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GB 23200.35-2016Food safety national standard -- Determination of Urea Pesticide Residues in Plant -- Derived Foods by Liquid Chromatography-Mass Spectrometry (English PDF)

植物源性食品中取代脲类农药残留量的测定液相色谱-质谱法

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Issued by

National Health and Family Planning Commission of the People 's Republic of China

Level / Type

National · Mandatory

Issue date

December 18, 2016

Implementation date

June 18, 2017

Scope

GB 23200.35-2016 is the English-translated version of 植物源性食品中取代脲类农药残留量的测定液相色谱-质谱法.

GB 23200.35-2016 — This standard specifies the method for the determination of 15 substituted urea pesticides (see Appendix A) residues in plant-derived foods by liquid chromatography-mass spectrometry.

This standard applies to quantitative determination of 15 substituted urea pesticide residues in maize, soybeans, oranges, rice and Chinese cabbage. Other foods can refer to the implementation of other food can refer to the implementation.

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Document preview — GB 23200.35-2016

National Standard of the People's Republic of China

Classification: G 25
Replacing: SN/T 2213-2008

Issued by: National Health and Family Planning Commission of the People 's Republic of China

Foreword
1 Scope
2 Normative reference documents
3 Principle
4 Reagents and materials
4.1 Reagents
4.2 Solution preparation
4.3 Standards
4.4 Standard solution preparation
4.5 Materials
5 Instruments and equipment
6 Preparation and storage of samples
6.1 Preparation of the sample
6.2 Sample storage
7 Analysis steps
7.1 Extraction
7.2 Purification
7.3 Instrument reference conditions
7.4 Standard working curve
7.5 Determination
7.6 Blank experiment
8 Results are calculated and expressed
9 Precision
10.1 Quantitation limits
10.2 Recovery rate
15 Basic information on substituted urea pesticides

Foreword

This standard replaces SN/T 2213-2008 "Determination of Urea Pesticide Residues in Import and Export Plant-derived Foods Liquid Chromatography-Mass Spectrometry /Mass spectrometry ".

Compared with SN/T 2213-2008, the main changes are as follows.

- Standard text format is modified to national standard text format for food safety;

- the name of the "import and export of plant-derived food" to "plant-derived food";

- increase the "other food reference implementation" in the standard range.

This standard replaced the previous version of the standard release.

-SN/T 2213-2008.

National standards for food safety Determination of Urea Pesticide Residues in Plant - derived Foods by Liquid Chromatography - Mass Spectrometry

1 Scope

This standard specifies the method for the determination of 15 substituted urea pesticides (see Appendix A) residues in plant-derived foods by liquid chromatography-mass spectrometry.

2 Normative reference documents

The following documents are indispensable for the application of this document. For dated references, only the dated edition applies to this article Pieces. For undated references, the latest edition (including all modifications) applies to this document.

GB 2763 National Standard for Food Safety - Maximum Residue Limit of Pesticides in Foodstuffs GB/T 6682 Analytical laboratory water specifications and test methods

3 Principle

The samples were extracted with acetonitrile, cleaned up by HLB solid phase extraction column, and determined by liquid chromatography-mass spectrometry and quantified by external standard method.

4 Reagents and materials

Unless otherwise specified, all reagents are of analytical grade and water is in accordance with the primary water specified in GB/T 6682.

4.1 Reagents

4.1.1 Methanol (CH3OH, 67-56-1). Chromatographic Purification.

4.1.2 acetonitrile (CH3CN, 75-05-8). chromatographic purity.

4.1.3 Sodium chloride (NaCl, 7647-14-5).

4.1.4 acetic acid (CH3COOH, 64-19-7). chromatographic purity.

4.2 Solution preparation

4.2.1 Acetic acid - Aqueous solution (1 -> 1000). Accurately absorb 1 mL of acetic acid in a 1 000 mL volumetric flask, add water to the scale line, shake Evenly used.

