CN109298111A - In fruits and vegetables a variety of agricultures it is residual and meanwhile detection method - Google Patents
In fruits and vegetables a variety of agricultures it is residual and meanwhile detection method Download PDFInfo
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Abstract
The present invention relates to the residual detection technique field of agriculture, provide that a variety of agricultures in a kind of fruits and vegetables are residual while the method for detection, including sample treatment: including extracting and purification；It establishes standard curve: the hybrid standard working solution of various concentration is gone up into machine testing respectively, be ordinate by the characteristic ion peak area measured, corresponding concentration of standard solution is abscissa, draws standard curve；The content that each agriculture is residual in institute's sample is calculated according to standard curve；Upper machine testing method is HPLC-MS method.Whereby, the present invention passes through sample treatment；Establish standard curve；The content that each agriculture is residual in institute's sample is finally calculated according to standard curve.The result shows that method is easy to operate, extraction is quick, accuracy is high, repeatability is strong, avermectin and organic phosphorus, carbamate pesticide residue amount analysis measurement are detected simultaneously suitable for fruit and vegetable.
Description
Technical field
Residual the present invention relates to a variety of agricultures in the residual detection technique field of agriculture more particularly to a kind of fruits and vegetables while detection method.
Background technique
Avermectin is one of most popular product in current biological pesticide market.According to Chinese pesticide toxicity grading criteria,
Avermectin category high poison insecticide.
At present in the pesticide residue of agricultural product, avermectin detection only has always independent detection method, and extracting method is multiple
Miscellaneous detection efficiency it is low and cannot simultaneously with the residual common detection of other agricultures.
In summary, the existing technology has inconveniences and defects in actual use, so it is necessary to be improved.
Summary of the invention
For above-mentioned defect, residual the purpose of the present invention is to provide a variety of agricultures in a kind of fruits and vegetables while detection method,
Pass through sample treatment；Establish standard curve；The content that each agriculture is residual in institute's sample is finally calculated according to standard curve.As a result table
Bright, method is easy to operate, extraction is quick, accuracy is high, repeatability is strong, suitable for fruit and vegetable simultaneously detect avermectin and
Organic phosphorus, carbamate pesticide residue amount analysis measurement.
To achieve the goals above, the present invention provides that a variety of agricultures in a kind of fruits and vegetables are residual while the method for detection, including as follows
Step:
Sample treatment: including extracting: weighing 20g sample in centrifuge tube, 7g sodium chloride and 20mL acetonitrile, whirlpool is added
After mixing, 10000r/min homogeneous 3min；4000r/min is centrifuged 5min later.Supernatant 10mL is taken, 40 DEG C of nitrogen, which are blown, closely to be done, residual
Methanol solution of the excess containing 2% methylene chloride redissolves；
Purification: it will redissolve on the solid-phase extraction column after liquid is loaded into activation, collect efflux；40 DEG C of nitrogen of efflux of collection
It blows and closely does, cross 0.22 μm of miillpore filter after rinsing solid-phase extraction column with methanol solution；
Take machine testing on the liquid filtered out；
Establish standard curve: equivalent pipettes each 100 μ L of standard pesticide solution of same concentrations in 10mL volumetric flask, methanol
It is settled to 10mL, obtaining concentration is 1 μ g/mL hybrid standard working solution；
The hybrid standard working solution of each concentration is gone up into machine testing respectively, is ordinate by the characteristic ion peak area measured,
Corresponding concentration of standard solution is abscissa, draws standard curve；
The content that each agriculture is residual in institute's sample is calculated according to standard curve；
The upper machine testing method is HPLC-MS method.
A variety of agricultures are residual in fruits and vegetables according to the present invention while the method for detection, and the upper machine testing includes:
Chromatographic condition
Chromatographic column: C18 chromatographic column (1.9 μm, 100 × 2.1mm)；Mobile phase: A: methanol, C: 0.2% formic acid of addition is water-soluble
The ammonium acetate of liquid；Flow velocity: 0.3mL/min；Column temperature: 40 DEG C；Sample volume: 5 μ L；Gradient elution；
Mass Spectrometry Conditions:
Ion mode: ESI
Scanning mode: positive ion mode.
