CN110967417A - Method for determining pesticide residues in vegetables and fruits - Google Patents
Method for determining pesticide residues in vegetables and fruits Download PDFInfo
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- CN110967417A CN110967417A CN201811152469.1A CN201811152469A CN110967417A CN 110967417 A CN110967417 A CN 110967417A CN 201811152469 A CN201811152469 A CN 201811152469A CN 110967417 A CN110967417 A CN 110967417A
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000000447 pesticide residue Substances 0.000 title claims abstract description 13
- 235000013311 vegetables Nutrition 0.000 title claims abstract description 12
- 235000013399 edible fruits Nutrition 0.000 title claims abstract description 11
- 238000000746 purification Methods 0.000 claims abstract description 27
- 238000001514 detection method Methods 0.000 claims abstract description 14
- 238000000605 extraction Methods 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 239000000945 filler Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 9
- 238000004811 liquid chromatography Methods 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 238000010829 isocratic elution Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 230000005526 G1 to G0 transition Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000003905 agrochemical Substances 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000004587 chromatography analysis Methods 0.000 abstract 1
- 238000012856 packing Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000000575 pesticide Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000006228 supernatant Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 3
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 244000099147 Ananas comosus Species 0.000 description 2
- 235000007119 Ananas comosus Nutrition 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 244000269722 Thea sinensis Species 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 238000012271 agricultural production Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 235000013569 fruit product Nutrition 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000005180 public health Effects 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004885 tandem mass spectrometry Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
本发明涉及一种测定蔬果中农药残留的方法，属于分析化学技术领域。本发明所述方法包括样品前处理步骤和检测步骤；所述样品前处理步骤包括提取步骤、净化步骤；所述提取步骤为：将农产品溶解，均质，离心，分离得到待净化样品；所述净化步骤为采用装有填料的净化管净化，净化步骤简单，色谱分析测定结果准确。本发明获得了满意的分离效果和检测灵敏度。The invention relates to a method for determining pesticide residues in vegetables and fruits, belonging to the technical field of analytical chemistry. The method of the invention includes a sample pretreatment step and a detection step; the sample pretreatment step includes an extraction step and a purification step; the extraction step is: dissolving, homogenizing, centrifuging and separating agricultural products to obtain a sample to be purified; the The purification step is to use a purification tube equipped with packing, the purification steps are simple, and the chromatographic analysis and determination results are accurate. The present invention obtains satisfactory separation effect and detection sensitivity.
Description
Technical Field
The invention relates to a method for determining pesticide residues in vegetables and fruits, belonging to the technical field of analytical chemistry
Background
The pesticide is used as an important agricultural production material, plays a vital role in protecting crops from being damaged by diseases, pests and weeds, improving the agricultural production efficiency, guaranteeing the crop yield and the like, but simultaneously, because the pesticide is unreasonably used, the pesticide residue exceeds the standard, and the harm is also caused to the public health and the food safety. With the continuous progress of the pesticide industry, the types and the amount of pesticides used at present are also continuously increased. The safety problem of agricultural products is always the focus of social attention, and is directly related to public health and ecological environment safety. At present, a pesticide residue analysis method is one of important means for evaluating the quality safety level of agricultural products. Among them, the gas (liquid) chromatography-tandem mass spectrometry technology is popular with researchers of pesticide residue because of its advantages of high sensitivity, strong selectivity, reliable qualitative means, short analysis time and the like, and is widely used for detecting trace substances under the background of complex matrix.
Vegetables and fruits are one of the most important edible agricultural products in the world, and along with the improvement of the social and economic level of China, the proportion of the vegetables and fruits in the public diet is continuously improved. Meanwhile, most vegetables and fruits have the characteristics of short interval between market and harvesting, common plant diseases and insect pests and high economic value of crops, so that the types and the using amount of pesticides applied in production are relatively more, and the problem of overproof pesticide residues in the vegetables and fruits is obvious.
The existing method for detecting the pesticide in the vegetables and the fruits usually adopts a gas chromatography-mass spectrometry method and a liquid chromatography-tandem mass spectrometry method, and generally comprises the steps of extracting pesticide residues in fruit trees, purifying an extracting solution and the like. In the prior art, the extracting solution is generally required to be purified by a solid-phase extraction column, and due to the characteristics of the solid-phase extraction column, the operation steps are complex, the key control points of the method are more, so that the purification cost is more time, and the overall detection efficiency is reduced.
Disclosure of Invention
The invention adopts the method of combining the solid-phase extraction pretreatment with the liquid chromatography, establishes the determination method of the pesticides in various agricultural products, and overcomes the defect of qualitative and quantitative detection of pesticide residues in various agricultural products by the existing method.