4.2.2 acetic acid - methanol solution (7 3). accurately measure 70 mL of acetic acid - water solution (1 -> 1000) and 30 mL of methanol, shake back.

4.3 Standards

4.3.1 Substituted Urea Pesticide Reference Material. See Appendix A, purity greater than 99%.

4.4 Standard solution preparation

4.4.1 substituted urea pesticide standard stock solution (100 mg/L). were accurately weighed 10.0mg substituted urea pesticide reference substance, with B Nitrile dissolved, transferred to 100 mL volumetric flask, with acetonitrile volume capacity. The standard solution is stored at -18 ° C for a period of 6 months.

4.4.2 Substituted Urea Pesticide Standard Intermediate (1.0 mg/L). Accurate extraction of 1.00 mL of each substituted urea standard stock solution (100 Mg/L) to 100 mL volumetric flask, with acetonitrile volume. 4 °C dark preservation, the shelf life of 1 month.

4.5 Materials

4.5.1 HLB solid phase extraction column. 6 mL 500 mg, or equivalent.

4.5.2 Microporous membrane. 0.22 µm, organic phase type.

5 Instruments and equipment

5.1 Liquid Chromatography-Mass Spectrometer, Distribution Spray Ion Source (ESI).

5.2 Analysis of balance. 0.01 g and 0.0001 g.

5.3 Crusher.

5.4 Tissue crusher.

5.5 Centrifuge. 5 000 r/min.

5.6 Homogenizer.

5.7 blowing nitrogen enrichment instrument.

5.8 Scroll Mixer.

5.9 Solid phase extraction unit with vacuum pump.

5.10 pipette. 10-100 L, 100-1000 L.

5.11 Polypropylene centrifuge tube. 15mL, 50 mL, with plug.

5.12 volumetric flask. 25 mL, 100 mL.

6 Preparation and storage of samples

6.1 Preparation of the sample

6.1.1 Corn, soybeans, rice

Take a representative sample 500 g, fully pulverized with a pulverizer, all of which were passed through a standard screen of 425 µm. Mix well and prepare good samples are divided into two, into a clean sample container, sealed and marked.

6.1.2 Oranges, Chinese cabbage

Take a representative sample of 100 g, cut it (not with water), and use a mashed machine to process the sample into homogenate. Prepared samples are divided into two, into a clean sample container, sealed and marked.

Note. The above sample sampling site according to GB 2763 Appendix A implementation.

6.2 Sample storage

Corn, soybeans and rice samples stored at room temperature; orange, cabbage and other samples in -18 °C below frozen storage.

During the operation of the sample preparation, the sample should be protected from contamination or changes in the content of the residue.

7 Analysis steps

7.1 Extraction

For corn, soybeans, rice samples, weigh 5 g sample (accurate to 0.01 g) in 50 mL stoppered centrifuge tube, add 10 mL of water, After mixing for 1 h; for orange and Chinese cabbage samples, weigh 5 g of the sample (accurate to 0.01 g) in a 50 mL stoppered centrifuge tube. Joined the amount of sodium chloride, so that the aqueous solution to saturation, then add 15 mL of acetonitrile high-speed homogeneous extraction 3 min, 5 000 r/min centrifugation 5 min, acetonitrile Layer transferred to a 25 mL volumetric flask. The residue was extracted again with 10 mL of acetonitrile and the extracts were combined and bound to 25 mL with acetonitrile. Take 5 ML of the extract was centrifuged in a 15 mL centrifuge tube and purged with nitrogen at 45 ° C.

7.2 Purification

The HLB solid-phase extraction column was installed on a solid-phase extraction vacuum filtration device, and the extraction column was pre-eluted with 5 mL of acetonitrile.

Lotion. The extract was transferred to an HLB solid phase extraction column and the sample solution was passed through a solid phase extraction column at a flow rate of about 1 drop/s and then 2 mL of acetonitrile Rinse and dry the solid phase extraction column, collect all the effluent in 15 mL centrifuge tube, below 45 °C with nitrogen blowing to near dry, the residue with acetic acid -the methanol solution was set to 1.0 mL. After vortex mixing, the microporous membrane was determined by liquid chromatography-mass spectrometry.

