GB 23200.3-2016Food safety national standard -- Methods for the determination of herbicide residues -- Part 3: Determination of cyclohexanone herbicides in food by liquid chromatography-mass spectrometry / mass spectrometry (English PDF)

4.1 Reagents

4.1.1 Acetonitrile (CH3CN). Chromatographically pure.

4.1.2 Acetic acid (CH3COOH) (99.5%).

4.1.3 Formic acid (HCOOH) (88.0%).

4.1.4 Sodium acetate (CH3COONa).

4.1.5 Sodium chloride (NaCl).

4.1.6 anhydrous magnesium sulfate (MgSO4). 650 °C burning 4 h, placed in the dryer to spare.

4.2 Solution preparation

4.2.1 1% acetic acid acetonitrile solution. take 10 mL of acetic acid, add 990 mL of acetonitrile, mix.

4.2.2 60% acetonitrile aqueous solution. take 60 mL of acetonitrile, add 40 mL of water, mix.

4.2.3 Formic acid - Aqueous solution (0.2 999.8, V/V). Take 0.2 mL of formic acid, dissolve with water and dilute to 1000 mL.

4.3 Standards

4.3.1 Cyclohexenone standards. Clethodim, CAS. 99129-21-2, purity >=99%; pyranone

(Tepraloxydim) CAS. 149979-41-9, purity >=99%; thiadenone (Cycloxydim), CAS. 101205-02-1, purity >=93.5%; Tralkoxydim, CAS. 87820-88-0, purity >=93.5%; Alloxydim, CAS.

55634-91-8, purity >=98%; Profoxydim, CAS. 139001-49-3, purity >=98.5%; butanone (Butroxydim), CAS. 138164-12-2; Purity >=99%; Sethoxydim CAS. 74051-80-2; Purity >=99%.

4.4 Standard solution preparation

4.4.1 Cyclohexenone Standard Reserve Solution. Accurately weigh the standard amount of cyclohexenone, dissolve with acetonitrile and set to 100 mL of brown Color container, the concentration of 100 µg/mL standard stock solution, the solution stored in dark.

4.4.2 mixed standard intermediate solution. accurate extraction of cyclohexene ketone standard stock solution of 2.5mL in 50mL brown volumetric flask, with acetonitrile Diluted to a concentration of 5.0 µg/mL mixed standard intermediate solution, the solution stored in dark.

4.4.3 Mixing standard working solution. Prepare the appropriate standard working solution with a blank sample matrix prior to use.

4.5 Materials

4.5.1 Graphitized Carbon Black Adsorbent. 120 µm to 400 µm.

4.5.2 N-propyl ethylenediamine (PSA) adsorbent. 40 µm to 100 µm.

4.5.3 Octadecylsilane (ODS) Bonded phase. 40 µm to 100 µm.

4.5.4 Water phase filter. 0.22 µm.

6.1 Preparation of the sample

6.1.1 Oranges, blueberries, spinach, onions

Take a representative sample of about 500 g (can not be washed with water), cut it, and then use the tissue crusher to process the sample into a slurry, the net container is sealed as a sample, marked and marked.

6.1.2 Soybean, rice, tea, walnut

Approximately 500 g of representative sample, crushed and mixed with a pulverizer, packed in a clean container as a sample, sealed and marked.

6.1.3 Pork, bovine liver, chicken liver

Take a representative sample of about 500 g, chopped, with the tissue crusher will be fully mashed evenly, into the clean container as a sample, sealed and mark the mark.

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

6.2 Sample storage

Soybeans, rice, tea, walnut and milk and other samples at 0 °C ~ 4 °C preservation; oranges, blueberries, spinach, onions, pork, Chicken liver and other samples stored at -18 °C below.

During the operation of the sample preparation, the contamination of the sample or the change in the content of the residue should be prevented.

7.1 Extraction

7.1.1 Soybean, rice, tea and walnut

Weigh the sample 5 g (tea sample 2 g, accurate to 0.01 g) in 50 mL screw cap polypropylene centrifuge tube, add 10 mL of water, Vortex mixer for 30 min, placed 15 min. Add 3 g of anhydrous magnesium sulfate, 1 g of sodium chloride, 1 g of sodium acetate and 15 mL of 1% acetonitrile solution, the homogenizer was centrifuged at 10 000 r/min for 2 min and 4 000 r/min for 5 min. The supernatant was transferred to a 25 mL volumetric flask. Reuse 10 mL 1% acetic acid acetonitrile solution to extract once again, the combined extract in the same 25 mL volumetric flask, and acetonitrile volume to the scale, to be purified.

