CN109932461A - A kind of pesticide residue method in QuEChERS pretreatment technology combination gas Chromatographic Determination tealeaves - Google Patents
A kind of pesticide residue method in QuEChERS pretreatment technology combination gas Chromatographic Determination tealeaves Download PDFInfo
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- CN109932461A CN109932461A CN201910095965.6A CN201910095965A CN109932461A CN 109932461 A CN109932461 A CN 109932461A CN 201910095965 A CN201910095965 A CN 201910095965A CN 109932461 A CN109932461 A CN 109932461A
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- gas chromatographic
- chromatographic determination
- combination gas
- pretreatment technology
- pesticide residue
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Abstract
The invention discloses a kind of pesticide residue methods in QuEChERS pretreatment technology combination gas Chromatographic Determination tealeaves, comprising the following steps: takes powdered tea leaves sample, is placed in centrifuge tube, acetonitrile water mixed solution is added, homogeneous extracts, and adds sodium chloride, it is vortexed and mixes, centrifugation takes supernatant；By gained supernatant, nitrogen is blown to close dry, addition hexane acetone mixed solution constant volume in water-bath, and vortex mixing adds cleanser, is vortexed and mixes, and filter membrane, upper machine measures.Measuring method of the invention is simple, conveniently, material benefit, suitable for the low routine testing residual to tealeaves agriculture with laboratory.
Description
Technical field
The present invention relates to agricultural product quality and safety detection technique field more particularly to a kind of QuEChERS pretreatment technology knots
Close the pesticide residue method in gas Chromatographic Determination tealeaves.
Background technique
About the Detecting Pesticide of tealeaves in GB2763-2016 standard, the national standard or rower recommended are substantially
It is completed with makings and liquid matter.And instrument provisioned in many quality inspection stations at county level or general detection company is all conventional gas phase and liquid
Phase can not carry out Pesticide Residues in Tea detection.
QuEChERS technology is extracted with acetonitrile, and magnesium sulfate and sodium chloride are removed water and saltoutd layering, takes acetonitrile
Extracting solution is purified with magnesium sulfate and N- propyl ethylenediamine (PSA), is finally detected with GC/MS.This method is simple, efficient, real because of it
Favour and favored in the industry, be initially the Detecting Pesticide for vegetables and fruit, such as U.S.'s pesticide residue detection method
AOAC2007.01 and CEN standard method 156627.It is adjusted by changing the methods of pretreatment process extracts and purify effect
Fruit can be applied in the usual residual detection of tealeaves agriculture so as to QuEChERS technology combination gas-chromatography, be suitable for laboratory configuration
Lower quality inspection station at county level and detection company use, and have a vast market foreground.
Summary of the invention
In order to solve the problems, such as to be previously mentioned in above-mentioned background technique, the present invention provides a kind of QuEChERS pretreatment technologies
In conjunction with the pesticide residue method in gas Chromatographic Determination tealeaves, low laboratory of matching is enable to apply simple and fast detection method to tea
The residual carry out routine testing of Ye Nong.
A kind of pesticide residue method in QuEChERS pretreatment technology combination gas Chromatographic Determination tealeaves, including following step
It is rapid:
(1) it extracting: taking powdered tea leaves sample, be placed in centrifuge tube, acetonitrile water mixed solution is added, homogeneous extracts, then plus
Enter sodium chloride, be vortexed and mix, centrifugation takes supernatant spare；
(2) purify: by gained supernatant, nitrogen is blown to close dry, addition hexane acetone mixed solution constant volume in water-bath,
It is vortexed and mixes, add cleanser, be vortexed, filter membrane, upper machine measurement.
Further, the extraction of the step (1) specifically: 4g powdered tea leaves sample is weighed in 50mL centrifuge tube,
22mL acetonitrile water mixed solution is added, homogeneous extracts 2-3min in the homogeneous instrument that revolving speed is 9000-10000r/min, and 1- is added
2g sodium chloride is vortexed and mixes, and is centrifuged 4-5min under conditions of revolving speed is 5000-6000r/min, takes 10mL supernatant spare.