In fruits and vegetables according to the present invention a variety of agricultures it is residual and meanwhile detection method, the pesticide be avermectin, carbamic acid
Esters and organic phosphates.
A variety of agricultures are residual in fruits and vegetables according to the present invention while the method for detection, and the pesticide is 21 kinds, respectively Avermectin
Element, flolimat, Aldicarb, Aldicarb sulfone, Tinidazole glucose injection, carbendazim, Diacloden, imidacloprid, carbofuran, 3- hydroxyl gram hundred
Prestige, Acetamiprid, Methomyl, metrifonate, demeton, MTMC, carbaryl, Mobucin, Bassa, pyrimethanil, methylamino AVM hereinafter
Rhzomorph and pyridaben.
A variety of agricultures are residual in fruits and vegetables according to the present invention while the method for detection, the methanol solution in the sample handling procedure
In containing 2% methylene chloride.
A variety of agricultures are residual in fruits and vegetables according to the present invention while the method for detection, in the sample handling procedure, using containing
The methanol solution of 2% methylene chloride rinses solid-phase extraction column twice.
In fruits and vegetables according to the present invention a variety of agricultures it is residual and meanwhile detection method, the solid-phase extraction column be PSA column.
In fruits and vegetables according to the present invention a variety of agricultures it is residual and meanwhile detection method, the solid-phase extraction column be amino graphite it is compound
Column.
A variety of agricultures are residual in fruits and vegetables according to the present invention while the method for detection, and the condition of gradient elution is shown in Table 1.
Residual the purpose of the present invention is to provide a variety of agricultures in a kind of fruits and vegetables while detection method, by from sample pre-treatments
Start with, has investigated influence of the different extracting solutions to experimental result；Secondly, analyzing the optimal method of Solid Phase Extraction；Finally, from
Three detection pattern, object ion selection, the selection of mobile phase and proportion directions are explored and are optimized to experiment condition.Pass through
Linear equation and the range of linearity are established, the measurement of the rate of recovery and precision carries out quantitative analysis, to find optimal experiment side
Method improves detection efficiency.The result shows that method is easy to operate, extraction is quick, accuracy is high, repeatability is strong, it is suitable for fruit vegetable
Avermectin and organic phosphorus, carbamate pesticide residue amount analysis measurement are detected in dish simultaneously.
Detailed description of the invention
Fig. 1 is the typical chromatogram of avermectin of the invention；
Fig. 2 is the typical chromatogram of flolimat of the invention；
Fig. 3 is the typical chromatogram of Aldicarb of the invention；
Fig. 4 is the typical chromatogram of Aldicarb sulfone of the invention；
Fig. 5 is the typical chromatogram of Tinidazole glucose injection of the invention；
Fig. 6 is the typical chromatogram of carbendazim of the invention；
Fig. 7 is the typical chromatogram of Diacloden of the invention；
Fig. 8 is the typical chromatogram of imidacloprid of the invention；
Fig. 9 is the typical chromatogram of carbofuran of the invention；
Figure 10 is the typical chromatogram of 3- hydroxyl carbofuran of the invention；
Figure 11 is the typical chromatogram of Acetamiprid of the invention；
Figure 12 is the typical chromatogram of Methomyl of the invention；
Figure 13 is the typical chromatogram of metrifonate of the invention；
Figure 14 is the typical chromatogram of demeton of the invention；
Figure 15 is the typical chromatogram of MTMC of the invention；
Figure 16 is the typical chromatogram of carbaryl of the invention；
Figure 17 is the typical chromatogram of Mobucin of the invention；
Figure 18 is the typical chromatogram of Bassa of the invention；
Figure 19 is the typical chromatogram of pyrimethanil of the invention；
Figure 20 is the typical chromatogram of emamectin benzoate of the invention；
Figure 21 is the typical chromatogram of pyridaben of the invention.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
The present invention provides that a variety of agricultures in a kind of fruits and vegetables are residual while the method for detection, includes the following steps:
Sample treatment: including extracting: weighing 20g sample in centrifuge tube, 7g sodium chloride and 20mL acetonitrile, whirlpool is added
After mixing, 10000r/min homogeneous 3min；4000r/min is centrifuged 5min later.Supernatant 10mL is taken, 40 DEG C of nitrogen, which are blown, closely to be done, residual
Methanol solution of the excess containing 2% methylene chloride redissolves；
Purification: it will redissolve on the solid-phase extraction column after liquid is loaded into activation, collect efflux；40 DEG C of nitrogen of efflux of collection
It blows and closely does, cross 0.22 μm of miillpore filter after rinsing solid-phase extraction column with methanol solution；
Preferably, the present invention rinses solid-phase extraction column twice using the methanol solution containing 2% methylene chloride, to have
Ingredient is imitated to wash out.
