CN106596801B - Sample-pretreating method and agriculture residual detection method when for fruit and vegetable residual pesticide detection - Google Patents
Sample-pretreating method and agriculture residual detection method when for fruit and vegetable residual pesticide detection Download PDFInfo
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Abstract
The present invention provides a kind of purifying adsorbent of sample pre-treatments when detection for garden stuff pesticide residue, the raw materials including following parts by weight: 0~50 part of C18,0~50 part of ketjenblack EC and 10~50 parts of Fe3O4@SiO2@PSA.Sample pre-treatments are carried out using purifying adsorbent provided by the invention, two steps of the extraction of pre-treating method process and purification it can will be incorporated in a step completion in the prior art, to effectively save the operating time and be omitted in the centrifugation step between extraction, purifying step；Elapsed time relative to existing widely used quick pretreatment method QuECHERS reduces 61.1%, it is only necessary to which 70min can be completed at the same time the pretreatment process of 50 samples.
Description
Technical field
The present invention relates to the Detection Technologies of Pesticide Residues fields, and in particular to sample when one kind is for garden stuff pesticide residue detection
Purifying adsorbent, sample-pretreating method and the residual detection method of agriculture.
Background technique
Pesticide Residue is with pesticide mass production and to be widely used and generate, and the applications of pesticide do not have in the latter period
It is decomposed and remains on the crops such as fruits and vegetables, remaining pesticide food chain is eventually transferred in people or carcass.Up to the present,
Nearly 2,000,000 tons of chemical pesticide annual output in the world, there are about more than 1000 kinds of artificial-synthetic compounds be used as insecticide, fungicide,
The classes pesticide such as algicide, insecticide, defoliant.Pesticide especially organic agricultural chemicals is largely applied, and serious pollution by pesticides is caused to ask
Topic, becomes and seriously threatens to human health, thus, fast and accurately pesticide residue determination method of establishing can be in fruits and vegetables
Reasonable, the effective monitoring of pesticide residue important technical support is provided.
Persticide residue in a large amount of fruits and vegetables sample is detected in actually detected middle needs, pesticide is remaining in fruits and vegetables
On the one hand detection time depends on sample instrument analytical method, on the other hand also depend on the speed of fruits and vegetables sample pre-treatments.Mesh
Before, the method for most popular garden stuff pesticide residue test sample pre-treatment is QuEChERS method, and step can be simple
It concludes are as follows: (1) sample comminution；(2) single solvent acetonitrile extracts centrifugation；(3) in the supernatant for being centrifugally separating to obtain acetonitrile extraction
Middle addition MgSO4Equal salts carry out centrifugation water removal；(4) ethylenediamine-N- propyl silicon is added in the supernatant being centrifugally separating to obtain
The adsorbents such as alkane (PSA) carry out centrifugation removal of impurities；(5) supernatant carries out GC-MS, LC-MS detection.This method with before other samples
Reason method is more quick compared to, but multiple centrifugation steps still will limit the pre-treatment speed of sample, therefore, need a kind of processing
Sample-pretreating method high-efficient, easy to operate.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of purifications for garden stuff pesticide residue test sample pre-treatment
Adsorbent can be improved the rate of sample pre-treatments.
The object of the invention is also to provide a kind of method of garden stuff pesticide residue test sample pre-treatment, the used time is few, net
It is good to change effect.
It is including following the present invention provides a kind of purifying adsorbent of sample pre-treatments when detection for garden stuff pesticide residue
The raw material of parts by weight: 0~50 part of C18,0~50 part of ketjenblack EC and 10~50 parts of Fe3O4@SiO2@PSA。
Preferably, C18, ketjenblack EC, Fe in the purifying adsorbent3O4@SiO2The mass ratio of@PSA is 0~30:0
~50:10~30.
Sample when being detected the present invention provides a kind of garden stuff pesticide residue using purifying adsorbent described in above-mentioned technical proposal
The method of product pre-treatment, comprising the following steps:
(1) fruits and vegetables homogenised sample to be measured is mixed with acetonitrile, obtains the first mixture；
(2) the first mixture that the step (1) obtains is mixed with sodium chloride and anhydrous magnesium sulfate, obtains the second mixing
Object；
(3) the second mixture that the step (2) obtains is mixed with purifying adsorbent described in above-mentioned technical proposal, is obtained
Magnetic suck mixture；
(4) the magnetic suck mixture that the step (3) obtains is separated with external magnetic field, obtains magnetic suck precipitating and supernatant mentions
Take liquid；
(5) the supernatant extracting solution for taking step (4) to obtain uses filtering with microporous membrane after mixing with water, obtains the sample for detection
Product.
Preferably, the quality of fruits and vegetables homogenised sample to be measured is 1.5~2.5g in the step (1)；With fruits and vegetables to be measured homogenate
On the basis of the quality of sample, the volume of the acetonitrile is 1.5~2.5ml.
Preferably, the mass ratio of sodium chloride and anhydrous magnesium sulfate is 1:3~5 in the step (2).
It is furthermore preferred that fruits and vegetables homogenised sample in the gross mass of the sodium chloride, anhydrous magnesium sulfate and first mixture
Mass ratio be 1.25~2.25:1.5~2.
