CN103869025A - Pretreatment method for detecting pesticide residues in fresh tea leaves - Google Patents
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Abstract
The invention provides a pretreatment method for detecting pesticide residues in fresh tea leaves. The method comprises the following steps: selecting a dispersing agent which has high adsorptive property on pesticides such as organic chloride and pyrethroid, directly mixing and grinding the dispersing agent with a fresh leaf sample, so that the cell disruption degree of the sample is improved, and the sample is finally uniformly dispersed; obtaining a mixture in a half-dry state and taking the mixture as a filler, feeding the filler in a chromatographic column in which a certain amount of adsorbents and water removal agents are fed in advance, eluting by using a mixed organic solvent, concentrating an eluant, so that the eluant can be directly subjected to instrumental analysis. According to the method, the operations of extraction and purification of the sample are integrated, and loss of the measured substance caused by sample homogenization, precipitation, centrifugation, dissolution, emulsification and concentration is avoided. Moreover, the method is simple and convenient to operate, high in recovery rate, small in solvent consumption and low in analysis cost and is a green and environment-friendly sample pretreatment method.
Description
Technical field
The present invention relates to agricultural product security detection field, be specifically related to the pre-treating method of the fresh leaf Pesticide Residues of a kind of matrix solid phase dispersion detection tea.
Background technology
Tea is the Chinese state drink of generally acknowledging, is the cultural Symbol that compatriots regard as an honour.China has become the first in the world Chan Cha big country, and 2012, tea place area reached 238.5200 ten thousand hectares, and tea yield reaches 1,780,000 tons, and cultivated area and output all occupy first place in the world; 31.3 ten thousand tons of tea exports in 2012, earn foreign exchange and break through 1,000,000,000 dollars.Drink tea and become most Chinese one way of life customs, tea has become indispensable health drink and spiritual drink in social life.And along with popularizing of health of people consumption idea, tea is accepted, is liked and pursue by increasing people.But tea export is faced with the non-tariff barriers of serious quality and safety aspect, relates to the aspects such as heavy metal, residues of pesticides and microorganism always.Wherein, Pesticide Residue is the most outstanding, is the principal element that hinders China's tea export scale rapid growth.In recent years, European Union, Japan, Korea S etc. constantly implement new more strict Pesticide Residues in Tea standard, strengthen the residual monitoring dynamics of agriculture of import agricultural byproducts, and formally forbid that 320 kinds of agricultural chemicals that contain chemically reactive substance are in domestic sale, wherein, relating to the agricultural chemicals that China produces, uses and sell has 62 kinds, uses the agricultural product of these agricultural chemicals in the time of the above-mentioned area of outlet, is frequently returned goods or destroys.
Therefore, the Ministry of Public Health of China combines with the Ministry of Agriculture and has issued national food safety standard " Pesticide maximum residue limit " GB2763-2012, in formal enforcement on March 1st, 2013, this standard has substituted 10 standards such as " GB2763-2005 ", related pesticide species increases to 322 kinds by original 136 kinds, and the residual limitation of agriculture in tealeaves is increased to 25 by original 19.
At present, research multi-focus both domestic and external is in commodity tealeaves, or the deep processed product such as instant tea, tea extract, and Pesticide Residue in the fresh leaf of less research tea.There are some researches show, the process of tealeaves can't cause significantly degraded or the loss of remains of pesticide in fresh leaf, and what fresh leaves of tea plant was sampled tea as one-tenth processes raw material, and its persticide residue is by residual the agriculture that directly affects tealeaves and deep processed product thereof the problem that exceeds standard.The fresh leaf Pesticide Residues of tea level, can be used as the quality safety index whether tea place can exploit, and has important practical significance for reducing China's Pesticide Residues in Tea level.Therefore, set up the detection method of residual convenient, efficient, inexpensive, the environmental protection of the fresh leaf middle peasant of tea, be conducive to relevant enterprise and control from source the quality of product, hold raw-material quality, reduce residual the caused loss that exceeds standard of agriculture of product.
