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Food safety national standard -- Determination of difluomide residues in food by liquid chromatography-mass spectrometry
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GB 23200.45-2016
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Basic data | Standard ID | GB 23200.45-2016 (GB23200.45-2016) | | Description (Translated English) | Food safety national standard -- Determination of difluomide residues in food by liquid chromatography-mass spectrometry | | Sector / Industry | National Standard | | Classification of Chinese Standard | G25 | | Word Count Estimation | 13,126 | | Date of Issue | 2016-12-18 | | Date of Implementation | 2017-06-18 | | Older Standard (superseded by this standard) | SN/T 0528-2012 | | Regulation (derived from) | State Health Commission, Ministry of Agriculture, Food and Drug Administration Notice No. 16 of 2016 | | Issuing agency(ies) | National Health and Family Planning Commission of the People's Republic of China, State Food and Drug Administration |
GB 23200.45-2016: Food safety national standard -- Determination of difluomide residues in food by liquid chromatography-mass spectrometry ---This is a DRAFT version for illustration, not a final translation. Full copy of true-PDF in English version (including equations, symbols, images, flow-chart, tables, and figures etc.) will be manually/carefully translated upon your order.
Food safety national standard - Determination of difluomide residues in food by liquid chromatography - mass spectrometry
National Standards of People's Republic of China
GB
Replace SN 0528-2012
National standards for food safety
Determination of diflubenzuron Residue in Food
Liquid chromatography - mass spectrometry
National food safety standards-
Determination of diflubenzuron residue in foods
Liquid chromatography mass spectrometry
2016-12-18 Release.2017-06-18 Implementation
National Health and Family Planning Commission of the People 's Republic of China
Issued by the Ministry of Agriculture of the People 's Republic of China
State Administration of Food and Drug Administration
Foreword
This standard replaces SN/T 0528-2012 "High performance liquid chromatography - mass spectrometry/mass spectrometry" for the detection of diflubes in export food.
Compared with SN/T 0528-2012, the main changes are as follows.
- Standard text format is modified to national standard text format for food safety;
- the name of the "export food" to "food";
- increase the "other food reference implementation" in the standard range.
This standard replaced the previous version of the standard release.
-SN 0528-1996;
-SN/T 0528-2012.
National standards for food safety
Determination of difluomide residues in food by liquid chromatography - mass spectrometry
1 Scope
This standard specifies the method of liquid chromatography-mass spectrometry for the removal of diflubenzuron in food.
This standard applies to rice, corn, soybeans, wheat, peanuts (peanuts), oranges, apples, celery, onions, mushrooms (fresh), honey,
Mushrooms (dry), tea, chicken, beef, pork, pig liver in the determination and removal of insecticides, other food can refer to the implementation.
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
file. 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 pyrethroids in the samples were extracted with acetonitrile and dispersed by solid phase extraction and purified by liquid chromatography-tandem mass spectrometry.
Quantitative.
4 reagents and materials
Unless otherwise stated, the reagents used were of analytical grade and water was a primary water specified in GB/T 6682.
4.1 Reagents
4.1.1 Acetonitrile (CH3CN). Chromatographically pure.
4.1.2 n-hexane (C6H14).
4.1.3 glacial acetic acid (CH3COOH).
4.1.4 anhydrous sodium acetate (CH3COONa).
4.1.5 sodium chloride (NaCl). 450 ℃ burning 4 h, sealed standby.
4.1.6 anhydrous sodium sulfate (Na2SO4). 650 ℃ burning 4 h, storage dryer in reserve.
4.1.7 anhydrous magnesium sulfate (MgSO4. 650 ℃ burning 4 h, storage dryer in the spare.
4.1.8 Primary secondary amine (PSA). PSA filler or equivalent, particle size 40 μm.
4.1.9 Octadecyl silane bonded phase (C18). C18 filler or equivalent, particle size 50 μm.
4.2 solution preparation
4.2.1 glacial acetic acid - acetonitrile solution (0.1 99.9, V/V). take 0.1 mL of glacial acetic acid by adding 99.9 mL of acetonitrile, mix and spare.
4.3 standards
4.3.1 Pesticide standard. CAS No.. 35367-38-5, purity greater than or equal to 96%.
4.4 standard solution preparation
4.4.1 Pesticide standard stock solution. accurately weighed appropriate amount of insecticides (accurate to 0.1 mg), with acetonitrile prepared into a concentration of 1.0
Mg/mL standard stock solution, set -18 ℃ refrigerator to save, the shelf life of 6 months.