Preferably, in the step (3) in purifying adsorbent and the second mixture the mass ratio of fruits and vegetables homogenised sample be 1~
6:150~250.
Preferably, the aperture of miillpore filter is 0.22~0.45 μm in the step (5).
Preferably, in the step (1) after mixing further include: by 0.5~2min of obtained mixture vortex；Step (2)
After the mixing further include: by 0.5~2min of obtained mixture vortex；After step (3) described mixing further include: by what is obtained
0.3~1min of mixture vortex.
The present invention provides a kind of detection methods of garden stuff pesticide residue, comprising the following steps: with preceding solution institute
The method processing sample to be tested stated, obtains sample to be tested；The sample to be tested is subjected to LC-MS/MS detection.
Compared with prior art, the invention has the following advantages that
Purifying adsorbent provided by the invention for garden stuff pesticide residue detection when sample pre-treatments when, can be to avoid preceding
Multiple centrifugation in treatment process, to effectively shorten time of pre-treatment.The sample pre-treatments in garden stuff pesticide residue detection
It is middle to use purifying adsorbent provided by the invention, pre-treating method process it can will extract and purify two steps in the prior art
It is incorporated in a step to complete, to effectively save the operating time and be omitted in the centrifugation step between extraction, purifying step.
Meanwhile purifying adsorbent provided by the invention is merged in pretreatment process by that will extract, purify two steps,
Sample is set to be not necessarily to repeatedly be transferred while multiple centrifugation, so that the loss of sample to be tested content is reduced, it is effective to improve
Detection accuracy.
The present invention also provides it is a kind of using above-mentioned purifying adsorbent carry out garden stuff pesticide residue detection pre-treating method,
Experiments have shown that reducing 61.1% relative to existing pre-treating method QuECHERS elapsed time, it is only necessary to 70min
It is completed at the same time the pre-treatment work of 50 samples.Rate of recovery comparative test is also demonstrates that by pre-treating method provided by the invention and surveys
Fixed result can also improve the accuracy rate of detection.The thus method energy of garden stuff pesticide residue detection pre-treatment provided by the invention
Enough accuracys rate for shortening the processing time, improving detection.
Specific embodiment
It is including following the present invention provides a kind of purifying adsorbent of sample pre-treatments when detection for garden stuff pesticide residue
The raw material of parts by weight: 0~50 part of C18,0~50 part of ketjenblack EC and 10~50 parts of Fe3O4@SiO2@PSA。
Purifying adsorbent provided by the invention preferably includes 10~30 parts of Fe3O4@SiO2@PSA, when handled to be measured
Fruits and vegetables more preferably include 10 parts of Fe when being green vegetables, tomato, eggplant, capsicum, sponge gourd or kidney bean3O4@SiO2@PSA, when described
Fruits and vegetables to be measured preferably include 20 parts of Fe when being cucumber3O4@SiO2@PSA.Fe of the present invention3O4@SiO2@PSA is by Chinese special
The method that sharp CN104525128 is recorded is prepared, in the present invention, the Fe3O4@SiO2@PSA is exchanged with weak anionic
Function can form non-covalent bond with the hydroxyl in the molecules such as organic acid, carbohydrate in test substance, so that Adsorption is to be measured
Impurity in sample.In the present invention, the Fe3O4@SiO2The particle size range of@PSA is 531~955nm.In the present invention, institute
State Fe3O4@SiO2Kernel is the Fe that partial size is 470~650nm in@PSA3O4Microballoon.
In the present invention, the C18 is the silica gel material for being bonded octadecane hydrocarbon, and C18 can adsorb non-in sample to be tested
Polarity chaff interferent such as pigment, sterol, volatile oil etc.；When in sample to be tested including the apolar substance of mentioned kind, the present invention
The purifying adsorbent of offer includes C18, specifically, Fe described in techniques described above scheme3O4@SiO2On the basis of the parts by weight of@PSA,
10~30 parts of C18 are preferably included, preferably include 30 parts of C18 when the fruits and vegetables to be measured are eggplant, when the fruits and vegetables to be measured are peppery
10 parts of C18 are preferably included when green pepper.In the present invention, the average particle size of the C18 is preferably 40~60 μm.
In the present invention, when sample to be tested is the more fruits and vegetables such as green vegetables etc. of pigment content, purification provided by the invention
Adsorbent includes ketjenblack EC, being capable of pigment in primary attachment sample to be tested.Specifically, described in techniques described above scheme
Fe3O4@SiO2On the basis of the parts by weight of@PSA, 10~50 parts of ketjenblack EC is preferably included, when the fruits and vegetables to be measured are green vegetables
Being preferably includes 50 parts of ketjenblack ECs.In the present invention, the granularity of the ketjenblack EC is preferably 40~60 μm.
The present invention does not have any restriction to the source of C18 and ketjenblack EC, using commercial goods.
The present invention according to Adsorption is needed in sample to be tested dopant species and content selection purifying adsorbent combination and
Its content, so that more effectively Adsorption sample to be tested impurity, improves the accuracy in detection of pesticide residue.