7.1.2 Pork, Bovine Liver, Chicken Liver, Milk, Oranges, Spinach and Onion

Weigh the sample about 5 g (accurate to 0.01 g) in a 50 mL screw cap polypropylene centrifuge tube, add 5 mL of water, 3 g of anhydrous magnesium sulfate, 1 g Sodium chloride, 1 g of sodium acetate and 15 mL of 1% acetic acid in acetonitrile, homogenized at 10 000 r/min homogenized for 2 min, 4 000 r/min centrifuged 5 Min. The supernatant was transferred to a 25 mL volumetric flask. And then 10 mL 1% acetic acid acetonitrile solution repeated extraction time, combined extract in the same 25 mL Volumetric flask, and fixed to the scale with acetonitrile, to be purified.

7.1.3 Blueberry

Weigh the sample about 5 g (accurate to 0.01 g) in a 50 mL screw cap polypropylene centrifuge tube, add 5 mL of water, 3 g of anhydrous magnesium sulfate, 1 g Sodium chloride, 1 g sodium acetate and 15 mL acetonitrile, homogenized at 10 000 r/min homogenization for 2 min and 4 000 r/min for 5 min. Will be on the supernatant was transferred to a 25 mL volumetric flask. And then 10 mL of acetonitrile repeated extraction time, combined extract in the same 25 mL volumetric flask, and acetonitrile Constant volume to scale, to be purified.

7.2 Purification

7.2.1 Soybeans, rice, walnuts, pork, beef liver, milk, onions

Remove 8 mL of the above extract in a 15 mL screw cap polypropylene centrifuge tube, add 300 mg of anhydrous magnesium sulfate, 250 mg of PSA and 500 mg ODS, mixed on a vortex mixer for 2 min, and centrifuged at 4 000 r/min for 5 min. Accurately remove 5 mL of the wash solution in 15 mL glass Tube, by 60 °C nitrogen blowing machine after drying, with 60% acetonitrile aqueous solution and set the volume of 1.0 mL, 0.22 µm filter for liquid chromatography-mass spectrometry / Mass spectrometer.

7.2.2 Chicken liver, orange, spinach, blueberry, tea

Remove 8 mL of the above extract in a 15 mL screw cap polypropylene centrifuge tube, add 300 mg of anhydrous magnesium sulfate, 250 mg PSA, 500 mg ODS and 10 mg of graphitized carbon black were mixed on a vortex mixer for 2 min and centrifuged at 4 000 r/min for 5 min. Accurately remove 5 mL of the purified solution at 15 mL Glass with a plug centrifuge tube, by 60 °C nitrogen blowing machine after drying, with 60% acetonitrile aqueous solution and volume 1.0 mL, 0.22 µm filter for liquid Determination by mass spectrometry/mass spectrometry/mass spectrometry.

7.3 Determination

7.3.1 Liquid Chromatographic Reference Conditions

7.3.1.1 Column. C18, 50 mm × 2.1 mm (id), particle size 1.7 µm, or equivalent;

7.3.1.2 Mobile phase. see gradient elution program Table 1;

Table 1 gradient elution program table

7.3.1.3 Flow rate. 0.25 mL/min;

7.3.1.4 Column temperature. 30 ° C;

7.3.1.5 Injection volume. 5 µL;

7.3.2 Mass spectrometry reference conditions

See Appendix A.

7.3.3 Liquid Chromatography - Mass Spectrometry/Mass Spectrometry Detection and Verification

According to the content of the sample in the sample solution, the selected concentration and sample solution similar to the standard working solution. Standard working solution and sample solution the ketene response value should be within the linear range of the instrument. The standard working solution and sample solution were measured by volume injection. In the above liquid phase color the retention time of cyclohexene ketone was 2.83 min, 3.40 min, thiazolone 3.81 min, Oxaliplatin 3.89 min, olefinic acid 4.05 min, lettuceone 4.08 min, trimethylbenzenone 4.17 min, cycloasproxone 4.83 min.