Further, the purification of the step (2) specifically: by supernatant in 45-55 DEG C of water-bath nitrogen blow it is close dry,
Hexane acetone mixed solution is added and is settled to 5mL, is vortexed and mixes, addition 310mg cleanser, vortex 2-4min, filter membrane, on
Machine measurement.
Further, the cleanser be by ketjenblack EC, N- propyl ethylenediamine, inactivation florisil silica mixing and
At.
Further, the ketjenblack EC, N- propyl ethylenediamine, inactivate florisil silica weight ratio be 6:15:10.
Further, the inactivation florisil silica is that florisil silica is toasted 3-4 in 600-700 DEG C of Muffle furnace
Hour, distilled water is added after cooling and carries out inactivation processing.
Further, the acetonitrile water mixed solution in the step (1) is the acetonitrile and pure water for being 10:1 by volume ratio
It mixes.
Further, the hexane acetone mixed solution in the step (2) be by volume ratio be 1:9 acetone and just oneself
Alkane mixes.
The beneficial effects of the present invention are:
1, the present invention adopts acetonitrile water mixed solvent in a volume ratio of 10:1 and extracts, while guaranteeing the rate of recovery,
It extracts impurity less as far as possible, eases off the pressure to purification process below.
2, the present invention and first purify compared with the method being concentrated afterwards using the method that after-purification is first concentrated, and effect is more preferable, general
When constant volume solvent is changed to the hexane acetone mixed solvent progress constant volume that volume ratio is 1:9 by n-hexane, part is substantially increased
The rate of recovery of index.
3, the cleanser mixed by ketjenblack EC, N- propyl ethylenediamine, inactivation florisil silica is added in the present invention,
Its effect is the impurity such as depigmentation, organic acid, and by the composition as cleanser, the rate of recovery is high, good purification.
4, measuring method of the invention it is simple, conveniently, material benefit, suitable for the low routine testing residual to tealeaves agriculture with laboratory.
Detailed description of the invention
Fig. 1 is the chromatogram that GC-ECD measures matrix standard liquid organochlorine class and pyrethrin pesticide.
Fig. 2 is the chromatogram that GC-FPD measures matrix standard liquid organophosphorus insecticide.
Fig. 3 is the chromatogram that GC-ECD measures organochlorine class and pyrethrin pesticide in green tea sample.
Fig. 4 is the chromatogram that GC-FPD measures organophosphorus insecticide in green tea sample.
Fig. 5 is the chromatogram that GC-ECD measures organochlorine class and pyrethrin pesticide in black tea sample.
Fig. 6 is the chromatogram that GC-FPD measures organophosphorus insecticide in green tea sample.
Specific embodiment
Technical solution of the present invention is described in more detail With reference to embodiment.
The configuration of singly mark solution: the accurate 1mL100ug/mL organochlorine or pyrethrin pesticide standard items drawn is in 10mL capacity
In bottle, it is settled to 10mL with n-hexane, obtains the singly mark solution of 10ug/mL organochlorine or pyrethrin pesticide；It is accurate to draw
1mL100ug/mL organophosphorus insecticide standard items are settled to 10mL with acetone, it is organic phosphorus to obtain 10ug/mL in 10mL volumetric flask
The singly mark solution of class pesticide.
Hybrid standard product solution allocation: accurate organochlorine, pyrethroids class and the organic phosphates agriculture for drawing 1mL 10ug/mL respectively
The singly mark solution of medicine is settled to 10mL with n-hexane in 10mL volumetric flask, obtains the hybrid standard product solution of 1ug/mL.