The fresh leaf of tea includes the organic component of the multiple different attributes such as polyphenol, amino acid, alkaloid, carbohydrate, protein, pigment, the residues of pesticides component that will detect in analysis often content is extremely low, may also have various ingredients to coexist, so, how to carry out effective sample pretreatment, from fresh leaf, the target components of enriched with trace or even ultratrace often becomes the key of effective detection, is also the bottleneck of present analysis test job and the weak link of domestic and international research.The classical sample pretreating method such as Soxhlet extraction, liquid-liquid extraction, complex steps, not only consuming time, consume a large amount of organic solvents, and extraction efficiency is lower.Equally, existing GB/T23205-2008 and GB/T23204-2008 national standard method, for finished tea, measure simultaneously wherein 448 kinds and 519 kinds of agricultures residual, the method that it all adopts acetonitrile high-speed homogenization extraction-solid phase extraction column to purify, also there are the following problems: 1, complicated and time consumption, generally needs 3.0～3.5 hours; 2, cost is high, the solid phase extraction column expensive (100～120 yuan /) using in purification process, and can only disposablely use; 3, in preprocessing process, poisonous and hazardous organic solvent consumes more (80～120 milliliters), and environment and analyst are worked the mischief.
Summary of the invention
In order to solve problems of the prior art, the object of the invention is for the fresh leaf sample pretreatment of tea, provide a kind of matrix solid phase dispersion method of convenient, efficient, inexpensive, environmental protection, for the fast detecting of the fresh leaf organochlorine of tea and pyrethroid pesticide remained amount.
In order to realize the object of the invention, the invention provides a kind of pre-treating method that detects the fresh leaf Pesticide Residues of tea, described method comprises the steps:
1) in glass chromatography column, fill out in advance successively adsorbent and deicer, for subsequent use;
2) fresh tea leaf is cleaned, smashes, mixed, make testing sample, take the fresh leaf testing sample of tea in glass mortar, add spreading agent fully to grind, testing sample is dispersed in Fo Luoli tripoli, after milled mixtures is transferred to the chromatographic column of step 1); Described spreading agent is 60-100 order Fo Luoli tripoli;
3) rap glass chromatography column outer wall spreading agent is tamped, then insert anhydrous sodium sulfate;
4) in glass chromatography column, add normal hexane and acetone mixture solvent elution, the mixture volume ratio of described mixture solvent is normal hexane: acetone=9:1; Collect after eluent be concentrated into≤0.5 milliliter, object be agricultural chemicals in very big degree concentrate eluant so that instrument detects, be settled to after 1.0 milliliters with normal hexane, cross 0.45 μ m organic system filter membrane, for gas chromatograph-mass spectrometer (GCMS) analyzing and testing.
As preferably, described adsorbent is 60-100 object Fo Luoli tripoli; Described deicer is anhydrous sodium sulfate.
Further, described residues of pesticides refer to organochlorine and pyrethroid pesticide remained in the fresh leaf of tea.
Further, described method is specially:
1) fill out in advance successively 3.0 Ke Foluoli tripoli and 1 centimetre of high anhydrous sodium sulfate in glass chromatography column lower end;
2) fresh tea leaf is cleaned, smashes, mixed, accurately take 1.0 grams in glass mortar, add 4.0 grams of 60-100 order Fo Luoli tripoli, fully grind, testing sample is dispersed in Fo Luoli tripoli, milled mixtures is transferred to glass chromatography column;
3) rap glass chromatography column outer wall milled mixtures is tamped, then insert 1 centimetre of high anhydrous sodium sulfate;
4) in glass chromatography column, add 20 ml n-hexanes and acetone mixture solvent elution, after collection eluent, be concentrated into≤0.5 milliliter, be settled to 1.0 milliliters with normal hexane, cross 0.45 μ m organic system filter membrane, for gas chromatograph-mass spectrometer (GCMS) analyzing and testing.
As preferably, described glass chromatography column is that internal diameter 1 cm x is high 30 centimetres.