7.3 Instrument reference conditions

7.3.1 Liquid Chromatographic Reference Conditions

A) Column. Acquity BEH C18 column, 50 mm × 2.1 mm (id), 1.7 µm, or equivalent;

B) Column temperature. 40 ° C;

C) Injection volume. 10 µL;

D) The mobile phase, flow rate and gradient elution conditions are shown in Table 1.

Table 1 Mobile phase, flow rate and gradient elution conditions

time

Min

Flow rate

ML/min

Acetic acid-water solution (1 -> 1000) Methanol 0 0.3 70 30 6 0.3 0 100 7.5 0.3 70 30

7.3.2 Mass spectrometry conditions

A) ionization mode. electrospray ion source;

B) Scanning mode. positive ion scanning;

C) Detection method. Multiple reaction monitoring (MRM);

D) Resolution. Unit resolution;

See Appendix B for other reference mass spectrometry conditions.

7.4 Standard working curve

Accurately absorb the appropriate amount of substituted urea pesticide standard intermediate (1.0 mg/L), with blank sample extraction solution concentration of 0,5.0,10.0, 20.0, 50.0, 100 µg/L of the matrix mixed standard working solution. Pro preparation. Determination of the peak area by liquid chromatography-mass spectrometry as the ordinate, the matrix mixed standard working solution concentration for the abscissa to draw the standard working curve.

7.5 Determination

7.5.1 Qualitative determination

Each selected component selected one parent ion, two or more child ions, in the same experimental conditions, the sample retention time of the material to be tested, and the substrate standard solution retention time deviation within ± 2.5%; and the sample of each component of the relative abundance of ions and concentrations close to the matrix Comparing the relative abundance of the corresponding qualitative ions in the standard working solution, the deviation does not exceed the range specified in Table 2, There is a corresponding test substance in the product.

Table 2 The maximum allowable deviation of relative ion abundance when qualitative confirmation

Relative ion abundance > 50% > 20% to 50% > 10% to 20% <=10% Maximum permissible deviation ± 20% ± 25% ± 30% ± 50%

7.5.2 Quantitative determination

In the best working conditions of the instrument, the standard solution of the mixed working solution of the matrix, with the peak area as the ordinate, the matrix mixed standard working solution Liquid concentration for the abscissa to draw the standard working curve, with the standard working curve of the sample quantitative, the sample solution to be measured the response value should be in the linear range of the instrument determination. A multi-reaction monitoring (MRM) chromatogram of 15 substituted urea pesticide reference materials is given in Figure C.1 in Appendix C.

7.6 Blank experiment

In addition to the sample, according to the above determination steps.

8 Results are calculated and expressed

The content of each substituted urea pesticide in the sample was calculated according to the following formula (1) Vc X ii .. (1) where.

Xi - Residual content of each substituted urea pesticide in the sample, in micrograms per kilogram (g/kg);

Ci - the concentration of the solution to be measured from the standard working curve, in micrograms per liter (g/L);

V - the final volume of the sample solution in milliliters (mL);

M - the amount of sample represented by the final sample solution in grams (g).

Note. The result of the calculation shall be deducted from the blank value. The result of the measurement shall be expressed as the arithmetic mean of the parallel measurement, and two valid digits shall be retained.

9 Precision

9.1 The ratio of the absolute difference between the two independent determinations obtained under reproducibility and its arithmetic mean (percentage) shall be in accordance with Appendix E requirements.

9.2 The ratio of the absolute difference between the two independent determinations obtained under reproducibility and its arithmetic mean (percentage) shall be in accordance with Appendix F requirements.

10% limit and recovery rate

10.1 Quantitation limits

The limit of quantification for 15 substituted urea pesticides was 10.0 µg/kg.

