0.9998 | 1-100 |
| 9 | Hostathion | Y=23848.60+16789.016X | 0.9975 | 2.5-50 |
| 10 | Propiconazole | Y=2309.82 +10771.45X | 0.9998 | 0.5-100 |
| 11 | Difenoconazole | Y=-20691.04 +15507.45X | 0.9997 | 5-100 |
| 12 | Methomyl | Y=-6075.41+2271.91X | 0.9972 | 4-400 |
| 13 | Mobucin | Y=3790.28+6340.68X | 0.9997 | 5-100 |
| 14 | Sevin | Y=1732.63+5112.59X | 0.9996 | 1-100 |
| 15 | Carbofuran | Y=-10974.34+9293.81X | 0.9999 | 5-100 |
| 16 | Menite | Y=4468.00+3224.25X | 0.9999 | 10-200 |
| 17 | Methiocarb | Y=7594.55+5179.86X | 0.9985 | 5-100 |
| 18 | Carbicron | Y=-12404.04+9690.47X | 0.9993 | 5-100 |
| 19 | Aphox | Y=-5807.90+53950.79X | 0.9985 | 0.5-10 |
| 20 | Metrifonate | Y=-3243.01+4956.86X | 0.9992 | 1-100 |
Claims (1)
1. the pre-treating method of the agricultural chemicals determination of residual amount in the tealeaves is characterized in that matrix dispersion SPME method, and method step is: take by weighing 1 gram sample; Be accurate to 0.01 gram, place the polypropylene centrifuge tube of 10 milliliters of tool plugs, add 3 milliliters of acetonitriles; Vibrated 3 minutes, with 4000 rev/mins centrifugal 3 minutes, pipette supernatant to another centrifuge tube; In residue, add 3 milliliters of acetonitriles again, repeat above step, merge extracted twice liquid; 40 degrees centigrade of nitrogen blow to doing, and accurately pipette 1.00 milliliters of acetonitriles and redissolve, and add 150 milligrams of ODS reagent and 50 milligrams of PSA reagent; Vortex is 90 seconds on turbine mixer; 4000 rev/mins centrifugal 3 minutes, after getting supernatant and crossing 0.22 micron filter membrane, feed flow phase chromatograph-mas spectrometer is measured.
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Cited By (6)
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| CN103808545A (en) * | 2014-02-24 | 2014-05-21 | 福建出入境检验检疫局检验检疫技术中心 | Natural matrix standard sample for 13 pesticide residues in tea and preparation thereof |
| CN103901137A (en) * | 2012-12-28 | 2014-07-02 | 中粮营养健康研究院有限公司 | Tea pretreatment method for detecting organophosphorus pesticides and application of as well as method for detecting organophosphorus pesticides in tea |
| CN104698114A (en) * | 2014-10-28 | 2015-06-10 | 陈溪 | Method for detecting 205 kinds of pesticide residues in rice |
| CN105784453A (en) * | 2016-03-16 | 2016-07-20 | 吉林省水产科学研究院 | Pretreatment method for detecting avermectin (AVM) and ivermectin (IVM) residues in fish |
| CN111207958A (en) * | 2020-01-08 | 2020-05-29 | 中国农业科学院农业质量标准与检测技术研究所 | Pretreatment agent and pretreatment package for organophosphorus pesticide detection and application thereof |
| CN111855873A (en) * | 2020-07-15 | 2020-10-30 | 中国水产科学研究院长江水产研究所 | Method for determining triazine herbicide residue in aquatic product by ultra-high performance liquid chromatography-tandem mass spectrometry |
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|---|---|---|---|---|
| CN103901137A (en) * | 2012-12-28 | 2014-07-02 | 中粮营养健康研究院有限公司 | Tea pretreatment method for detecting organophosphorus pesticides and application of as well as method for detecting organophosphorus pesticides in tea |
| CN103808545A (en) * | 2014-02-24 | 2014-05-21 | 福建出入境检验检疫局检验检疫技术中心 | Natural matrix standard sample for 13 pesticide residues in tea and preparation thereof |
| CN103808545B (en) * | 2014-02-24 | 2016-02-24 | 福建出入境检验检疫局检验检疫技术中心 | The natural basal body standard model of 13 kinds of residues of pesticides and preparation thereof in tealeaves |
| CN104698114A (en) * | 2014-10-28 | 2015-06-10 | 陈溪 | Method for detecting 205 kinds of pesticide residues in rice |
| CN105784453A (en) * | 2016-03-16 | 2016-07-20 | 吉林省水产科学研究院 | Pretreatment method for detecting avermectin (AVM) and ivermectin (IVM) residues in fish |
| CN105784453B (en) * | 2016-03-16 | 2018-04-13 | 吉林省水产科学研究院 | The pre-treating method of avermectin and ivermectin residue detection in the flesh of fish |
| CN111207958A (en) * | 2020-01-08 | 2020-05-29 | 中国农业科学院农业质量标准与检测技术研究所 | Pretreatment agent and pretreatment package for organophosphorus pesticide detection and application thereof |
| CN111207958B (en) * | 2020-01-08 | 2022-08-02 | 中国农业科学院农业质量标准与检测技术研究所 | Pretreatment agent and pretreatment package for organophosphorus pesticide detection and application thereof |
| CN111855873A (en) * | 2020-07-15 | 2020-10-30 | 中国水产科学研究院长江水产研究所 | Method for determining triazine herbicide residue in aquatic product by ultra-high performance liquid chromatography-tandem mass spectrometry |
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Application publication date: 20120815 |