Take machine testing on the liquid filtered out；
Establish standard curve: equivalent pipette concentration be 100 μ g/mL each 100 μ L of standard pesticide solution in 10mL volumetric flask
In, methanol constant volume to 10mL, obtaining concentration is 1 μ g/mL hybrid standard working solution；
The hybrid standard working solution of each concentration is gone up into machine testing respectively, is ordinate by the characteristic ion peak area measured,
Corresponding concentration of standard solution is abscissa, draws standard curve；
The content that each agriculture is residual in institute's sample is calculated according to standard curve；
Upper machine testing method of the invention is HPLC-MS method.
Embodiment
The present invention selects the foundation of apple or the standard curve of cabbages leaves progress Multiple Pesticides using preceding method.It selects
Pesticide is avermectin, carbamates and organic phosphates.21 kinds of specific choice, respectively avermectin, flolimat, tears
Go out prestige, Aldicarb sulfone, Tinidazole glucose injection, carbendazim, Diacloden, imidacloprid, carbofuran, 3- hydroxyl carbofuran, Acetamiprid, go out it is more
Prestige, metrifonate, demeton, MTMC, carbaryl, Mobucin, Bassa, pyrimethanil, emamectin benzoate and pyridaben.
The instrument and equipment that the present invention uses includes: liquid chromatography mass combined instrument TSQ Quantum Ultra；C18 color
It composes column (100 × 2.1mm, 1.9 μm of particle size, Thermo Fisher Scientific companies)；Refrigerated centrifuge；
Solid-phase extraction device (Agilent Technologies)；Full-automatic homogenizer (the farsighted section in Xiamen)；Electronic balance；Vortex mixer；Nitrogen is blown
Instrument.
Upper machine testing includes:
Chromatographic condition
Chromatographic column: C18 chromatographic column (1.9 μm, 100 × 2.1mm)；Mobile phase: A: methanol, C: 0.2% formic acid of addition is water-soluble
The ammonium acetate of liquid；Flow velocity: 0.3mL/min；Column temperature: 40 DEG C；Sample volume: 5 μ L；Gradient elution；
Mass Spectrometry Conditions:
Ion mode: ESI
Scanning mode: positive ion mode.
Condition of gradient elution of the invention is shown in Table 1.
1 gradient elution of table
Inventor has investigated the separating effect of each component when column temperature is 25 DEG C, 30 DEG C, 35 DEG C and 40 DEG C, and discovery column temperature is herein
Can be efficiently separated in range, as temperature increases, appearance time slightly shortens, but column temperature be 40 DEG C when each component peak shape point
Sharp and separating degree is preferable, therefore selects column temperature for 40 DEG C.
The optimization of extractant
Inventor's extractant has attempted acetone, methanol, acetonitrile, methylene chloride, since all kinds of objects are in different solvents
Different solubility, be maximal efficiency raising extraction efficiency, compared a variety of extractants and mixing extractant: acetone volatility
By force, it cannot be come into full contact with sample in homogenizing process；Methylene chloride has more virulent property；Methanol can the water in sample dissolve each other,
Lack the method for efficiently separating；Acetonitrile can sufficiently dissolve avermectin and all kinds of objects, and mutual with saturated sodium chloride solution
Do not allow, toxicity is relatively light.The condition of various aspects is combined, it is final to determine acetonitrile as Extraction solvent.