The present invention does not have special limitation to the preparation method of the purifying adsorbent, by component described in above-mentioned technical proposal
It is mixed according to parts by weight.The Fe contained in purifying adsorbent of the present invention3O4@SiO2@PSA is that a kind of magnetism is received
Rice grain enables purifying adsorbent to be adsorbed by magnetic field, thus purifying adsorbent provided by the invention after absorption without into
The step of row centrifugation can be separated by solid-liquid separation, can simplify sample pre-treatments while adsorption efficiency is high, saves the operating time.
When being detected the present invention also provides a kind of garden stuff pesticide residue using purifying adsorbent described in above-mentioned technical proposal
The method of sample pre-treatments, comprising the following steps:
(1) fruits and vegetables homogenised sample to be measured is mixed with acetonitrile, obtains the first mixture；
(2) the first mixture that the step (1) obtains is mixed with sodium chloride and anhydrous magnesium sulfate, obtains the second mixing
Object；
(3) the second mixture that the step (2) obtains is mixed with purifying adsorbent described in above-mentioned technical proposal, is obtained
To magnetic suck mixture；
(4) the magnetic suck mixture that the step (3) obtains is separated with external magnetic field, obtains magnetic suck precipitating and supernatant mentions
Take liquid；
(5) filtering with microporous membrane after the supernatant extracting solution for taking step (4) to obtain is mixed with water, obtains the sample for detection
Product.
Fruits and vegetables sample to be measured is carried out broken homogenate by the present invention, obtains fruits and vegetables homogenised sample to be measured.In the present invention, described
Fruits and vegetables include green vegetables, tomato, eggplant, capsicum, cucumber, sponge gourd, kidney bean.Broken homogenate side of the present invention to the fruits and vegetables sample
Formula does not have any restriction, using the broken homogenate mode of this field routine, as manual homogenization, mechanical homogenisation, ultrasound homogenate,
Multigelation.Fruits and vegetables sample broke to be measured is homogenized to sample in uniform paste by the present invention, and without obvious particulate material
?.
The present invention mixes fruits and vegetables to be measured homogenised sample described in 1.50~2.50g with 1.50~2.50ml acetonitrile, obtains
One mixture.In the present invention, the fruits and vegetables homogenised sample to be measured preferably weighs 2.00g；With the matter of fruits and vegetables homogenised sample to be measured
On the basis of amount, preferred acetonitrile volume is 2.00ml.The present invention is vortexed after preferably mixing fruits and vegetables homogenised sample to be measured with acetonitrile
0.5~2min obtains the first mixture；The vortex time is more preferably 1min.The present invention is even by fruits and vegetables to be measured using acetonitrile
Remains of pesticide in slurry samples is leached into organic solvent.
In some embodiments, present invention only requires obtain 1.50~2.50g fruits and vegetables homogenised sample to be measured, relative to
Existing pre-treating method, sample sample weighting amount reduce 4 times or more.Meanwhile the present invention is reduced by reducing sample sample weighting amount
Extraction process and the sample size in purification process are poor, so that extraction and purification process be made to complete in same operation system as can
Energy.
After obtaining the first mixture, the present invention mixes first mixture with sodium chloride and anhydrous magnesium sulfate, obtains
Second mixture.0.5~2min of vortex, obtains after the present invention preferably mixes the first mixture with sodium chloride and anhydrous magnesium sulfate
Second mixture；The vortex time is more preferably 1min.In the present invention, the mass ratio of the sodium chloride and anhydrous magnesium sulfate
For 1:3~5, more preferably 1:4.In the present invention, the sodium chloride, anhydrous magnesium sulfate and above-mentioned steps obtain first mixes
The mass ratio of fruits and vegetables homogenised sample is 1.25~2.25:1.5~2, preferably 1.25~2.00:2 in object.
In the present invention, sodium chloride and anhydrous magnesium sulfate can promote the solution in mixture to saltout layering, make to be measured residual
Pesticide is stayed more fully to enter acetonitrile layer, the addition of anhydrous magnesium sulfate can also remove moisture extra in mixture.
After obtaining the second mixture, the present invention mixes the second mixture and purifying adsorbent described in above-mentioned technical proposal
It closes, obtains magnetic suck mixture.When mixing with the purifying adsorbent, purifying adsorbent can be first prepared, then with described second
Mixture mixing, raw material components described in above-mentioned technical proposal can also be mixed with second mixture, suitable to the mixing
Sequence does not have special limitation.0.3~1min of vortex after the present invention preferably mixes the second mixture with the purifying adsorbent, more
Preferably 0.5min.In the present invention, in the purifying adsorbent and the second mixture the mass ratio of fruits and vegetables homogenised sample be 1~
6:150~250, more preferably 1~6:200.The present invention utilizes polarity, non polar impurities in purifying adsorbent adsorbent solution,
It separates the interference impurity for influencing testing result with pesticide, improves sample purification effect.
Existing garden stuff pesticide residue pre-treating method such as QuECHERS need after sodium chloride and anhydrous magnesium sulfate is added
Centrifugally operated is carried out to the mixture of sample and acetonitrile, the supernatant after taking centrifugation carries out subsequent purification processing.It is of the present invention
Purifying adsorbent is applied in garden stuff pesticide residue test sample pre-treating method, extraction and purifying step can be made same
It is completed in container, without being centrifuged after the extraction, effectively saves the time being centrifugated in extraction step, improved
Pre-treatment efficiency.