10.2 Recovery rate

When the added levels were 10.0, 20.0, 50.0 µg/kg, the recoveries of 15 substituted urea pesticides in different matrices were given in Appendix D.

Appendix A

(Informative)

15 Basic information on substituted urea pesticides

Table A.1 Basic information on 15 substituted ureasic pesticides

Pesticide name English name CAS number Molecular formula Molecular weight Non-grassland fenuron 101-42-8 C9H12N2O 164.20 Methoxy Long metoxuron.19937-59-8 C10H13ClN2O2 228.68 Mycelia monomon 150-68-5 C9H11ClN2O 198.68 Chlorotoluron 15545-48-9 C10H13ClN2O 212.70 Methylbenzene thiazone methabenzthiazuron 18691-97-9 C10H11N3OS 221.28 Fluoxetil fluometuron 2164-17-2 C10H11F3N2O 232.20 Diuron 330-54-1 C9H10Cl2N2O 233.09 Cyclomethasone cycluron 2163-69-1 C11H22N2O 198.31 Isoproton isoproturon 34123-59-6 C12H18N2O 206.28 Isosaurus 28805-78-9 C13H22N2O 222.33 Cyclobalanopsis siduron 1982-49-6 C14H20N2O 232.32 Acetylate buturon 3766-60-7 C12H13ClN2O 236.70 Li Gu Long linuron 330-55-2 C9H10Cl2N2O2 249.09 Mango ramen difenoxuron 14214-32-5 C16H18N2O3 286.33 Bacillus sp. Kelp Appendix B (Informative) Reference mass spectrometry conditions 1 B.1 electrospray voltage. 3000 V;

B.2 Auxiliary gas flow rate. 700 L/h;

B.3 Collision gas. argon;

B.4 Curtain air flow rate. 50 L/h;

B.5 Ion source temperature. 105 ° C;

B.6 Auxiliary gas temperature. 350 °C;

B.7 Qualitative ion pair, quantitative ion pair, acquisition time, cone hole voltage and collision energy are shown in Table B.1.

Table B.1 Mass Spectrometric Parameters of Substituted Urea Pesticides

When mass spectrometry is segmented Set between Analyte Reference retention time / Min Parent ion Acquisition time / S Cone hole voltage / V Collision energy / EV 0 ~ 2 min Non-grassland 1.22 165 72 * 0.05 34 Methoxy Long 1.81 229 72 * 0.05 50 2 ~ 3.5 min Herbicide 2.17.199 72 * 0.05 44 Green Meilong 2.81 213 72 * 0.05 42 Methylphenothiazone 2.89 222 0.05 34 165 * 17 Fluorothilone 2.77 233 72 * 0.05 24 the enemy of the sword 3.09 233 72 * 0.05 24 2.8 ~ 6min Cycloxacron 3.14.199 69 * 0.05 40 Isoproterenol 3.05 207 72 * 0.05 44 the grass is well 3.50 223 72 * 0.05 52 Cycloft oxalate 3.53 233 0.05 40 137 * 17 Acetylate 3.05 237 84 * 0.05 48 Lee Valley Long 3.51 249 160 * 0.05 30

1 Non-commercial declaration. The reference mass spectrometry conditions listed in Appendix A are performed on a Waters Quattro Premier LC/MS List the test instrument model only for reference, does not involve commercial purposes, to encourage standard users to try different manufacturers or models of equipment.

Vanilla 3.08 287

0.05 58

Bacillus sp. 3.97 291 72 * 0.05 22 * For the quantitative ions, for different mass spectrometry equipment, instrument parameters may be different, should be measured before the mass spectrometry parameters to optimize the best.