In preceding method, the chromatographic condition of described gas chromatograph-mass spectrometer (GCMS) analyzing and testing is: chromatographic column: DB-5(5%Phenyl Methyl Siloxane, 30 meters × 0.25 millimeter × 0.25 micron); Injector temperature: 290 degrees Celsius; Detector temperature: 300 degrees Celsius; Heating schedule: 40 degrees Celsius of initial temperatures (keeping 1.0 minutes), are warming up to 130 degrees Celsius with the speed of 30 degrees celsius/minute, then are warming up to 300 degrees Celsius (keeping 5.0 minutes) with the speed of 5 degrees celsius/minute; Input mode: Splitless injecting samples; Carrier gas: high-purity helium (99.999%); Post flow: 1.0 ml/min; Dottle pin purge flow rate: 3.0 ml/min; Sample size: 1 microlitre; Sample injection time: 1.5 minutes; Quantivative approach: external standard method.
In preceding method, the mass spectrum condition of described gas chromatograph-mass spectrometer (GCMS) analyzing and testing is: ionization mode: electron impact ion source; Ion source temperature: 230 degrees Celsius; Interface temperature: 280 degrees Celsius; Scan mode: select ion monitoring (SIM) mode; 4.0 minutes solvent mute times; 1.0 kilovolts of detector voltage; 4.5～43.0 minutes sweep times; Sweep limit: 50～650m/z.
The present invention also provides preceding method application in organochlorine and pyrethroid pesticide remained amount in the fresh leaf of fast detecting tea.
Beneficial effect of the present invention is:
1, the inventive method preprocessing process is fairly simple, integrates extraction, purifies, and has greatly shortened analysis time.
2, the inventive method is with respect to additive method, especially national standard method, and the quantity of solvent of this method consumption greatly reduces (needing 20 milliliters), more friendly to environment, is a kind of sample pretreating method of environmental protection.
3, the consumptive material of the inventive method except eluting solvent, a small amount of Fo Luoli tripoli spreading agent (7.0 grams) and anhydrous sodium sulfate deicer (totally 2 centimetres high) are only used, the complex matrices of effectively getting rid of fresh leaf disturbs, and reduces analysis cost, economic, practical.
4, the inventive method has been avoided sample homogenizing, precipitation, centrifugal, the loss that turns molten, emulsification, the measured object causing such as concentrated, and easy and simple to handle, extraction efficiency is high, and recovery of standard addition is high, reduced the loss of measured target compound, and relative standard deviation between recovery result is little.
Therefore, the inventive method is convenient, efficient, inexpensive, environmental protection, and accuracy is good, and precision is high, is easy to repetition, is suitable for organochlorine and pyrethroid pesticide remained mensuration in the fresh leaf sample of tea, has stronger practical value and social effect.
Brief description of the drawings
Fig. 1 is the operational flowchart of the fresh leaf sample-pretreating method of tea of the present invention;
Fig. 2 is the total ions chromatogram (TIC) that the gas chromatography-mass spectrometry instrument of 7 kinds of organo-chlorine pesticides of the present invention and 7 kinds of pyrethroid pesticides detects, wherein the chromatographic peak of mark 1～14 successively corresponding agricultural chemicals object be: 1. α-benzene hexachloride; 2. β-benzene hexachloride; 3. γ-benzene hexachloride; 4. δ-benzene hexachloride; 5. β-5a,6,9,9a-hexahydro-6,9-methano-2,4; 6.p, p '-DDD; 7.p, p '-DDT; 8. Fenpropathrin; 9. Biphenthrin; 10. Cyhalothrin; 11. cyfloxylates; 12. cypermethrins; 13. fenvalerates; 14. decises.
