CN107561194A - A kind of more Fast Determination of Pesticide Residue methods of fruits and vegetables - Google Patents
A kind of more Fast Determination of Pesticide Residue methods of fruits and vegetables Download PDFInfo
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- CN107561194A CN107561194A CN201711032525.3A CN201711032525A CN107561194A CN 107561194 A CN107561194 A CN 107561194A CN 201711032525 A CN201711032525 A CN 201711032525A CN 107561194 A CN107561194 A CN 107561194A
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Abstract
The invention discloses a kind of more Fast Determination of Pesticide Residue methods of fruits and vegetables, comprise the following steps：The preprocessed samples of 15 ± 0.5g are weighed into reagent bottle, 90mL ethyl acetate is added, shakes up, sodium acid carbonate and anhydrous sodium sulfate is added, shakes up again；Reagent bottle was placed in 30 ± 3 DEG C of water-baths after a period of time and taken out, is placed in homogeneous 1 minute in homogenizer；By reagent bottle, clear liquid is filtered at the middle and upper levels, collects filter liquor；Measure respectively in two parts of filter liquor to pear shape bottles, be placed in 35 DEG C of ± 3 DEG C of water-baths, a filter liquor is concentrated under reduced pressure into dry, forms residue, and another filter liquor is concentrated under reduced pressure near dry etc..This detection method disclosure satisfy that the detection of most of vegetable and fruit matrix sample, pass through a pre-treatment step, agricultural chemicals object of different nature is detected using gas phase and liquid phase tandem mass spectrometer respectively, reduce the usage amount of chemical reagent in pretreatment process, shorten the time of pretreatment process, detection and analysis efficiency is improved, while obtains accurately and reliably analysis result.
Description
Technical field
The present invention relates to trace chemical detection technique field, and in particular to a kind of more Fast Determination of Pesticide Residue of fruits and vegetables
Method.
Background technology
Persticide residue is one of important indicator of agricultural product quality and safety.Countries in the world, particularly developed country is to agriculture
Medicine residue problem is paid much attention to, and increasingly stricter limit standard is all defined to various agricultural byproducts Pesticide Residues.Outlet
Enterprise more needs to pay close attention to change of the various countries to the control measures and Pesticide Residue standard of agricultural chemicals.At home, GB2763《In food
Agricultural chemicals MRL》National standard enforces on October 1st, 2005.Up to the present, it is specified that 433 kinds of agricultural chemicals
4140 residue limits in 13 big agricultural products.Meanwhile government organs will strengthen the monitoring of Pesticide Residues amount, agricultural chemicals
Remaining exceeded or containing height banned pesticides products will be difficult to enter market.At present, the standard method for being related to multi-pesticide residue has
A lot, but these methods there is narrow application range, sample requirement is harsh, detection efficiency is low the problem of.
Therefore, prior art also needs to further improve and develop.
The content of the invention
The invention aims to provide a kind of fruits and vegetables more Fast Determination of Pesticide Residue methods, it is intended to solve current fruits and vegetables
The problem of more Fast Determination of Pesticide Residue method narrow application ranges, sample requirement are harsh, detection efficiency is low.
Used technical scheme is：
A kind of more Fast Determination of Pesticide Residue methods of fruits and vegetables, method comprise the following steps：
The preprocessed samples of 15 ± 0.5g are weighed into reagent bottle, 90mL ethyl acetate is added, shakes up, add sodium acid carbonate
And anhydrous sodium sulfate, shake up again；Reagent bottle was placed in 30 ± 3 DEG C of water-baths after a period of time and taken out, is placed in homogenizer
Matter 1 minute；By reagent bottle, clear liquid is filtered at the middle and upper levels, collects filter liquor；Measure respectively in two parts of filter liquor to pear shape bottles,
35 DEG C of ± 3 DEG C of water-baths are placed in, a filter liquor is concentrated under reduced pressure into dry, formation residue, and another filter liquor, which is concentrated under reduced pressure into, closely to be done；
The portion for forming residue to residue dissolve with methanol and after filter membrane, load and LC- is carried out in sample introduction bottle
MSMS is analyzed；
By SPE (Cleanert PC/NH2) pillar on the portion for forming nearly dry filter liquor, eluent is collected with centrifuge tube,
Pear shape bottle is cleaned with ethyl acetate-acetone-toluene mixture liquid again, is transferred to again on SPE (Cleanert PC/NH2) pillar, from
Heart pipe collects eluent, repeats successively twice；Centrifuge tube is put on nitrogen evaporator, nitrogen is blown in 40 DEG C of ± 3 DEG C of water baths
It is near dry, 100 μ L 5mg/L TPP (triphenyl) is added into centrifuge tube, then with ethyl acetate constant volume to 0.5mL,
Load in sample introduction bottle, carry out GC MS or GCMSMS analysis.