Appendix C

(Informative)

Standard multi-reaction monitoring (MRM) chromatograms

Figure C.1 10.0 µg/L Substituted Urea Pesticide Standard Solution Multiple Reaction Monitoring (MRM) Chromatogram

Fluorouracil Long Fluoride Long Cyclic atracurium Appendix D (Informative) Addition Recovery of 15 Substituted Urea Pesticides in Different Substrates

Table D.1 Recovery rates of 15 substituted urea pesticides in different matrices

The name of the compound Add level Mg/kg corn Recovery rate range Soybeans Recovery rate range orange Recovery rate Rice Recovery rate range Cabbage Recovery rate range Non-grassy 10.0 73.2 ~ 78.9 85.1 ~ 91.4 87.6 ~ 104 69.3 ~ 77.4 68.2 ~ 78.4 20.0 73.5 ~ 84.5 80.5 ~ 94.0 99.5 ~ 110 70.2 ~ 76.1 68.7 ~ 74.9 50.0 83.0 to 89.4 85.2 to 95.6 94.2 to 101 76.6 to 87.0 62.7 to 67.5 Methoxy Long 10.0 79.3 ~ 91.7 81.2 ~ 86.8 90.5 ~ 102 69.3 ~ 76.5 76.1 ~ 80.4 20.0 90.5 to 104 79.0 to 83.5 94.5 to 108 68.7 to 74.2 73.1 to 80.6 50.0 87.0 ~ 102 77.4 ~ 83.2 86.0 ~ 92.6 74.2 ~ 93.1 66.4 ~ 69.7 Herbicide 10.0 76.7 to 88.9 78.0 to 86.9 85.1 to 106 72.2 to 77.8 69.5 to 75.8 20.0 80.5 ~ 87.0 72.5 ~ 81.0 94.0 ~ 109 65.3 ~ 74.6 74.2 ~ 80.8 50.0 84.2 ~ 94.4 71.4 ~ 78.6 85.4 ~ 103 73.3 ~ 88.4 74.9 ~ 78.0 Green Macaroni 10.0 77.0 ~ 88.0 78.3 ~ 86.9 90.4 ~ 97.6 75.2 ~ 80.1 69.6 ~ 75.8 20.0 80.0 to 87.0 75.5 to 82.0 91.0 to 103 72.2 to 84.3 73.9 to 82.1 50.0 81.0 ~ 96.6 74.0 ~ 84.4 77.6 ~ 90.2 77.3 ~ 86.6 63.9 ~ 69.4 Methyl benzene thiophene 10.0 73.3 ~ 82.9 71.0 ~ 77.5 80.1 ~ 95.6 64.8 ~ 76.4 70.1 ~ 74.4 20.0 77.5 to 88.5 77.0 to 85.0 82.5 to 100 67.9 to 73.2 71.3 to 83.7 50.0 80.4 ~ 86.6 71.4 ~ 78.6 81.0 ~ 85.4 72.0 ~ 80.9 74.7 ~ 82.7 Fluroxides 10.0 76 ~ 87.8 77.1 ~ 84.7 86.7 ~ 96.3 84.2 ~ 96.8 82.8 ~ 86.8 20.0 79.5 to 92.0 74.0 to 88.5 92.0 to 102 83.2 to 98.5 82.6 to 87.0 50.0 83.4 ~ 92.0 76.6 ~ 81.8 83.6 ~ 86.8 75.2 ~ 85.7 77.3 ~ 81.7 Rival 10.0 66.7 to 81.4 70.7 to 84.2 81.0 to 94.4 82.6 to 92.2 71.9 to 82.6 20.0 84.5 ~ 95.0 75.0 ~ 84.0 86.0 ~ 102 77.8 ~ 96.7 75.5 ~ 85.6 50.0 81.6 ~ 91.6 76.2 ~ 82.2 84.0 ~ 91.8 76.2 ~ 87.7 62.1 ~ 75.0 Cyclomide 10.0 79.8 ~ 89.1 