The invention provides a method for determining pesticide residue in agricultural products, which comprises a sample pretreatment step; the sample pretreatment step comprises an extraction step and a purification step
The extraction steps are as follows: dissolving the vegetable and fruit products by using an organic solvent, homogenizing, centrifuging, and separating to obtain a sample to be purified;
the purification steps are as follows: moving a sample to be purified into a purification pipe filled with filler, carrying out vortex mixing for 1-2 min, and carrying out centrifugal separation treatment to obtain upper and lower layered liquid; adding anhydrous magnesium sulfate, PSA and C18 filler, wherein the volume ratio of the anhydrous magnesium sulfate to the PSA to the C18 is 4: 1-3: 3-1;
the detection step is liquid chromatography detection; the liquid chromatography conditions are as follows:
a chromatographic column: a silica gel column;
mobile phase: mobile phase A: water, mobile phase B: acetonitrile;
isocratic elution: 30-50% of A.
Based on the technical scheme, preferably, the organic solvent is any one of methanol, n-hexane and acetonitrile.
Based on the above technical solution, preferably, the specification of the chromatographic column is preferably: 2mm x 80-100 mm.
Based on the above technical scheme, preferably, the particle size of the stationary phase is 5-8 μm.
Based on the technical scheme, the flow rate of the mobile phase is preferably 0.2-0.25 mL/min.
Based on the technical scheme, the preferable column temperature of the chromatographic column is 35-45 ℃.
Based on the technical scheme, preferably, the injection volume is preferably 10-15 mu L.
Has the advantages that:
the method comprises a sample pretreatment step; the sample pretreatment step comprises an extraction step and a purification step; the extraction steps are as follows: dissolving the vegetable and fruit products, homogenizing, centrifuging, and separating to obtain a sample to be purified; the purification steps are as follows: the purification is carried out by adopting the purification tube filled with the filler, the operation steps are simple, and the satisfactory separation effect and the satisfactory detection sensitivity are obtained. The method overcomes the defect of qualitative and quantitative detection of pesticide residue in various agricultural products by the existing method.
Detailed Description
Example 1
A method for determining residual pesticide levels in agricultural products, said method comprising the steps of:
a sample pretreatment step:
the extraction step comprises: adding 10g of pineapple sample into a mixed solution of 30mL of water and 30mL of dichloromethane, homogenizing at 20000r/min for 2min, centrifuging at 5000r/min for 5min, and separating supernatant to obtain a sample to be purified;
a purification step: adding 400mg of anhydrous magnesium sulfate, 100mg of PSA and 300mg of C18 filler into a purification tube to obtain the purification tube filled with the filler; measuring 7mL of a sample to be purified into a purification tube filled with a filler, carrying out vortex mixing for 2min, and carrying out centrifugal separation treatment to obtain upper and lower layered liquid; drying the supernatant in the upper and lower layered liquid, and dissolving with a mobile phase;
a liquid chromatography detection step:
chromatographic conditions are as follows:
a chromatographic column: silica gel column (2 mm. times.100 mm, 5 μm);
mobile phase: mobile phase A: water, mobile phase B: acetonitrile;
isocratic elution: 50% of A;
the flow rate of the mobile phase is 0.22 mL/min;
the temperature of the chromatographic column is 40 ℃;
the injection volume was 10. mu.L.
The limit of quantitation of the pineapple sample is 0.008 mg/kg.
Example 2
A method for determining residual pesticide levels in agricultural products, said method comprising the steps of:
a sample pretreatment step:
the extraction step comprises: adding 1g of Longjing tea sample into 20mL of water, homogenizing for 2min at 20000r/min, centrifuging for 5min at 5000r/min, separating supernatant, adding equal volume of dichloromethane, extracting, and discarding dichloromethane layer to obtain a sample to be purified;
a purification step: adding 400mg of anhydrous magnesium sulfate, 100mg of PSA and 300mg of C18 filler into a purification tube to obtain the purification tube filled with the filler; measuring 7mL of a sample to be purified into a purification tube filled with a filler, carrying out vortex mixing for 2min, and carrying out centrifugal separation treatment to obtain upper and lower layered liquid; drying the supernatant in the upper and lower layered liquid, and dissolving with a mobile phase;
a liquid chromatography detection step:
chromatographic conditions are as follows:
a chromatographic column: silica gel column (2 mm. times.100 mm, 5 μm);
mobile phase: mobile phase A: water, mobile phase B: acetonitrile;
isocratic elution: 30% of A;
the flow rate of the mobile phase is 0.22 mL/min;
the temperature of the chromatographic column is 40 ℃;
the injection volume was 10. mu.L.