Sodium acid carbonate and anhydrous sodium sulfate are sequentially added in reagent bottle, are first added 5~6g sodium acid carbonates, are shaken up, and add 35
~40g anhydrous sodium sulfates, shake up again.
Reagent bottle is placed in 30 ± 3 DEG C of water-baths and taken out after 20 minutes.
Homogenizer rotating speed is at 20000 revs/min.
By reagent bottle, clear liquid is filtered at the middle and upper levels, is collected filter liquor and is specially：Glass funnel is put into 150mL graduated cylinders
On, and put the filter paper folded into funnel, by bottle, clear liquid gently pours into funnel at the middle and upper levels, makes it after filter paper filters
Graduated cylinder is flowed into, collects filter liquor.
Measure in partial filtrate to pear shape bottle, be placed in 35 DEG C of ± 3 DEG C of water-baths, be concentrated under reduced pressure into form into residue, use first
After alcohol dissolved residue and filter membrane, loading progress LC-MSMS analyses in sample introduction bottle is specially：50mL filter liquors are measured to arrive
In 150mL pear shape bottle, 35 DEG C of ± 3 DEG C of water-baths are concentrated under reduced pressure into dry, with 5mL methanol dissolved residues, are filled after crossing 0.22 μm of filter membrane
Enter and LC-MSMS analyses are carried out in sample introduction bottle.
SPE (Cleanert PC/NH2) pillar specification：Agilent Carbon/Amino SPE cart., 6ml500mg,
It is previously placed on the more menifolds of vacuum, with 5mL ethyl acetate-acetones-toluene mixture liquid activation balance, ethyl acetate-acetone-toluene
Ethyl ester, acetone, the volume ratio of toluene are 3 in mixed liquor:1:1.
In ethyl acetate-acetone-toluene mixture liquid cleaning pear shape bottle ethyl ester-acetone-toluene mixture liquid used by ethyl ester,
Acetone, toluene are 3 according to volume ratio:1:1 mixes.
By SPE pillars on the portion for forming nearly dry filter liquor, eluent is collected with centrifuge tube, then with ethyl acetate-acetone-
Toluene mixture liquid cleans pear shape bottle, is transferred to again on SPE (Cleanert PC/NH2) pillar, and centrifuge tube collects eluent, successively
Repeat twice；Centrifuge tube is put on nitrogen evaporator, nitrogen is blown near do specially in 40 DEG C of ± 3 DEG C of water baths：With 15mL glass
Glass centrifuge tube collects eluent, then cleans pear shape bottle with 3mL ethyl acetate-acetones-toluene mixture liquid, is transferred to SPE pillars again
On, eluent is collected, repeats successively twice, centrifuge tube is put on nitrogen evaporator, 40 DEG C of ± 3 DEG C of water-baths, nitrogen is blown near dry.
Sample pretreating method is：There is representative according to sample size and state random selection and using the selection of cone quartering
The sample about 1kg of property, it is using clean food masher that sample comminution is uniform, two parts are divided into, is respectively charged into sample sack
It is interior, label is posted, room temperature, freezing and stored refrigerated to be measured are distinguished according to sample state.
Beneficial effect：The present invention provides a kind of more Fast Determination of Pesticide Residue methods of fruits and vegetables, and this detection method disclosure satisfy that
The detection of most of vegetable and fruit matrix sample, by a pre-treatment step, distinguished using gas phase and liquid phase tandem mass spectrometer
Agricultural chemicals object of different nature is detected, reduces the usage amount of chemical reagent in pretreatment process, shortens pretreatment process
Time, improve detection and analysis efficiency, while obtain accurately and reliably analysis result.
Embodiment
To make the objects, technical solutions and advantages of the present invention clearer, clear and definite, one is entered to the present invention by the following examples
Step describes in detail.
A kind of more Fast Determination of Pesticide Residue methods of fruits and vegetables, method comprise the following steps：
S1：The interception of sample.Sample message is checked in sample advice note, fills in sample sent by, date, confirmatory sample is interim
The information such as deposit position, recipient, sample packaging whether with require consistent.
S2：The reception of sample.
S3：The pretreatment of sample.
Specific method is：Representational sample is selected according to sample size and state random selection and using cone quartering
About 1kg, it is using clean food masher that sample comminution is uniform, two parts are divided into, is respectively charged into sample sack, posts mark
Label, room temperature, freezing and stored refrigerated to be measured are distinguished according to sample state.
S4：The preparation of standard liquid.