The present invention separates the magnetic suck mixture with external magnetic field, obtains magnetic suck precipitating and supernatant extracting solution.This hair
The bright external magnetic field is preferably provided at the lower section for containing magnetic suck mixture container, and the present invention is to the external magnetic field without any
It limits, there is magnetic absorption effect, such as magnet.
After Magneto separate, the present invention will obtain filtering with microporous membrane after supernatant extracting solution is mixed with water, obtain for detection
Sample.The present invention preferably by supernatant extracting solution with water to mix in equal volume, for diluting sample to be tested concentration.In the present invention,
The aperture of the miillpore filter is preferably 0.22~0.45 μm, and more preferably 0.22 μm.Garden stuff pesticide residue provided by the invention
Detection method be not necessarily to that treated that solution is centrifuged to purifying adsorbent, since purifying adsorbent has certain magnetic
Property, the purifying adsorbent after adsorbing when by external magnetic field, which can be gathered in, to be tended to external magnetic field direction, quickly and effectively make to purify
Adsorbent is separated with solution.
The present invention provides a kind of detection methods of garden stuff pesticide residue, comprising the following steps: is remembered with preceding solution
The pre-treating method of load handles sample to be tested, obtains sample to be tested；The sample to be tested is subjected to LC-MS/MS detection.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.It is aobvious
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Embodiment 1
By the broken homogenate of green vegetables, above-mentioned green vegetables homogenised sample 2.00g is weighed, Fluoxastrobin standard items are added, make sample to be tested
The concentration of middle Fluoxastrobin is 100 μ g/kg, stands 30min.Green vegetables homogenised sample 2.00g and 2.00ml acetonitrile after weighing mark-on
Mixing, vortex 1min obtain the first mixture；It is mixed with 0.35g sodium chloride and 1.4g anhydrous magnesium sulfate, vortex 1min is obtained
Second mixture；Second mixture is mixed with 60mg purifying adsorbent, vortex 0.5min obtains magnetic suck mixture, described
Purifying adsorbent is by 10mg Fe3O4@SiO2@PSA and 50mg ketjenblack EC composition；Make magnetic suck under the action of external magnetic field
Mixture is separated by solid-liquid separation, and is drawn 0.5ml supernatant extracting solution and is mixed with 0.5ml water, with 0.22 μm of filtering with microporous membrane, gained filtering
Solution is sample to be tested.
Sample to be tested is subjected to LC-MS/MS detection, measures the concentration of Fluoxastrobin in sample to be tested.
Measurement result shows that it is 4.0% that the rate of recovery of Fluoxastrobin, which is 95.1%, RSD value, in sample.
Embodiment 2
By the broken homogenate of tomato, above-mentioned tomato homogenate sample 2.00g is weighed, triazolone standard items are added, make sample to be tested
The concentration of middle triazolone is 100 μ g/kg, stands 30min.Tomato homogenate sample 2.00g and 2.00ml acetonitrile after weighing mark-on
Mixing, vortex 1min obtain the first mixture；It is mixed with 0.3g sodium chloride and 1.2g anhydrous magnesium sulfate, vortex 1min is obtained
Second mixture；Second mixture is mixed with 10mg purifying adsorbent, vortex 0.5min obtains magnetic suck mixture, described
Purifying adsorbent is by 10mg Fe3O4@SiO2@PSA composition；It is separated by solid-liquid separation magnetic suck mixture under the action of external magnetic field,
It draws 0.5ml supernatant extracting solution to mix with 0.5ml water, with 0.22 μm of filtering with microporous membrane, gained filtering solution is to test sample
Product.
Sample to be tested is subjected to LC-MS/MS detection, measures the concentration of triazolone in sample to be tested.
Measurement result shows that it is 1.7% that the rate of recovery of triazolone, which is 93.2%, RSD value, in sample.
Embodiment 3
By the broken homogenate of eggplant, above-mentioned eggplant homogenised sample 1.50g is weighed, Fluoxastrobin standard items are added, make sample to be tested
The concentration of middle Fluoxastrobin is 100 μ g/kg, stands 30min.Eggplant homogenised sample 1.50g and 1.50ml acetonitrile after weighing mark-on
Mixing, vortex 0.5min obtain the first mixture；It is mixed with 0.25g sodium chloride and 1.0g anhydrous magnesium sulfate, vortex 0.5min,
Obtain the second mixture；Second mixture is mixed with 40mg purifying adsorbent, vortex 0.3min obtains magnetic suck mixture,
The purifying adsorbent is by 10mg Fe3O4@SiO2@PSA and 30mgC18 composition；Make magnetic suck mixed under the action of external magnetic field
It closes object to be separated by solid-liquid separation, draws 0.5ml supernatant extracting solution and mixed with 0.5ml water, with 0.45 μm of filtering with microporous membrane, gained filtering is molten
Liquid is sample to be tested.
Sample to be tested is subjected to LC-MS/MS detection, measures the concentration of Fluoxastrobin in sample to be tested.
Measurement result shows that it is 1.3% that the rate of recovery of Fluoxastrobin, which is 102.3%, RSD value, in sample.