The configuration of matrix standard liquid: take 4g blank Tea Samples same according to (1), (2), (3), (4) the step of following embodiment 1
The pre-treating method of sample is handled.Vehicle solution is obtained, takes the hybrid standard product solution of 1mL1ug/mL in 10mL capacity
In bottle, it is settled to 10mL with vehicle solution, obtains the matrix standard liquid of 0.1ug/mL.
Embodiment 1
Detect the pesticide residue in green tea:
(1) preparation of cleanser: florisil silica is toasted into 4h in 650 DEG C of Muffle furnace, cooled to room temperature adds
Enter 5% distilled water and carry out inactivation processing, resulting material weighs 100mg, with 60mg ketjenblack EC, 150mgN- propyl ethylenediamine
Mixing, obtains cleanser；
(2) preparation of acetonitrile water mixed solution, hexane acetone mixed solution: being the acetonitrile of 10:1 and pure by volume ratio
Water mixing, obtains acetonitrile water mixed solution；Acetone and n-hexane that volume ratio is 1:9 are mixed, hexane acetone mixed solution is obtained；
(3) it extracts: weighing 4g blank powdered green tea sample in 50mL centrifuge tube, the mixing of 400uL 1ug/mL is added
Standard solution is vortexed and mixes, and places for 24 hours, 22mL acetonitrile water mixed solution is added, in the homogeneous instrument that revolving speed is 10000r/min
Middle homogeneous extracts 2min, and 1g sodium chloride is added, and is vortexed and mixes, and is centrifuged 5min under conditions of revolving speed is 5000r/min, takes 10mL
Supernatant is spare；
(4) purify: by supernatant, nitrogen is blown to close dry, addition hexane acetone mixed solution constant volume in 50 DEG C of water-bath
It to 5mL, is vortexed and mixes, 310mg cleanser, vortex 3min is added, filter membrane obtains sample solution；
(5) it measures: being had using gas chromatography-electron capture detector (GC-ECD) measurement matrix standard liquid and sample solution
Machine chlorine and pyrethrin pesticide measure matrix standard liquid and sample solution using gas-chromatography-flame photometric detector (GC-FPD)
Organophosphorus insecticide, retention time is qualitative, uses quantified by external standard method (post processing extraction solvent consumption is converted as acetonitrile)；
Wherein, measure organochlorine and the chromatographic condition of pyrethrin pesticide is: chromatographic column is HP-5 Fused-silica capillary column
(30m*0.25mm*0.25um)；Injector temperature is 200 DEG C, and electron capture detector temperature is 320 DEG C；Temperature program: initial temperature
90 DEG C, 190 DEG C are warming up to 25 DEG C of speed per minute, is kept for 1 minute, is then warming up to 275 with 30 DEG C of speed per minute
DEG C, it is kept for 10 minutes；Column flow 1mL/min；Tail blows 60mL/min；
Measure the chromatographic condition of organophosphorus insecticide are as follows: chromatographic column is DB-17 Fused-silica capillary column (30m*
0.25mm*0.25um)；Injector temperature is 220 DEG C, and flame photometric detector temperature is 250 DEG C；Temperature program: 90 DEG C of initial temperature,
190 DEG C are warming up to 25 DEG C of speed per minute, is kept for 1 minute, is then warming up to 275 DEG C with 30 DEG C of speed per minute, protected
It holds 10 minutes；Column flow 4.5mL/min；Tail blows 60mL/min；Air mass flow 100mL/min；Hydrogen flowing quantity 110mL/min.
Method detection limit: being detection with standard concentration corresponding to 3 times of signal-to-noise ratio (S/N=3) under this experiment condition
Limit, to calculate the detection limit of this method, detection limit is in 0.002mg/kg-0.006mg/kg.
Embodiment 2
Detection black tea in pesticide residue: take the powdered black tea sample of the blank of 4g, according to method identical with example 1 into
Row pre-treatment and measurement.