77.6 ~ 89.0 86.3 ~ 104 73.2 ~ 76.6 71.2 ~ 77.3 20.0 83.0 to 94.5 77.0 to 88.0 92.0 to 102 70.9 to 78.0 78.7 to 84.8 50.0 83.6 ~ 93.6 80.6 ~ 88.2 88.0 ~ 93.4 76.9 ~ 87.6 68.6 ~ 73.8 Isoproturon 10.0 70.8 ~ 82.4 72.6 ~ 80.1 84.1 ~ 96.9 78.1 ~ 83.3 68.1 ~ 71.6 20.0 90.5 to 98.5 81.0 to 85.0 86.0 to 94.5 72.1 to 81.1 71.0 to 78.6 50.0 87.4 ~ 94.0 78.0 ~ 82.4 82.2 ~ 89.6 75.7 ~ 87.6 68.9 ~ 75.8 the grass is too long 10.0 70 ~ 80.3 79.2 ~ 87.2 81.3 ~ 93.2 70.4 ~ 75.8 71.7 ~ 80.0 20.0 90.5 ~ 98.0 83.0 ~ 86.5 85.5 ~ 95.0 69.8 ~ 76.4 74.2 ~ 82.0 50.0 87.8 ~ 99.2 79.8 ~ 85.6 79.2 ~ 84.4 80.6 `90.8 75.9 ~ 81.8 Huan grass Long 10.0 69.7 ~ 75.7 84.9 ~ 95.5 89.5 ~ 104 67.5 ~ 81.7 70.7 ~ 81.6 20.0 83.5 to 92.5 82.5 to 92.0 93.5 to 98.0 71.8 to 84.6 77.7 to 80.9 50.0 86.0 ~ 92.0 88.0 ~ 95.4 86.6 ~ 93.6 76.4 ~ 85.6 67.6 ~ 79.5 Clenbuterol 10.0 74.7 ~ 86.8 72.0 ~ 84.5 75.9 ~ 99.8 70.7 ~ 82.7 60.8 ~ 77.2 20.0 84.0 ~ 95.0 75.5 ~ 85.5 89.0 ~ 97.0 74.5 ~ 89.1 72.3 ~ 80.5 50.0 84.6 ~ 95.2 75.6 ~ 84.2 83.0 ~ 88.0 75.7 ~ 87.6 68.0 ~ 77.5 Lee Valley Long 10.0 68.8 to 86.5 65.7 to 82.0 78.2 to 88.9 68.3 to 77.6 72.2 to 77.6 20.0 76.0 ~ 86.0 70.5 ~ 77.0 84.5 ~ 99.0 70.3 ~ 84.7 64.3 ~ 71.5 50.0 76.2 ~ 83.6 70.6 ~ 79.2 81.4 ~ 86.8 71.2 ~ 75.8 60.1 ~ 69.0 Soot 10.0 69.6 to 83.0 70.7 to 77.3 92.2 to 112 68.1 to 74.8 64.4 to 73.9 20.0 82.0 to 91.0 75.0 to 83.0 91.5 to 107 69.3 to 76.2 60.9 to 70.5 50.0 80.2 ~ 90.8 72.2 ~ 79.6 89.0 ~ 103 70.3 ~ 87.6 61.4 ~ 76.9 Bacon Long 10.0 68.7 ~ 75.5 71.5 ~ 79.2 70.6 ~ 82.7 60.9 ~ 73.6 67.6 ~ 74.2 20.0 73.0 ~ 79.5 69.5 ~ 82.0 74.0 ~ 82.0 70.1 ~ 84.9 64.1 ~ 75.7 50.0 70.4 ~ 75.6 71.4 ~ 77.8 68.8 ~ 73.8 70.1 ~ 75.1 62.3 ~ 78.5 Appendix E (Normative appendix) Laboratory repeatability requirements

Table E.1 Laboratory repeatability requirements

Measured component content Mg/kg Precision <=0.001 36 > 0.01 > 1 14 Appendix F (Normative appendix) Inter-laboratory reproducibility requirements

Table F.1 Inter-laboratory reproducibility requirements

Measured component content Mg/kg Precision <=0.001 54 > 0.01 > 1 19

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