Embodiment 4
By the broken homogenate of cucumber, 2.50g cucumber homogenised sample is weighed, Aphox standard items are added, makes to resist in sample to be tested
The concentration of aphid prestige is 100 μ g/kg, stands 30min.Cucumber homogenised sample 2.50g and 2.50ml acetonitrile after weighing mark-on is mixed
It closes, vortex 2min obtains the first mixture；It is mixed with 0.35g sodium chloride and 1.40g anhydrous magnesium sulfate, vortex 2min is obtained
Second mixture；Second mixture is mixed, vortex 1min with 20mg purifying adsorbent, obtains magnetic suck mixture, it is described net
Change adsorbent by 20mg Fe3O4@SiO2@PSA composition；It is separated by solid-liquid separation magnetic suck mixture under the action of external magnetic field, inhales
0.5ml supernatant extracting solution is taken to mix with 0.5ml water, with 0.22 μm of filtering with microporous membrane, gained filtering solution is sample to be tested.
Sample to be tested is subjected to LC-MS/MS detection, measures the concentration of Aphox in sample to be tested.
Measurement result shows that it is 2.6% that the rate of recovery of Aphox, which is 91.2%, RSD value, in sample.
Embodiment 5
By the broken homogenate of capsicum, above-mentioned capsicum homogenised sample 2.00g is weighed, oxygen ring azoles standard items are added, make sample to be tested
The concentration of middle oxygen ring azoles is 100 μ g/kg, stands 30min.Capsicum homogenised sample 2.00g and 2.00ml acetonitrile after weighing mark-on
Mixing, vortex 1min obtain the first mixture；It is mixed with 0.3g sodium chloride and 1.2g anhydrous magnesium sulfate, vortex 1min is obtained
Second mixture；Second mixture is mixed with 20mg purifying adsorbent, vortex 0.5min obtains magnetic suck mixture, described
Purifying adsorbent is by 10mg Fe3O4@SiO2@PSA and 10mgC18 composition；Make magnetic suck mixture under the action of external magnetic field
It is separated by solid-liquid separation, draws 0.5ml supernatant extracting solution and mixed with 0.5ml water, with 0.22 μm of filtering with microporous membrane, gained filtering solution is
For sample to be tested.
Sample to be tested is subjected to LC-MS/MS detection, measures the concentration of oxygen ring azoles in sample to be tested.
Measurement result shows that it is 1.5% that the rate of recovery of Aphox, which is 95.6%, RSD value, in sample.
Embodiment 6
By the broken homogenate of green vegetables, above-mentioned green vegetables homogenised sample 2.00g is weighed, Fluoxastrobin standard items, imidacloprid standard are added
Product and 3- hydroxyl carbofuran standard items, making the concentration of Fluoxastrobin in sample to be tested, imidacloprid and 3- hydroxyl carbofuran is 100 μ
G/kg stands 30min.Green vegetables homogenised sample 2.00g after weighing mark-on is mixed with 2.00ml acetonitrile, vortex 1min, obtains
One mixture；It is mixed with 0.35g sodium chloride and 1.4g anhydrous magnesium sulfate, vortex 1min obtains the second mixture；By the second mixing
Object is mixed with 60mg purifying adsorbent, vortex 0.5min, obtains magnetic suck mixture, the purifying adsorbent is by 10mg Fe3O4@
SiO2@PSA and 50mg ketjenblack EC composition；It is separated by solid-liquid separation magnetic suck mixture under the action of external magnetic field, draws
0.5ml supernatant extracting solution is mixed with 0.5ml water, and with 0.22 μm of filtering with microporous membrane, gained filtering solution is sample to be tested.
Sample to be tested is subjected to LC-MS/MS detection, measures Fluoxastrobin in sample to be tested, imidacloprid and 3-OH carbofuran
Concentration.
Measurement result shows that it is 4.0% that the rate of recovery of Fluoxastrobin, which is 95.1%, RSD value, in sample；The rate of recovery of imidacloprid
It is 12.9% for 89.1%, RSD value；The rate of recovery of 3- hydroxyl carbofuran is that 90.7%, RSD value is 6.2%.
Embodiment 7
By the broken homogenate of tomato, tomato homogenate sample 2.00g is weighed, triazolone standard items, paclobutrazol standard items, nitrile are added
Bacterium azoles standard items, thimet sulfoxide standard and Fipronil sulfone standard items, make triazolone in sample to be tested, paclobutrazol, nitrile bacterium azoles,
The concentration of thimet sulfoxide and Fipronil sulfone is 100 μ g/kg, stands 30min.Tomato homogenate sample after weighing above-mentioned mark-on
2.00g is mixed with 2.00ml acetonitrile, and vortex 1min obtains the first mixture；It is mixed with 0.3g sodium chloride and 1.2g anhydrous magnesium sulfate
It closes, vortex 1min obtains the second mixture；Second mixture is mixed with 10mg purifying adsorbent, vortex 0.5min obtains magnetic
Mixture is adsorbed, the purifying adsorbent is by 10mg Fe3O4@SiO2@PSA composition；Make magnetic suck under the action of external magnetic field
Mixture is separated by solid-liquid separation, and is drawn 0.5ml supernatant extracting solution and is mixed with 0.5ml water, with 0.22 μm of filtering with microporous membrane, gained filtering
Solution is sample to be tested.