Precision and recovery testu 1
It takes 4g blank powder green tea that the hybrid standard product solution of 1ug/mL is added, carries out in the same manner as in Example 1
Pre-treatment and measurement carry out 6 parallel laboratory tests, calculate precision and the rate of recovery, as a result as follows:
Precision and recovery testu 2
It takes 4g blank powder black tea that the hybrid standard product solution of 1ug/mL is added, carries out in the same manner as in Example 1
Pre-treatment and measurement carry out 6 parallel laboratory tests, calculate precision and the rate of recovery, as a result as follows:
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although referring to aforementioned reality
Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features.It is all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of pesticide residue method in QuEChERS pretreatment technology combination gas Chromatographic Determination tealeaves, which is characterized in that
The following steps are included:
(1) it extracts: taking powdered tea leaves sample, be placed in centrifuge tube, acetonitrile water mixed solution is added, homogeneous extracts, and adds chlorine
Change sodium, be vortexed and mix, centrifugation takes supernatant spare；
(2) purify: by gained supernatant, nitrogen is blown to close dry, addition hexane acetone mixed solution constant volume, vortex in water-bath
It mixes, adds cleanser, be vortexed, filter membrane, upper machine measurement.
2. the pesticide residue side in QuEChERS pretreatment technology combination gas Chromatographic Determination tealeaves according to claim 1
Method, which is characterized in that the extraction of the step (1) specifically: weigh 4g powdered tea leaves sample in 50mL centrifuge tube, be added
22mL acetonitrile water mixed solution, homogeneous extracts 2-3min in the homogeneous instrument that revolving speed is 9000-10000r/min, and 1-2g chlorine is added
Change sodium, be vortexed and mix, is centrifuged 4-5min under conditions of revolving speed is 5000-6000r/min, takes 10mL supernatant spare.
3. the pesticide residue side in QuEChERS pretreatment technology combination gas Chromatographic Determination tealeaves according to claim 1
Method, which is characterized in that the purification of the step (2) specifically: nitrogen blows close dry in 45-55 DEG C of water-bath by supernatant, adds
Enter hexane acetone mixed solution and be settled to 5mL, be vortexed and mix, 310mg cleanser, vortex 2-4min, filter membrane, upper machine is added
Measurement.
4. the pesticide residue side in QuEChERS pretreatment technology combination gas Chromatographic Determination tealeaves according to claim 1
Method, which is characterized in that the cleanser is mixed by ketjenblack EC, N- propyl ethylenediamine, inactivation florisil silica.
5. the pesticide residue side in QuEChERS pretreatment technology combination gas Chromatographic Determination tealeaves according to claim 4
Method, which is characterized in that the ketjenblack EC, N- propyl ethylenediamine inactivate the weight ratio of florisil silica as 6:15:10.
6. the pesticide in QuEChERS pretreatment technology combination gas Chromatographic Determination tealeaves according to claim 4 or 5 is residual
Stay method, which is characterized in that the inactivation florisil silica is that florisil silica is toasted 3- in 600-700 DEG C of Muffle furnace
4 hours, distilled water is added after cooling and carries out inactivation processing.
7. the pesticide residue side in QuEChERS pretreatment technology combination gas Chromatographic Determination tealeaves according to claim 1
Method, which is characterized in that the acetonitrile water mixed solution in the step (1) is mixed by acetonitrile and pure water that volume ratio is 10:1
It forms.
8. the pesticide residue side in QuEChERS pretreatment technology combination gas Chromatographic Determination tealeaves according to claim 1
Method, which is characterized in that the hexane acetone mixed solution in the step (2) is the acetone and n-hexane for being 1:9 by volume ratio
It mixes.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111024845A (en) * | 2019-12-21 | 2020-04-17 | 刘军虎 | Method for rapidly determining pesticide residues in vegetables, fruits and edible fungi |
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| CN111024845A (en) * | 2019-12-21 | 2020-04-17 | 刘军虎 | Method for rapidly determining pesticide residues in vegetables, fruits and edible fungi |
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Application publication date: 20190625 |