Embodiment
Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
Embodiment 1 measures 7 kinds of organo-chlorine pesticides and the 7 kinds of pyrethroid pesticide remained amounts in the fresh leaf of tea
Fresh tea leaf is cleaned, smash, mix, accurately take 1.0 grams in glass mortar, shown in Fig. 1, first add 4.0 Ke Foluoli tripoli (60-100 order), fully grind, testing sample is dispersed in Fo Luoli tripoli, with scuppit, milled mixtures is transferred to glass chromatography column (internal diameter 1 cm x is high 30 centimetres) again, as shown in Figure 1, pillar lower end is inserted 3.0 Ke Foluoli tripoli (60-100 order) and 1 centimetre of high anhydrous sodium sulfate successively in advance, rapping pillar outer wall tamps milled mixtures, insert again 1 centimetre of high anhydrous sodium sulfate, with 20 ml n-hexanes: acetone (9:1, V:V) wash-out, after collection eluent, be concentrated into≤0.5 milliliter, be settled to 1.0 milliliters with normal hexane, cross 0.45 μ m organic system filter membrane, detect for gas chromatograph-mass spectrometer (GCMS).
Chromatographic condition: chromatographic column: DB-5(5%Phenyl Methyl Siloxane, 30 meters × 0.25 millimeter × 0.25 micron); Injector temperature: 290 degrees Celsius; Detector temperature: 300 degrees Celsius; Heating schedule: 40 degrees Celsius of initial temperatures (keeping 1.0 minutes), are warming up to 130 degrees Celsius with the speed of 30 degrees celsius/minute, then are warming up to 300 degrees Celsius (keeping 5.0 minutes) with the speed of 5 degrees celsius/minute; Input mode: Splitless injecting samples; Carrier gas: high-purity helium (99.999%); Post flow: 1.0 ml/min; Dottle pin purge flow rate: 3.0 ml/min; Sample size: 1 microlitre; Sample injection time: 1.5 minutes; Quantivative approach: external standard method.
Mass spectrum condition: ionization mode: electron impact ion source; Ion source temperature: 230 degrees Celsius; Interface temperature: 280 degrees Celsius; Scan mode: select ion monitoring (SIM) mode; 4.0 minutes solvent mute times; 1.0 kilovolts of detector voltage; 4.5～43.0 minutes sweep times; Sweep limit: 50～650m/z.
The relative retention time of each agricultural chemicals object, qualitative ion, quota ion are in table 1, the total ions chromatogram (TIC) that its gas chromatography-mass spectrometry instrument detects is shown in Fig. 2, and 1～No. 14 agricultural chemicals object of sequence number in table 1 is successively corresponding to the chromatographic peak of 1～14 labelled notation in Fig. 2.
The relative retention time of table 17 kind of organo-chlorine pesticide and 7 kinds of pyrethroid pesticides, qualitative ion, quota ion
This method is highly sensitive, and detection limit, between 0.205～4.794 μ g/kg (table 2), reaches 10
-9(ppb) order of magnitude; In the range of linearity of 0.0～2.0mg/L, it is linear good, and related coefficient is (table 2) more than 0.9979; The mensuration that is applied to the fresh leaf sample of tea, the recovery is (table 3) between 76.40～114.6.
Detection limit, linear equation, related coefficient and the range of linearity of table 27 kind of organo-chlorine pesticide and 7 kinds of pyrethroid pesticides
| Sequence number | Object | Detection limit (μ g/kg) | Equation of linear regression | Coefficient R | The range of linearity (mg/L) |
| 1 | α-benzene hexachloride | 0.205 | Y=0.126X+0.008 | 0.9995 | 0.0～2.0 |
| 2 | β-benzene hexachloride | 0.522 | Y=0.387X-0.008 | 0.9994 | 0.0～2.0 |