Sample to be tested is subjected to LC-MS/MS detection, measures triazolone, paclobutrazol, nitrile bacterium azoles, thimet in sample to be tested
The concentration of sulfoxide and Fipronil sulfone.
Measurement result shows that it is 1.7% that the rate of recovery of triazolone, which is 93.2%, RSD value, in sample；The rate of recovery of paclobutrazol
It is 6.1% for 95.4%, RSD value；The rate of recovery of nitrile bacterium azoles is that 90.5%, RSD value is 7.3%；The rate of recovery of thimet sulfoxide
It is 5.9% for 101.9%, RSD value；The rate of recovery of Fipronil sulfone is that 92.0%, RSD value is 4.0%.
Embodiment 8
By the broken homogenate of eggplant, above-mentioned eggplant homogenised sample 1.50g is weighed, Fluoxastrobin standard items and Entex standard is added
Product, making the concentration of Fluoxastrobin and Entex in sample to be tested is 100 μ g/kg, stands 30min.Eggplant after weighing above-mentioned mark-on
Sub- homogenised sample 1.50g is mixed with 1.50ml acetonitrile, and vortex 0.5min obtains the first mixture；With 0.25g sodium chloride and 1.0g
Anhydrous magnesium sulfate mixing, vortex 0.5min obtain the second mixture；Second mixture is mixed with 40mg purifying adsorbent, whirlpool
0.3min is revolved, obtains magnetic suck mixture, the purifying adsorbent is by 10mg Fe3O4@SiO2@PSA and 30mgC18 composition；?
It is separated by solid-liquid separation magnetic suck mixture under the action of external magnetic field, draws 0.5ml supernatant extracting solution and mixed with 0.5ml water, used
0.45 μm of filtering with microporous membrane, gained filtering solution are sample to be tested.
Sample to be tested is subjected to LC-MS/MS detection, measures the concentration of Fluoxastrobin and Entex in sample to be tested.
Measurement result shows that it is 1.3% that the rate of recovery of Fluoxastrobin, which is 102.3%, RSD value, in sample；The recycling of Entex
Rate is that 97.3%, RSD value is 8.3%.
Embodiment 9
By the broken homogenate of sponge gourd, sponge gourd homogenised sample 2.50g is weighed, Prochloraz standard items, chloromethiuron standard items, water are added
Amine sulphur phosphorus standard items, paclobutrazol standard items, propiconazole standard items, Fipronil standard items and dimethomorph standard items, make to test sample
Prochloraz in product, chloromethiuron, isocarbophos, paclobutrazol, propiconazole, Fipronil and dimethomorph concentration be 100 μ g/kg,
Stand 30min.Sponge gourd homogenised sample 2.50g after weighing mark-on is mixed with 2.50ml acetonitrile, and vortex 2min obtains the first mixing
Object；It is mixed with 0.35g sodium chloride and 1.40g anhydrous magnesium sulfate, vortex 2min obtains the second mixture；By the second mixture with
The mixing of 40mg purifying adsorbent, vortex 1min obtain magnetic suck mixture, and the purifying adsorbent is by 10mg Fe3O4@SiO2@
PSA and 30mgC18 composition；It is separated by solid-liquid separation magnetic suck mixture under the action of external magnetic field, draws 0.5ml supernatant extracting solution
It is mixed with 0.5ml water, with 0.22 μm of filtering with microporous membrane, gained filtering solution is sample to be tested.
Sample to be tested is subjected to LC-MS/MS detection, measures Prochloraz, chloromethiuron, isocarbophos, multiple-effect in sample to be tested
The concentration of azoles, propiconazole, Fipronil and dimethomorph.
Measurement result shows that it is 3.1% that the rate of recovery of Prochloraz, which is 89.1%, RSD value, in sample；The rate of recovery of chloromethiuron
It is 7.2% for 88.5%, RSD value；The rate of recovery of isocarbophos is that 91.9%, RSD value is 11.7%；The rate of recovery of paclobutrazol is
96.1%, RSD value are 4.2%；The rate of recovery of propiconazole is that 100.4%, RSD value is 7.3%；The rate of recovery of Fipronil is
94.7%, RSD value are 2.7%；The rate of recovery of dimethomorph is that 88.2%, RSD value is 10.9%.
Embodiment 10
By the broken homogenate of kidney bean, kidney bean homogenised sample 2.00g is weighed, Fipronil sulfone standard items, Cyproconazole are added
Standard items, bromuconazole standard items and atrazine standard items go Fipronil sulfone, Cyproconazole, bromuconazole and green bristlegrass in sample to be tested
The concentration of saliva is 100 μ g/kg, stands 30min.Kidney bean homogenised sample 2.00g and 2.00ml acetonitrile after weighing mark-on is mixed
It closes, vortex 1min obtains the first mixture；It is mixed with 0.25g sodium chloride and 1.00g anhydrous magnesium sulfate, vortex 1min is obtained
Second mixture；Second mixture is mixed, vortex 1min with 20mg purifying adsorbent, obtains magnetic suck mixture, it is described net
Change adsorbent by 10mg Fe3O4@SiO2@PSA and 10mgC18 composition；Make magnetic suck mixture solid under the action of external magnetic field
Liquid separation is drawn 0.5ml supernatant extracting solution and is mixed with 0.5ml water, and with 0.22 μm of filtering with microporous membrane, gained filtering solution is
For sample to be tested.