4.4.2 Deicerurea standard working solution. according to the need to use acetonitrile standard stock solution diluted to the appropriate concentration of standard working fluid, temporary use
With
4.4.3 0.005 mol/L ammonium acetate aqueous solution. Weigh 0.3850 g ammonium acetate, dissolved in water to 1 L, over 0.45 μm filter preparation
use.
4.5 Materials
4.5.1 Microporous membrane. 0.22 μm, organic.
5 instruments and equipment
5.1 High Performance Liquid Chromatography-Tandem Mass Spectrometer. Triple quadrupole tandem mass spectrometry with electrospray ionization source (ESI).
5.2 Analysis of balance. 0.01 g and 0.0001 g.
5.3 with a plug centrifuge tube. 50 mL, polypropylene capped plastic centrifuge tube or equivalent; 10 mL, glass with a plug tube or equivalent.
5.4 Scroll Mixer.
5.5 Ultrasonic cleaner.
5.6 Centrifuge.
5.7 sample grinder.
5.8 Tissue crusher.
5.9 Sample Sieve. A pore size of 2 mm.
5.10 high-speed organization homogenizer.
6 Preparation and storage of samples
6.1 Preparation of the sample
6.1.1 rice, corn, soybeans, wheat, mushrooms (dry), tea
500 g of the sample was taken and crushed to make it all through the sample sieve, mixed into a clean container, sealed and identified.
6.1.2 peanuts (peanuts), oranges, apples, celery, onions, mushrooms (fresh)
Take a representative sample 500 g, crushed with a pulverizer. Mix, fit into a clean container, sealed and marked.
6.1.3 Chicken, beef, pork, liver
The samples were mashed with tissue mills and mixed thoroughly. Take 250 g mashed samples with high-speed tissue homogenizer to paste, if not immediately measured
You need to cryopreservation.
6.1.4 beef, beef liver, fish, chicken
Take a representative sample of 500 g, take the edible part of the crusher fully mashed evenly, into the clean sample container, sealed and marked
mark.
6.1.5 honey
To replace the sample 500 g, for non-crystalline honey samples, stir evenly. For a crystalline sample, in a closed case
, Below 60 ℃ in the water bath in the warm, shaking, until the sample all melt and stir well, quickly cooled to room temperature, stored at room temperature.
Note. The above sample sampling site according to GB 2763 Appendix A implementation.
6.2 Sample storage
Cereals, nuts, tea and other dehydration samples can be sealed at room temperature; fruit, vegetable samples should be sealed cold storage, such as
If you do not carry out immediate testing, you need to cryopreservation; livestock and poultry meat and their products need to be frozen.
During sample preparation and sample preservation, the contamination of the sample or the change in the content of the analyte should be prevented. All prepared samples should be placed in a clean, sealed
Container and make a mark. Water samples should be thoroughly mixed after thawing.
7 measurement steps
7.1 Extraction
7.1.1 rice, corn, soybeans, wheat, peanuts (kernel)
Weigh 5g sample (accurate to 0.01 g) in 50 mL stoppered centrifuge tube, add 5 mL of water to mix for 30 min. Add 10 mL
Glacial acetic acid - acetonitrile solution, add 1 g of anhydrous sodium acetate and 2 g sodium chloride, vortex oscillation 2 min, 30 ℃ constant temperature water bath ultrasonic extraction 30
Min after 5000 r/min centrifugation 10 min, the supernatant was filled with an appropriate amount of anhydrous sodium sulfate funnel collected in 50 mL with a plug centrifuge tube, adding
10 mL n-hexane saturated with acetonitrile, shaking 5 min, standing stratification, discarded n-hexane layer, to be purified.
7.1.2 Oranges, apples, celery, onions, mushrooms (fresh), honey
Weigh 5 g of sample (accurate to 0.01 g) in a 50 mL stoppered centrifuge tube. Add 5 mL of water to mix and place for 30 min. Add 10 mL of ice
Acetic acid-acetonitrile solution, add 1 g of anhydrous sodium acetate and 2 g sodium chloride, vortex oscillation 2 min, 30 ℃ constant temperature water bath ultrasonic extraction 30 min
5000 r/min centrifugal 10 min, the supernatant was filled with an appropriate amount of anhydrous sodium sulfate funnel collected in 50 mL with a plug centrifuge tube, to be purified.