The optimization of solid-phase extraction column
Solid-phase extraction column has attempted nh 2 column, Florey silicagel column, PSA column, amino graphite combined column and different elutions
Liquid proportion.Florey column is only obvious to the residual chaff interferent retention of organochlorine class agriculture, general to pigment organic acid reserve capability.
PSA column has stronger reservation to a variety of chaff interferents, but price is relatively expensive, and use cost is high.Nh 2 column is to pigment, organic acid, rouge
The chaff interferents such as fat acid have preferable reserve capability, cut it is weaker to the residual reserve capability of object agriculture, though cost performance is high, to vegetables with green leaves
The equal higher sample purification scarce capacity of pigment contents, therefore it is preferable to use amino graphite combined columns to carry out sample purification.
Elute the optimization of solution
Elution solution has attempted acetonitrile, methanol and dichloromethane methanol mixed liquor.Acetonitrile eluting power is too strong, interference
Object can not be retained on pillar, reduce clean-up effect；Pure methanol need to be eluted with larger volume, could effectively be eluted object
Get off, what is used is less economical；The methylene chloride for adding 1%-5% in methyl alcohol is attempted, discovery exists when methylene chloride additive amount
When 2%, need only 3-4mL eluent effectively remaining object can be eluted from nh 2 column.
Purification condition after final optimization pass are as follows: amino graphite combined column, the meoh eluate of 2% methylene chloride.
Mass Spectrometry Conditions optimization
In GB 23200.20-2016, the Mass Spectrometry Conditions of detection avermectin residue are electrochemical ion source (APCI
Source), negative ion mode.There is preferable Ionization Efficiency in the source APCI to non-polar compound, and negative ion mode is with respect to cation mould
Formula is relatively small to the response of target compound, but also bigger with respect to the interfering noise reduction that positive ion mode introduces.But consider
To the residual detection of a variety of agricultures of organic phosphorus, organochlorine, carbamates is taken into account, the electricity for being easier to ionize multiple compounds has been selected
Chemical ionization source (source ESI), positive ion mode, and by adjusting object ion pair, so that mass spectrograph is to avermectin and respectively
Class agriculture is residual preferable response.Avermectin exists in the case where the source ESI ionizes adds H+ fragment ion and plus Na+ fragment ion；But I
Ammonium acetate is introduced in mobile phase, therefore can obtain response preferably plus NH3+ fragment ion, both ensure that interference
Object effectively removes, and instrument response size has been combined, in this, as quota ion.Therefore preferred positive ion mode.
Liquid chromatogram isolation optimization
Existing national standard method uses acetonitrile as mobile phase, but acetonitrile eluting power is too strong, and all kinds of objects are in liquid chromatogram
Retention time on column is excessively concentrated relatively is easy to make object and impurity to enter mass spectrum jointly, influences mass spectrograph to object
Response, and acetonitrile toxicity is stronger.Methanol is lower with respect to acetonitrile toxicity, is slightly below acetonitrile, Neng Goushi to the eluting power of object
Existing object is efficiently separated with what impurity interfered, and makes each relatively reasonable distribution of object retention time.Add in mobile phase
Add appropriate formic acid, the Ionization Efficiency that all kinds of objects add H fragment can be effectively improved, improves mass spectrograph to the sound of object
It answers.Therefore, the proportion of mobile phase of final optimization pass is A: methanol, the aqueous formic acid (0.2%) of C:2mmol/L ammonium acetate.
The typical chromatogram of 21 kinds of pesticide standard specimens is shown in Fig. 1-Figure 21.
The range of linearity and detection limit of standard curve
Aforementioned mixed standard solution is analyzed.The mixed standard solution of six groups of various concentrations is taken, it is final to obtain six groups of test knots
Fruit.Using solution concentration as abscissa, linear regression is carried out by ordinate of corresponding peak area.Regression equation, related coefficient, inspection
Rising limit and the range of linearity are shown in Table 2.