Sample to be tested is subjected to LC-MS/MS detection, measures Fipronil sulfone, Cyproconazole, bromuconazole and green bristlegrass in sample to be tested
Go the concentration of saliva.
Measurement result shows that it is 5.2% that the rate of recovery of Fipronil sulfone, which is 91.8%, RSD value, in sample；Cyproconazole returns
Yield is that 98.6%, RSD value is 4.1%；The rate of recovery of bromuconazole is that 93.2%, RSD value is 3.6%；The rate of recovery of atrazine
It is 1.9% for 90.3%, RSD value.
The test result of Examples 1 to 10 shows, detection method provided by the invention is in single Detecting Pesticide and more
Good accuracy and precision are all had in Detecting Pesticide, the rate of recovery of each pesticide can be made to meet 60~130%, phase
Requirement to standard deviation less than 20% utilizes the fruits and vegetables pesticide of purifying adsorbent provided by the invention and the application adsorbent
Residue detection sample-pretreating method can make the pesticide residue Concentration Testing accuracy with higher in sample to be tested.
Comparative example
QuECHERS method is that the garden stuff pesticide residue of pre-treatment detects:
1) it extraction process: weighs fruits and vegetables homogenised sample 10.00g to be measured and is mixed with 10ml acetonitrile, then vortex 1min is added
1.5g sodium chloride and 4g anhydrous magnesium sulfate, vortex 1min are centrifuged 3min, the supernatant solution after centrifugation under the conditions of 7000r/min
Supernatant is as extracted.
2) purification process: accurately pipette acetonitrile extraction supernatant 1ml be added to containing 50mg PSA, 50 mg C18 and
In the 2ml centrifuge tube of 0.15g anhydrous magnesium sulfate, 3min acutely is centrifuged under the conditions of 7000 r/min after vortex 1min after concussion.
0.5ml supernatant is transferred to the water in 2ml centrifuge tube containing 0.5ml.It mixes, with 0.22 μm of membrane filtration, obtains sample to be tested.
Sample to be tested is subjected to UPLC-MS/MS analysis, measures the pesticide concentration in sample to be tested.
Embodiment 11
This experiment is to represent vegetable sample with capsicum and tomato, after capsicum or tomato are crushed homogenate respectively, is weighed
2.00g homogenised sample, is added Multiple Pesticides mixed standard solution, and specific pesticide species are shown in Table 1, make each in vegetable sample to be measured
Pesticide concentration is 100 μ g/kg, stands 30min.
The sample to be tested after mark-on is detected according to the method for embodiment 2, embodiment 5 and comparative example respectively, is had
Body the results are shown in Table 1.
According to the rate of recovery distribution of pesticide in the data statistics garden stuff pesticide residue detection method of table 1 and distinct methods
The comparing results such as required elapsed time, sample consumption are shown in Table 2 and table 3 respectively, wherein pesticide residue detection method in capsicum
Statistical result is shown in Table 2, and the statistical result of pesticide residue detection method is shown in Table 3 in tomato.
The recovery of standard addition and precision of 1 tomato of table, capsicum each pesticide when being fruits and vegetables sample
According to the data of table 1 it is found that the sample mark-on reclaims measured using pesticide residue detection method provided by the invention
Rate and precision RSD value are relative to the sample recovery of standard addition and essence measured with the extremely wide QuECHERS method of application at present
Density RSD value can make the rate of recovery of each pesticide meet 60~130%, relative standard deviation is less than 20% without significant difference
Requirement, illustrate that pre-treating method provided by the invention can satisfy in fruits and vegetables more pesticide residue analysis to accuracy and precision
Requirement.
Method elapsed time, sample consumption and the rate of recovery profiles versus that multi-pesticide residue is analyzed in 2 capsicum of table
As shown in Table 2, when handling capsicum sample, there are many places differences for two methods, from sample, organic solvent, water removal
Compare in the dosage of reagent and purifying adsorbent, the method that this patent provides is substantially less than at present should extensive QuECHERS
Method, thus, this method economy is more preferably.Compare from the rate of recovery distribution of each pesticide, the method that this patent provides is more
It concentrates within the scope of 70-100%, and there is the rate of recovery of some drugs to be then higher than 100% or be lower than in QuECHERS method
70%, although the rate of recovery value still can satisfy the standard requirements of multi-pesticide residue while measurement, the greater concentration of rate of recovery
Distribution can then embody this method and extract and purifying the advantage in fruits and vegetables in more pesticide residues.And maximum advantage is embodied in
In sample treatment speed, it is one group with 50 samples and handles simultaneously, it is all that the method that this patent provides only needs 70min can be completed
Sample treatment, and QuECHERS method needs 180min, is 2.57 times of this method, this method can reduce at least in other words
61.1% pre-treatment time.