S5：The extraction and purification of sample
The pretreated samples of 15 ± 0.5g accurately are weighed into 150ml reagent bottle, are added 90mL ethyl acetate, are shaken
It is even, 5~6g sodium acid carbonates are added, is shaken up with hydrotropy solution, is added 35~40g anhydrous sodium sulfates, shake up again, to prevent from luming；
Reagent bottle is placed in 30 DEG C ± 3 DEG C of water-bath, after placing 20 minutes, taken out, is placed in the homogeneous that rotating speed is 2000 revs/min
1 minute；Glass funnel is put on 150ml graduated cylinders, and puts the filter paper folded into funnel, by the supernatant liquor in bottle
Funnel is gently poured into, it is flowed into graduated cylinder after filter paper filters, collects filter liquor；Two parts of filter liquors are measured respectively to 150ml pears
In shape bottle, a 50ml is placed in 35 DEG C of ± 3 DEG C of water-baths, is concentrated under reduced pressure into dry, with 5mL methanol dissolved residues, crosses 0.22 μm of filter membrane,
Load LC-MSMS analyses, another 50ml in sample introduction bottle to be placed in 35 DEG C of ± 3 DEG C of water-baths, be concentrated under reduced pressure into dry；By SPE
(Cleanert PC/NH2) pillar is previously placed on the more menifolds of vacuum, is activated with 5ml ethyl acetate-acetones-toluene mixture liquid flat
Weighing apparatus, ethyl acetate, acetone, the volume ratio of toluene are 3:1:1；By SPE (Cleanert PC/ on the portion for forming nearly dry filter liquor
NH2) pillar, with 15mL glass centrifuge tubes collect eluent, then with 3ml volume ratios be 3：1:1 ethyl acetate-acetone-toluene
Mixed liquor cleans pear shape bottle, is transferred to again on SPE (Cleanert PC/NH2) pillar, collects eluent, repeats two successively
Time.Centrifuge tube is put on nitrogen evaporator, 40 DEG C of ± 3 DEG C of water-baths, nitrogen, which is blown to, closely to be done, and adds 100 μ L5mg/L's into centrifuge tube
TPP (triphenyl), then with ethyl acetate constant volume to 0.5ml, load in sample introduction bottle, GC MS or GCMSMS analysis.
S6：GC/MS analyzes extract.
S7：GC/MSMS analyzes extract.
S8：LC/MSMS analyzes extract.
S9：The evaluation of data and result.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can
To be improved or converted according to the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Protect scope.
Claims (10)
- A kind of 1. more Fast Determination of Pesticide Residue methods of fruits and vegetables, it is characterised in that the described method comprises the following steps：The preprocessed samples of 15 ± 0.5g are weighed into reagent bottle, 90mL ethyl acetate is added, shakes up, add sodium acid carbonate and nothing Aqueous sodium persulfate, shake up again；Reagent bottle was placed in 30 ± 3 DEG C of water-baths after a period of time and taken out, homogeneous 1 in homogenizer is placed in and divides Clock；By reagent bottle, clear liquid is filtered at the middle and upper levels, collects filter liquor；Measure in two parts of filter liquor to pear shape bottles, be placed in respectively 35 DEG C of ± 3 DEG C of water-baths, a filter liquor are concentrated under reduced pressure into dry, formation residue, and another filter liquor, which is concentrated under reduced pressure into, closely to be done；The portion for forming residue to residue dissolve with methanol and after filter membrane, load and LC-MSMS is carried out in sample introduction bottle Analysis；By SPE (Cleanert PC/NH2) pillar on the portion for forming nearly dry filter liquor, eluent is collected with centrifuge tube, then use Ethyl acetate-acetone-toluene mixture liquid cleaning pear shape bottle, is transferred on SPE (Cleanert PC/NH2) pillar, centrifuge tube again Eluent is collected, is repeated successively twice；Centrifuge tube is put on nitrogen evaporator, nitrogen is blown near dry in 40 DEG C of ± 3 DEG C of water baths, 100 μ L5mg/L TPP (triphenyl) is added into centrifuge tube, then with ethyl acetate constant volume to 0.5mL, load into In sample bottle, GC MS or GCMSMS analysis are carried out.
- 2. the more Fast Determination of Pesticide Residue methods of fruits and vegetables according to claim 1, it is characterised in that the sodium acid carbonate and Anhydrous sodium sulfate is sequentially added in reagent bottle, is first added 5~6g sodium acid carbonates, is shaken up, and adds 35~40g anhydrous sodium sulfates, then It is secondary to shake up.
- 3. the more Fast Determination of Pesticide Residue methods of fruits and vegetables according to claim 1, it is characterised in that the reagent bottle is placed in Taken out in 30 ± 3 DEG C of water-baths after 20 minutes.
- 4. the more Fast Determination of Pesticide Residue methods of fruits and vegetables according to claim 1, it is characterised in that the homogenizer rotating speed For at 20000 revs/min.