As shown in Table 2, related coefficient generally meets or exceeds 0.9876；With 3 times of signal-to-noise ratio computations, minimum detection
Limit: 0.2 μ g/kg；Range of linearity 1-20mg/L.It can effectively be detected in same matrix simultaneously within the most short time using this programme
Avermectin and organic phosphorus, carbamate chemicals for agriculture.
Recovery testu is carried out using negative sample as matrix respectively, weighs sample 20g, and do parallel laboratory test.Respectively
It is mixed into the standard mixed solution of two kinds of concentration of 2.0 μ g/kg and 20.0 μ g/kg in the sample, is sufficiently mixed uniformly, according to aforementioned side
The operating procedure of method is tested.It uses negative sample when pitch-based sphere is 10 μ g/kg, measures each pesticide standard continuous six times
The RSD of product.Measurement result is shown in Table 3.
As shown in Table 3, it is 1.23~2.64% that the rate of recovery of 21 kinds of pesticides of the invention, which is 93~105.2%, RSD,.It surveys
Determine the requirement that result meets pesticide residue detection and analysis, also shows detecting instrument and have good stability.
Result above is it is found that detection method of the invention meets the requirement of national standard.
Detection method of the invention can be generally applicable in and fruits and vegetables class, herein a different citing.
The present invention starts with from sample pre-treatments, determines acetonitrile as Extraction solvent；Secondly, analyzing the purification of Solid Phase Extraction
Condition are as follows: amino graphite combined column, the meoh eluate of 2% methylene chloride.Finally, from detection pattern, object ion selection, stream
Three directions of selection and proportion of dynamic phase are explored and optimized by experiment condition, it is determined that the source ESI positive ion mode, main mesh
Mark object ion pair and proportion of mobile phase.The result shows that: this method is easy to operate, extraction is quick, accuracy is high, repeatability is strong, fits
For avermectin and organic phosphorus, carbamate pesticide residue amount analysis measurement to be detected in fruit and vegetable simultaneously.
2 directrix curve regression equation of table, related coefficient and detection limit
3 rate of recovery of table and precision
In conclusion it is residual the purpose of the present invention is to provide a variety of agricultures in a kind of fruits and vegetables at the same detection method, by from
Sample pre-treatments are started with, and influence of the different extracting solutions to experimental result has been investigated；Secondly, analyzing the optimization side of Solid Phase Extraction
Method；Finally, being explored from three detection pattern, object ion selection, the selection of mobile phase and proportion directions to experiment condition
And optimization.By establishing linear equation and the range of linearity, the measurement of the rate of recovery and precision carries out quantitative analysis, to find
Optimal experimental method improves detection efficiency.The result shows that method is easy to operate, extraction is quick, accuracy is high, repeatability is strong,
Detect avermectin and organic phosphorus, carbamate pesticide residue amount analysis measurement simultaneously suitable for fruit and vegetable.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
It knows those skilled in the art and makes various corresponding changes and modifications, but these corresponding changes and change in accordance with the present invention
Shape all should fall within the scope of protection of the appended claims of the present invention.
Claims (9)
1. in a kind of fruits and vegetables a variety of agricultures it is residual and meanwhile detection method, which comprises the steps of:
Sample treatment: including extracting: weighing 20g sample in centrifuge tube, 7g sodium chloride and 20mL acetonitrile, whirlpool mixing is added
Afterwards, 10000r/min homogeneous 3min；4000r/min is centrifuged 5min later.Supernatant 10mL is taken, 40 DEG C of nitrogen blow close dry, residue
It is redissolved with the methanol solution containing 2% methylene chloride；
Purification: it will redissolve on the solid-phase extraction column after liquid is loaded into activation, collect efflux；40 DEG C of nitrogen of efflux of collection are blown closely
It is dry, 0.22 μm of miillpore filter is crossed after rinsing solid-phase extraction column with methanol solution；
Take machine testing on the liquid filtered out；
Establish standard curve: equivalent pipette concentration be 100 μ g/mL each 100 μ L of standard pesticide solution in 10mL volumetric flask, first
Alcohol is settled to 10mL, and obtaining concentration is 1 μ g/mL hybrid standard working solution；
The hybrid standard working solution of each concentration is gone up into machine testing respectively, is ordinate by the characteristic ion peak area measured, it is corresponding
Concentration of standard solution be abscissa, draw standard curve；
The content that each agriculture is residual in institute's sample is calculated according to standard curve；
The upper machine testing method is HPLC-MS method.