The limit of quantification of the Longjing tea sample is 0.015 mg/kg.
Example 3
A method for determining residual pesticide levels in agricultural products, said method comprising the steps of:
a sample pretreatment step:
the extraction step comprises: adding 2g of corn sample into 20mL of 25 v/v% acetone aqueous solution, homogenizing at 20000r/min for 2min, centrifuging at 5000r/min for 5min, separating supernatant, adding equal volume of dichloromethane, extracting, and removing dichloromethane layer to obtain a sample to be purified;
a purification step: adding 400mg of anhydrous magnesium sulfate, 100mg of PSA and 300mg of C18 filler into a purification tube to obtain the purification tube filled with the filler; measuring 7mL of a sample to be purified into a purification tube filled with a filler, carrying out vortex mixing for 2min, and carrying out centrifugal separation treatment to obtain upper and lower layered liquid; drying the supernatant in the upper and lower layered liquid, and dissolving with a mobile phase;
a liquid chromatography detection step:
chromatographic conditions are as follows:
a chromatographic column: silica gel column (2 mm. times.100 mm, 5 μm);
mobile phase: mobile phase A: water, mobile phase B: acetonitrile;
isocratic elution: 50% of A;
the flow rate of the mobile phase is 0.22 mL/min;
the temperature of the chromatographic column is 40 ℃;
the injection volume was 10. mu.L.
The limit of quantitation for the corn sample was 0.008 mg/kg.
It should be noted that, in this document, the term "comprises/comprising" or any other variation thereof is intended to cover a non-exclusive inclusion, so that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but also other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
All the embodiments in the present specification are described in a related manner, and the same and similar parts among the embodiments may be referred to each other, and each embodiment focuses on the differences from the other embodiments.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (7)
1. A method for measuring pesticide residues in vegetables and fruits is characterized by comprising the following steps: the method comprises a sample pretreatment step and a detection step;
the sample pretreatment step comprises an extraction step and a purification step;
the extraction steps are as follows: dissolving agricultural products with organic matters, homogenizing, centrifuging, and separating to obtain a sample to be purified;
the purification steps are as follows: moving a sample to be purified into a purification pipe filled with filler, carrying out vortex mixing for 1-2 min, and carrying out centrifugal separation treatment to obtain upper and lower layered liquid; adding anhydrous magnesium sulfate, PSA and C18 filler, wherein the volume ratio of the anhydrous magnesium sulfate to the PSA to the C18 is 4: 1-3: 3-1;
the detection step is liquid chromatography detection; the liquid chromatography conditions are as follows:
a chromatographic column: a silica gel column;
mobile phase: mobile phase A: water, mobile phase B: acetonitrile;
isocratic elution: 30-50% of A.
2. The method of claim 1, wherein: the organic solvent is any one of methanol, normal hexane and acetonitrile.
3. The method of claim 1, wherein: the specification of the chromatographic column is as follows: 2mm x 80-100 mm.
4. The method of claim 1, wherein: the particle size of the stationary phase is 5-8 μm.
5. The method of claim 1, wherein: the flow rate of the mobile phase is 0.2-0.25 mL/min.
6. The method for determining the residual amount of agricultural chemicals in agricultural products according to claim 1, wherein: the temperature of the chromatographic column is 35-45 ℃.
7. The method of claim 1, wherein: the injection volume is 10-15 μ L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811152469.1A CN110967417A (en) | 2018-09-29 | 2018-09-29 | Method for determining pesticide residues in vegetables and fruits |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811152469.1A CN110967417A (en) | 2018-09-29 | 2018-09-29 | Method for determining pesticide residues in vegetables and fruits |
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| Publication Number | Publication Date |
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| CN110967417A true CN110967417A (en) | 2020-04-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201811152469.1A Pending CN110967417A (en) | 2018-09-29 | 2018-09-29 | Method for determining pesticide residues in vegetables and fruits |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112798704A (en) * | 2020-12-28 | 2021-05-14 | 江西省食品检验检测研究院（江西国家果蔬产品及加工食品质量监督检验中心） | Method for detecting pesticide residue in plant-derived agricultural products |
-
2018
- 2018-09-29 CN CN201811152469.1A patent/CN110967417A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112798704A (en) * | 2020-12-28 | 2021-05-14 | 江西省食品检验检测研究院（江西国家果蔬产品及加工食品质量监督检验中心） | Method for detecting pesticide residue in plant-derived agricultural products |
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Application publication date: 20200407 |