Method elapsed time, sample consumption and the rate of recovery profiles versus that multi-pesticide residue is analyzed in 3 tomato of table
As shown in Table 3, in the sample-pretreating method for carrying out tomato sample, there are a variety of differences for two methods.From sample
Product, organic solvent, dehydration reagent and purifying adsorbent dosage on compare, the method that this patent provides is substantially less than and answers at present
The extensive QuECHERS method, thus, this method economy is more preferably.Compare from the rate of recovery distribution of each pesticide, two
Method focuses more in 80~110% ranges, and difference is little.And maximum advantage is embodied in sample treatment speed, with 50
A sample is one group and handles simultaneously, and the method that this patent provides only needs 70min that all samples can be completed to handle, and QuECHERS
Method needs 180min, is 2.57 times of this method, this method can reduce at least 61.1% pre-treatment time in other words.
In summary, garden stuff pesticide residue test sample pre-treating method provided by the invention is by reducing initial sample
Amount, significantly reduces the dosage of Extraction solvent, deicer and subsequent purification agent, improves the economy of this method；Go forward side by side one
Step is added makes the extraction of pre-treatment and purifying step can be merged into a stepping containing the purifying adsorbent including magnetic adsorbent
Row, and the centrifugal treating between the preceding each step of processing is eliminated, effectively improve the processing speed of sample pre-treatments.
Meanwhile rate of recovery result also verify this method can provide it is quite or more preferably quasi- with current widely used QuECHERS method
Exactness.Therefore, this method shows splendid application prospect in terms of practicability, economy.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (7)
1. a kind of method of sample pre-treatments when garden stuff pesticide residue detects, comprises the steps of:
(1) fruits and vegetables homogenised sample to be measured is mixed with acetonitrile, obtains the first mixture；
The quality of the fruits and vegetables homogenised sample to be measured is 1.5~2.5g；It is described on the basis of the quality of fruits and vegetables homogenised sample to be measured
The volume of acetonitrile is 1.5~2.5ml；
(2) the first mixture that the step (1) obtains is mixed with sodium chloride and anhydrous magnesium sulfate, obtains the second mixture；
(3) the second mixture and purifying adsorbent obtained the step (2) is 1~6: 150~250 mixed according to mass ratio
It closes, obtains magnetic suck mixture；
The purifying adsorbent, the raw material including following parts by weight: 0~50 part of C18,0~50 part of ketjenblack EC and 10~50
Part Fe3O4@SiO2@PSA；
(4) the magnetic suck mixture that the step (3) obtains is separated with external magnetic field, obtains magnetic suck precipitating and supernatant extracts
Liquid；
(5) the supernatant extracting solution for taking step (4) to obtain uses filtering with microporous membrane after mixing with water, obtains the sample for detection.
2. the method according to claim 1, wherein C18, ketjenblack EC, Fe in the purifying adsorbent3O4@
SiO2The mass ratio of@PSA is 0~30: 0~50: 10~30.
3. the method according to claim 1, wherein in the step (2) sodium chloride and anhydrous magnesium sulfate matter
Amount is than being 1: 3~5.
4. the method according to claim 1, wherein the gross mass of the sodium chloride, anhydrous magnesium sulfate with it is described
The mass ratio of fruits and vegetables homogenised sample is 1.25~2.25: 1.5~2 in first mixture.
5. the method according to claim 1, wherein in the step (5) miillpore filter aperture be 0.22~
0.45μm。
6. the method according to claim 1, wherein in the step (1) after mixing further include: mixed by what is obtained
Close 0.5~2min of object vortex；After step (2) described mixing further include: by 0.5~2min of obtained mixture vortex；Step (3)
After the mixing further include: by 0.3~1min of obtained mixture vortex.
7. a kind of detection method of garden stuff pesticide residue, which comprises the following steps: with any in claim 1~6
Method described in one handles sample to be tested, obtains sample to be tested；The sample to be tested is subjected to LC-MS/MS detection.
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| CN107957465B (en) * | 2017-12-28 | 2020-11-03 | 广东集菜送食品科技有限公司 | Method for accurately detecting pesticide residue of agricultural products |
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| CN108896525A (en) * | 2018-05-09 | 2018-11-27 | 江苏大学 | A kind of Raman spectrum method for detecting surface reinforcement of fruits and vegetables Organochlorine Pesticide Residues |
| CN108593824A (en) * | 2018-06-08 | 2018-09-28 | 中国水稻研究所 | A kind of pre-treatment purification method of gas chromatography mass spectrometry Detecting Pesticide |
| CN109001312A (en) * | 2018-07-04 | 2018-12-14 | 上海德易检测技术有限公司 | A kind of detection method of pesticide residues in fruits |
| CN109297777A (en) * | 2018-09-29 | 2019-02-01 | 浙江省农业科学院 | A kind of pre-treating method that grape pesticide residual detects and its purification adsorbent material used and application |
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| CN110133161B (en) * | 2019-05-31 | 2021-09-17 | 浙江省农业科学院 | Pretreatment method for determining multiple pesticide residues in seasoned vegetables based on modified magnetic nano material |
| CN110887926B (en) * | 2019-12-19 | 2022-02-25 | 浙江省农业科学院 | Sample pretreatment method for determining residual quantity of various pesticides in dendrobium officinale and detection method thereof |
| CN111151222A (en) * | 2020-03-06 | 2020-05-15 | 福州海关技术中心 | Preparation of magnetic composite adsorption material and application of magnetic composite adsorption material in detection of multiple pesticide residues in tea |
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