- 5. the more Fast Determination of Pesticide Residue methods of fruits and vegetables according to claim 1, it is characterised in that described by reagent bottle Supernatant liquor is filtered, and is collected filter liquor and is specially：Glass funnel is put on 150mL graduated cylinders, and puts one into funnel The filter paper folded is opened, clear liquid gently pours into funnel at the middle and upper levels by bottle, it is flowed into graduated cylinder after filter paper filters, and collection filters out Liquid.
- 6. the more Fast Determination of Pesticide Residue methods of fruits and vegetables according to claim 1, it is characterised in that described to measure part filter Go out in liquid to pear shape bottle, be placed in 35 DEG C of ± 3 DEG C of water-baths, form is concentrated under reduced pressure into residue, with methanol dissolved residue and filter membrane Afterwards, loading progress LC-MSMS analyses in sample introduction bottle is specially：50mL filter liquors are measured in 150mL pear shape bottle, 35 DEG C ± 3 DEG C of water-baths, are concentrated under reduced pressure into dry, with 5mL methanol dissolved residues, cross after 0.22 μm of filter membrane to load LC- is carried out in sample introduction bottle MSMS is analyzed.
- 7. the more Fast Determination of Pesticide Residue methods of fruits and vegetables according to claim 1, it is characterised in that the SPE (Cleanert PC/NH2) pillar specification：Agilent Carbon/Amino SPE cart., 6ml 500mg, it is previously placed in true On empty more menifolds, with 5mL ethyl acetate-acetones-toluene mixture liquid activation balance, the ethyl acetate-acetone-toluene mixture liquid Middle ethyl ester, acetone, the volume ratio of toluene are 3:1:1.
- 8. the more Fast Determination of Pesticide Residue methods of fruits and vegetables according to claim 1, it is characterised in that ethyl acetate-acetone- Ethyl ester-acetone-toluene mixture liquid used is according to volume ratio by ethyl ester, acetone, toluene in toluene mixture liquid cleaning pear shape bottle 3:1:1 mixes.
- 9. the more Fast Determination of Pesticide Residue methods of fruits and vegetables according to claim 1, it is characterised in that closely dry filter out will be formed SPE pillars on the portion of liquid, eluent is collected with centrifuge tube, then pear shape bottle is cleaned with ethyl acetate-acetone-toluene mixture liquid, It is transferred to again on SPE (Cleanert PC/NH2) pillar, centrifuge tube collects eluent, repeats successively twice；Centrifuge tube is put Enter on nitrogen evaporator, nitrogen is blown near do specially in 40 DEG C of ± 3 DEG C of water baths：Eluent is collected with 15mL glass centrifuge tubes, then Pear shape bottle is cleaned with 3mL ethyl acetate-acetones-toluene mixture liquid, is transferred to again on SPE pillars, eluent is collected, weighs again successively It is multiple twice, centrifuge tube is put on nitrogen evaporator, 40 DEG C of ± 3 DEG C of water-baths, nitrogen is blown near dry.
- 10. the more Fast Determination of Pesticide Residue methods of fruits and vegetables according to claim 1, it is characterised in that the specimen preprocessing Reason method is：Representational sample about 1kg is selected according to sample size and state random selection and using cone quartering, is made It is with clean food masher that sample comminution is uniform, two parts are divided into, is respectively charged into sample sack, posts label, according to Sample state difference room temperature, freezing and stored refrigerated to be measured.
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Cited By (3)
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| CN108776116A (en) * | 2018-08-15 | 2018-11-09 | 山东五洲检测有限公司 | A method of detection pesticide residues in fruits |
| CN113109471A (en) * | 2021-04-12 | 2021-07-13 | 诺安实力可商品检验（青岛）有限公司 | LCMSMS (liquid crystal display module medium) method for rapidly and simultaneously detecting chlorothalonil and metabolites thereof in vegetables and fruits |
| CN114720609A (en) * | 2022-04-13 | 2022-07-08 | 诺安实力可商品检验（青岛）有限公司 | Method for rapidly detecting chlorophthalic acid and dicamba in food based on non-phase-inversion derivatization |
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Cited By (3)
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|---|---|---|---|---|
| CN108776116A (en) * | 2018-08-15 | 2018-11-09 | 山东五洲检测有限公司 | A method of detection pesticide residues in fruits |
| CN113109471A (en) * | 2021-04-12 | 2021-07-13 | 诺安实力可商品检验（青岛）有限公司 | LCMSMS (liquid crystal display module medium) method for rapidly and simultaneously detecting chlorothalonil and metabolites thereof in vegetables and fruits |
| CN114720609A (en) * | 2022-04-13 | 2022-07-08 | 诺安实力可商品检验（青岛）有限公司 | Method for rapidly detecting chlorophthalic acid and dicamba in food based on non-phase-inversion derivatization |
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