7.1.3 Mushrooms (dry), tea
Weigh 2.5 g of sample (accurate to 0.01 g) in 50 mL stoppered centrifuge tube, add 10 mL of water to mix for 60 min. Add 10 mL
Glacial acetic acid - acetonitrile solution, add 1 g of anhydrous sodium acetate and 2 g sodium chloride, vortex oscillation 2 min, 30 ℃ constant temperature water bath ultrasonic extraction 30
Min after 5000 r/min centrifugal 10 min, the supernatant was filled with an appropriate amount of anhydrous sodium sulfate funnel collected in 50 mL with a plug centrifuge tube, to be net
The
7.1.4 Chicken, beef, pork, liver
Weigh 2.5 g of the sample (accurate to 0.01 g) in a 50 mL stoppered centrifuge tube. Add 10 mL of glacial acetic acid-acetonitrile solution and add 1 g
Anhydrous sodium acetate and 2 g sodium chloride, homogenized 2 min, 30 ℃ constant temperature water bath ultrasonic extraction 30 min after 5000 r/min centrifugal 10 min, the upper
The supernatant was filled with an appropriate amount of anhydrous sodium sulfate funnel collected in a 50 mL stoppered centrifuge tube, 10 mL of n-hexane saturated with acetonitrile,
Min, standing stratified, discarded n-hexane layer, to be purified.
7.2 Purification
Weigh 0.05 g PSA, 0.1 g C18, 0.15 g anhydrous magnesium sulfate in a 10 mL glass stopper centrifuge tube, accurately absorb 7.1
Extract 2.0 mL to the centrifuge tube, the exact vortex oscillation 1min, to 5000 r/min speed centrifugation 2 min. Take 1 mL supernatant
0.22 μm organic microporous membrane, for liquid chromatography - tandem mass spectrometry.
7.3 Determination
7.3.1 Liquid Chromatographic Reference Conditions
A) Column. C18 column, 150 mm × 2.1 mm (inner diameter), particle size 5 μm, or equivalent;
B) mobile phase. A (acetonitrile), B (0.005 mol/L ammonium acetate aqueous solution). The gradient elution conditions are given in Table A.1 in Appendix A;
C) Injection volume. 10 μL;
D) Column temperature. 30 ° C;
E) Flow rate. 0.2 mL/min.
7.3.2 Mass spectrometry reference conditions
A) ion source. electrospray ion source (ESI);
B) scanning mode. negative ion scanning;
C) Detection method. Multiple reaction monitoring (MRM);
D) monitoring of ion pair. parent ion 308.9 (m/z), quantitative ion pair 308.9/288.9 (m/z); qualitative ion pair of 308.9/288.9
(M/z), 308.9/92.9 (m/z);
E) Other mass spectrometry reference conditions are given in Tables A.2 and A.3 of Appendix A.
7.3.3 Quantitative determination
According to the sample in the sample content of the selected concentration of similar standard working solution together for chromatographic analysis. Diazepam in the sample solution to be tested
The response value should be within the linear range of the instrument detection. The standard working solution and the sample solution were measured by volume injection. In the above instrument strips
, The retention time of the insecticide was about 7.51 min. Liquid Chromatography - Tandem Mass Spectrometry Total Ion Flow and Mass Chromatogram See Appendix B Figure B.1.
7.3.4 Qualitative determination
According to the above conditions to determine the sample and the standard sample, the sample to be measured in the chromatographic peak retention time and the standard corresponding to the retention time deviation should be
The allowable deviation is less than ± 2.5%; and in the sample spectrum after subtracting the background, the relative abundance of each qualitative ion is close to the concentration
Under the same conditions obtained under the standard solution spectrum, the maximum allowable relative deviation does not exceed the range specified in Table 1, you can determine the sample
There is a corresponding measured object.
Table 1 Maximum allowable deviation of relative ion abundance when qualitative confirmation
Relative abundance (base) 50% 20% to 50% 10% to 20% ≤10%
Allowable relative deviation ± 20% ± 25% ± 30% ± 50%
7.4 blank experiment
In addition to the sample, according to the above determination steps.
8 results are calculated and expressed
Use the LC-MS/MS data processing software or calculate the content of diflubes in the sample by the following formula (1). The calculated result should be subtracted from the blank value.
MA
VcA
S
(1)
Where.
X - the content of the insecticides in the sample, in micrograms per kilogram (μg/kg);
A - the peak area of diflubenzuron in the sample solution;
C - the concentration of diflubenzuron in standard working solution in ng/ml (ng/mL);
V - the final volume of the sample solution in milliliters (mL);
As - the peak area of pyrethroid in standard working solution;
M - the mass of the final sample represented by the 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 reproducible conditions and their arithmetic mean (percentage) shall be in accordance with the
Record the requirements of D.
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 the
Record the requirements of E.