2. in fruits and vegetables according to claim 1 a variety of agricultures it is residual and meanwhile detection method, which is characterized in that the upper machine testing
Include:
Chromatographic condition
Chromatographic column: C18 chromatographic column (1.9 μm, 100 × 2.1mm)；Mobile phase: A: methanol, C: 0.2% aqueous formic acid of addition
Ammonium acetate；Flow velocity: 0.3mL/min；Column temperature: 40 DEG C；Sample volume: 5 μ L；Gradient elution；
Mass Spectrometry Conditions:
Ion mode: ESI
Scanning mode: positive ion mode.
3. in fruits and vegetables according to claim 2 a variety of agricultures it is residual and meanwhile detection method, which is characterized in that the pesticide be Ah
Tie up rhzomorph, carbamates and organic phosphates.
4. in fruits and vegetables according to claim 3 a variety of agricultures it is residual and meanwhile detection method, which is characterized in that the pesticide be 21
Kind, respectively avermectin, flolimat, Aldicarb, Aldicarb sulfone, Tinidazole glucose injection, carbendazim, Diacloden, imidacloprid, gram
It is Budweiser, 3- hydroxyl carbofuran, Acetamiprid, Methomyl, metrifonate, demeton, MTMC, carbaryl, Mobucin, Bassa, phonetic
Mould amine, emamectin benzoate and pyridaben.
5. in fruits and vegetables according to claim 1 a variety of agricultures it is residual and meanwhile detection method, which is characterized in that the sample treatment
In methanol solution in step containing 2% methylene chloride.
6. in fruits and vegetables according to claim 5 a variety of agricultures it is residual and meanwhile detection method, which is characterized in that the sample treatment
In step, solid-phase extraction column is rinsed twice using the methanol solution containing 2% methylene chloride.
7. in fruits and vegetables according to claim 1 a variety of agricultures it is residual and meanwhile detection method, which is characterized in that the Solid Phase Extraction
Column is PSA column.
8. in fruits and vegetables according to claim 1 a variety of agricultures it is residual and meanwhile detection method, which is characterized in that the Solid Phase Extraction
Column is amino graphite combined column.
9. in fruits and vegetables according to claim 2 a variety of agricultures it is residual and meanwhile detection method, which is characterized in that the gradient elution
Condition see the table below.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110514764A (en) * | 2019-09-05 | 2019-11-29 | 山东陆桥检测技术股份有限公司 | It is a kind of to measure the remaining detection method of Multiple Pesticides in non-fat property fruits and vegetables |
| CN114994228A (en) * | 2022-04-25 | 2022-09-02 | 曹天亚 | Method for measuring residual quantity of pyrimethanil in vegetables and fruits |
| EP4379062A1 (en) | 2022-11-30 | 2024-06-05 | Fundación AZTI - AZTI Fundazioa | Biosystem for pesticide detection |
-
2018
- 2018-12-07 CN CN201811492268.6A patent/CN109298111A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110514764A (en) * | 2019-09-05 | 2019-11-29 | 山东陆桥检测技术股份有限公司 | It is a kind of to measure the remaining detection method of Multiple Pesticides in non-fat property fruits and vegetables |
| CN114994228A (en) * | 2022-04-25 | 2022-09-02 | 曹天亚 | Method for measuring residual quantity of pyrimethanil in vegetables and fruits |
| EP4379062A1 (en) | 2022-11-30 | 2024-06-05 | Fundación AZTI - AZTI Fundazioa | Biosystem for pesticide detection |
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