| 3 | γ-benzene hexachloride | 0.239 | Y=0.133X+0.011 | 0.9990 | 0.0～2.0 |
| 4 | δ-benzene hexachloride | 0.686 | Y=0.087X+0.009 | 0.9996 | 0.0～2.0 |
| 5 | β-5a,6,9,9a-hexahydro-6,9-methano-2,4 | 0.130 | Y=0.468X+0.005 | 0.9996 | 0.0～2.0 |
| 6 | p,p′-DDD | 0.650 | Y=0.315X+0.012 | 0.9995 | 0.0～2.0 |
| 7 | p,p′-DDT | 0.324 | Y=0.147X+0.024 | 0.9999 | 0.0～2.0 |
| 8 | Biphenthrin | 0.555 | Y=0.118X+0.008 | 0.9983 | 0.0～2.0 |
| 9 | Fenpropathrin | 1.687 | Y=0.075X+0.003 | 0.9979 | 0.0～2.0 |
| 10 | Cyhalothrin | 0.441 | Y=0.074X+0.003 | 0.9996 | 0.0～2.0 |
| 11 | Cyfloxylate | 1.550 | Y=0.095X-0.002 | 0.9997 | 0.0～2.0 |
| 12 | Cypermethrin | 4.794 | Y=0.026X-0.000 | 0.9994 | 0.0～2.0 |
| 13 | Fenvalerate | 2.198 | Y=0.008X-0.001 | 0.9997 | 0.0～2.0 |
| 14 | Decis | 2.727 | Y=0.057X-0.000 | 0.9998 | 0.0～2.0 |
The experimental data that adds scalar and the recovery thereof of table 37 kind of organo-chlorine pesticide and 7 kinds of pyrethroid pesticides
| Sequence number | Object | Add scalar (mg/L) | The recovery (%) | Add scalar (mg/L) | The recovery (%) |
| 1 | α-benzene hexachloride | 0.1 | 94.36 | 1.0 | 108.3 |
| 2 | β-benzene hexachloride | 0.1 | 98.86 | 1.0 | 114.6 |
| 3 | γ-benzene hexachloride | 0.1 | 100.0 | 1.0 | 106.8 |
| 4 | δ-benzene hexachloride | 0.1 | 96.06 | 1.0 | 100.4 |
| 5 | β-5a,6,9,9a-hexahydro-6,9-methano-2,4 | 0.1 | 86.80 | 1.0 | 91.71 |
| 6 | p,p′-DDD | 0.1 | 89.95 | 1.0 | 97.67 |
| 7 | p,p′-DDT | 0.1 | 78.18 | 1.0 | 80.87 |
| 8 | Biphenthrin | 0.1 | 89.63 | 1.0 | 100.1 |
| 9 | Fenpropathrin | 0.1 | 76.40 | 1.0 | 77.22 |
| 10 | Cyhalothrin | 0.1 | 100.2 | 1.0 | 102.2 |
| 11 | Cyfloxylate | 0.1 | 90.18 | 1.0 | 107.8 |
| 12 | Cypermethrin | 0.1 | 91.81 | 1.0 | 106.3 |
| 13 | Fenvalerate | 0.1 | 84.59 | 1.0 | 92.88 |
| 14 | Decis | 0.1 | 80.11 | 1.0 | 90.71 |
Method of the present invention has plurality of advantages: easy and simple to handle, analysis time is short, extraction efficiency is high, environmental friendliness, cost are low etc., in the fresh leaf of tea, organochlorine and the residual context of detection of pyrethroid agriculture have important using value, are conducive to tealeaves and deep processing manufacturing enterprise thereof the strict residual problem exceeding standard of agriculture of controlling from raw material.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (9)
1. a pre-treating method that detects the fresh leaf Pesticide Residues of tea, is characterized in that, described method comprises the steps:
1) in glass chromatography column, fill out in advance successively adsorbent and deicer, for subsequent use;
2) fresh tea leaf is cleaned, smashes, is mixed, make testing sample, take the fresh leaf testing sample of tea in glass mortar, add spreading agent fully to grind, testing sample is dispersed in spreading agent, after milled mixtures is transferred to the chromatographic column of step 1);
Described spreading agent is 60-100 order Fo Luoli tripoli;
3) rap glass chromatography column outer wall milled mixtures is tamped, then insert anhydrous sodium sulfate;
4) in glass chromatography column, add normal hexane and acetone mixture solvent elution, the mixture volume ratio of described mixture solvent is normal hexane: acetone=9:1; After collection eluent, be concentrated into≤0.5 milliliter, be settled to after 1.0 milliliters with normal hexane, cross 0.45 μ m organic system filter membrane, for gas chromatograph-mass spectrometer (GCMS) analyzing and testing.