10% limit and recovery rate
10.1 Quantitation limits
The method of insecticides in rice, corn, soybeans, wheat, peanuts (peanuts), oranges, apples, celery, onions, mushrooms (fresh)
The quantitative limit of honey is 10.0 μg/kg, chicken, beef, pork, liver, mushroom (dry), tea limit of 20.0 μg/kg.
10.2 Recovery rate
The recovery of this method in the concentration of 10 ~ 500 μg/kg in different substrates is 65% ~ 115%. See Appendix C.
Appendix A
(Informative)
Reference Liquid Chromatography - Tandem Mass Spectrometry Conditions
Table A.1 Liquid Chromatography Elution Conditions
Time/min A /% B /%
0 ~ 1.0 40 60
3.0 to 8.0 70 30
8.1 to 10.0 95 5
10.1 to 15.0 40 60
Table A.2 Mass spectrometry conditions
Instrument parameter parameter value
Electromagnetic spray voltage (IS) -4500 V
Atomization gas pressure (GS1) 45 psi (nitrogen)
Air curtain gas pressure (CUR) 10 psi (nitrogen)
Auxiliary gas pressure (GS2) 50 psi (nitrogen)
Ion source temperature (TEM) 500 ° C
Table A.3 Multi-reaction monitoring conditions
Compounds
Mother ion
(M/z)
Ion
(M/z)
To cluster voltage
(V)
Collision voltage
(V)
Collision chamber
Port voltage /
(V)
Collision room out
Port voltage /
(V)
Dwell time /
(Msec)
Dexamethasone 308.9
288.9 *
-55
-15
-11
-6.200
92.9 -70 -8.200
* Ions are used for quantification.
1) Non-commercial statements. The parameters listed in Appendix A are done on the API4000 mass spectrometer, where the test instrument model is only listed
Is to provide a reference, does not involve commercial purposes, to encourage standard users to try to use different manufacturers or models of equipment.
Appendix B
(Informative)
Liquid Chromatography - Mass Spectrometry/Mass Spectrometry
Figure B.1 Multiple reactivity monitoring (MRM) chromatograms of deferir urea reference material (0.01 ng/mL)
Appendix C
(Informative)
The recovery of diflubenzuron in different substrates
Table C.1 Add level and recovery range
Sample Name Add Concentration/(μg/kg) Recovery Rate Range /%
Rice
10 73.3 ~ 82.6
20 70.5 to 101.5
50 77.2 ~ 107.1
corn
10 72.4 ~ 81.5
20 75.5 to 106.4
50 71.0 ~ 95.1
Soybeans
10 68.5 to 81.2
20 67.2 ~ 90.5
50 70.5 to 95.7
wheat
10 77.3 ~ 87.5
20 71.5 ~ 90.6
50 75.3 ~ 94.1
peanut kernel)
10 70.1 to 85.5
20 72.0 ~ 98.7
50 73.5 ~ 86.2
orange
50 85.6 ~ 107.6
100 87.2 ~ 115.4
500 79.5 ~ 109.5
apple
50 86.3 ~ 115.5
100 82.4 ~ 107.6
500 85.0 ~ 109.2
Celery
10 75.3 ~ 89.6
20 85.0 ~ 103.5
50 82.6 ~ 105.5
onion
10 81.2 ~ 94.8
20 75.0 ~ 112.8
50 72.4 ~ 102.5
Mushrooms (fresh)
10 72.1 to 101.5
20 76.0 ~ 87.6
50 71.2 ~ 94.6
honey
10 75.0 to 109.2
20 81.0 to 106.8
50 80.5 to 105.5
chicken
20 90.0 to 108.2
40 85.2 ~ 96.0
80 82.0 to 105.7
beef
20 87.5 ~ 102
40 89.0 ~ 98.5
80 80.0 to 103.7
pork
20 92.0 to 100.0
40 93.8 ~ 107.5
80 82.5 to 102.7
Liver
20 85.0 ~ 114.2
40 87.5 ~ 105.3
80 78.6 ~ 108.5
Mushrooms (dry)
20 65.4 to 92.1
50 77.2 ~ 87.6
100 70.3 ~ 81.6
20 70.0 to 85.2
50 68.8 ~ 87.4
100 72.3 ~ 85.0
Appendix D
(Normative appendix)
Laboratory repeatability requirements
Table D.1 Laboratory repeatability requirements
Measured component content
Mg/kg
Precision
0.001 36
> 0.01
> 1 14
Appendix E
(Normative appendix)
Inter-laboratory reproducibility requirements
Table E.1 Inter-laboratory reproducibility requirements
Measured component content
Mg/kg
Precision
0.001 54
> 0.01
> 1 19
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