2. method according to claim 1, is characterized in that, described adsorbent is 60-100 order Fo Luoli tripoli.
3. method according to claim 1, is characterized in that, described deicer is anhydrous sodium sulfate.
4. method according to claim 1, is characterized in that, described method is specially:
1) fill out in advance successively 3.0 Ke Foluoli tripoli and 1 centimetre of high anhydrous sodium sulfate in glass chromatography column lower end;
2) fresh tea leaf is cleaned, smashes, mixed, accurately take 1.0 grams in glass mortar, add 4.0 grams of 60-100 order Fo Luoli tripoli, fully grind, testing sample is dispersed in Fo Luoli tripoli, milled mixtures is transferred to glass chromatography column;
3) rap glass chromatography column outer wall milled mixtures is tamped, then insert 1 centimetre of high anhydrous sodium sulfate;
4) in glass chromatography column, add 20 ml n-hexanes and acetone mixture solvent elution, after collection eluent, be concentrated into≤0.5 milliliter, be settled to 1.0 milliliters with normal hexane, cross 0.45 μ m organic system filter membrane, for gas chromatograph-mass spectrometer (GCMS) analyzing and testing.
5. according to the method described in claim 1-4 any one, it is characterized in that, described glass chromatography column is that internal diameter 1 cm x is high 30 centimetres.
6. method according to claim 5, is characterized in that, described agricultural chemicals is organochlorine or pyrethroid pesticide.
7. method according to claim 5, is characterized in that, the chromatographic condition of described gas chromatograph-mass spectrometer (GCMS) analyzing and testing is: chromatographic column: DB-5(5%Phenyl Methyl Siloxane, 30 meters × 0.25 millimeter × 0.25 micron); Injector temperature: 290 degrees Celsius; Detector temperature: 300 degrees Celsius; Heating schedule: 40 degrees Celsius of initial temperatures (keeping 1.0 minutes), are warming up to 130 degrees Celsius with the speed of 30 degrees celsius/minute, then are warming up to 300 degrees Celsius (keeping 5.0 minutes) with the speed of 5 degrees celsius/minute; Input mode: Splitless injecting samples; Carrier gas: high-purity helium (99.999%); Post flow: 1.0 ml/min; Dottle pin purge flow rate: 3.0 ml/min; Sample size: 1 microlitre; Sample injection time: 1.5 minutes; Quantivative approach: external standard method.
8. method according to claim 5, is characterized in that, the mass spectrum condition of described gas chromatograph-mass spectrometer (GCMS) analyzing and testing is: ionization mode: electron impact ion source; Ion source temperature: 230 degrees Celsius; Interface temperature: 280 degrees Celsius; Scan mode: select ion monitoring (SIM) mode; 4.0 minutes solvent mute times; 1.0 kilovolts of detector voltage; 4.5～43.0 minutes sweep times; Sweep limit: 50～650m/z.
9. the application in organochlorine and pyrethroid pesticide remained amount in the fresh leaf of fast detecting tea of the method described in claim 1-8 any one.
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| CN106290662A (en) * | 2015-06-08 | 2017-01-04 | 中粮集团有限公司 | Organochlorine pesticide and the method for quick of pyrethroid pesticide and pre-treating method thereof in Folium Camelliae sinensis |
| CN105004593A (en) * | 2015-08-28 | 2015-10-28 | 湖南农业大学 | Pretreatment method for detecting simple sample of pesticide residue in tea soup |
| CN106918667A (en) * | 2015-12-25 | 2017-07-04 | 北京大学 | The micro- extraction equipment of one kind pressurization and the micro- extracting method of pressurization and its application |
| CN106918667B (en) * | 2015-12-25 | 2020-08-21 | 北京大学 | Pressurized micro-extraction equipment, pressurized micro-extraction method and application thereof |
| CN107490651A (en) * | 2017-10-16 | 2017-12-19 | 花锦 | Pyrethroid pesticide remained detection method in a kind of asparagus and its product |
| WO2020000215A1 (en) * | 2018-06-26 | 2020-01-02 | 江苏宏大环保科技有限公司 | Purifying column |
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