Cyclodextone Standards for Liquid Chromatography-Mass Spectrometry/Mass Spectrometry Multi-Reaction Monitoring Chromatograms are given in Appendix B, Figure B.1.

In the above liquid chromatography-mass spectrometry conditions, the retention time of the material to be measured in the sample is different from that of the standard working solution.

± 2.5%, and the relative ion abundance of the test substance in the sample is compared with the relative ion abundance of the standard working solution, the allowable relative deviation does not exceed the range specified in Table 2, it can be determined that there is a corresponding analyte in the sample.

Table 2 The 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 test

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

Time (min) formic acid aqueous solution (3.9),% acetonitrile,% 0.25 60 40 1.50 60 40 1.60 40 60 2.00 40 60 3.00 20 80 4.50 20 80 5.00 60 40 6.00 60 40

10.1 Quantitation limits

The quantification limit of this method is 5 µg/kg.

10.2 Recovery rate

The data for the concentration, recovery and precision of the sample are given in Appendix C.

Appendix A

(Informative)

Mass spectrometry reference conditions

Table A.1 Mass Spectrometry Reference Conditions

Ion source ESI, positive mode Scanning mode multiple reaction monitoring MRM Source temperature 110 °C Solvent gas flow rate 550 L/hr, nitrogen the solvent temperature was 350 ° C Taper hole air flow 50 L/hr, nitrogen Collision gas pressure 3.30 × 10 - 3 mbar, argon, purity >= 99.999% Capillary voltage 3.0 KV

Table A.2 Multi-reaction monitoring conditions

Compound parent ion

Ion

Dwell time

Cone hole voltage

Collision energy

Grass off

324.7 178.4

266.5 *

0.02 23 21

0.02 23 12

Thiadenone

326.4 180.2 0.02 20 20 280.3 * 0.02 20 13 Dilute pyridine 328.3 178.1 * 0.02 12 20 282.2 0.02 12 11 Trimethylbenzene 330.3 137.9 0.02 24 24 284.2 * 0.02 24 12 Pyranone 342.4 166.1 0.02 22 21 250.3 * 0.02 22 14 Oxadiazone 360.2 164.1 * 0.02 24 19 268.3 0.02 24 13 Butanone 400.4 138.1 0.02 28 23 354.3 * 0.02 28 15 Cyclohexanone 466.2 180.2 0.02 25 25 280.3 * 0.02 25 15 Note. The ions with "*" in Table A.2 are quantitative ions.

Non-commercial notices. The reference mass spectrometry conditions listed in Appendix A are performed on a Waters Quattro Premier LC/MS, where the test type is for reference only and does not involve commercial purposes and encourages standard users to attempt to use instruments of different manufacturers or models.

Appendix B

(Informative)

Cyclohexenone Standards Multi - Reaction Monitoring Chromatograms

Figure B.1 Cyclohexenone Standards Liquid Chromatography-Mass Spectrometry/Mass Spectrometry Multi-Reaction Monitoring Chromatogram

Appendix C

(Informative)

Recovery and precision

Table C.1 Data on the concentration, recovery and precision of the sample

(%) Concentration (%) Concentration of sample compound concentration (µg/kg) Recovery range (%) Precision (%) Concentration (%) Concentration (%) Concentration (%) Concentration (% Pyranone 5 75.20 to 101.00 10.16 Pyrione 4 76.40 ~ 98.40 8.58 10 81.30 ~ 103.80 8.93 10 79.50 ~ 103.50 9.03 50 77.04 ~ 102.64 9.72 50 80.80 ~ 102.84 8.91 Herbs off 5 76.80 ~ 101.00 9.95 Herbs off 5 80.80 ~ 103.20 8.29 10 75.60 ~ 101.10 8.24 10 78.90 ~ 102.60 7.77 50 80.52 ~ 101.40 7.59 50 78.26 ~ 102.36 9.49 Thiabendone 5 76.4 ~ 102.20 9.73 Thiadenone 5 76.20 ~ 98.40 6.54 10 81.70 ~ 107.00 9.16 10 81.00 ~ 104.30 9.35 50 79.40 ~ 102.20 8.20 50 86.32 ~ 103.36 5.84 Oxadiazone 5 76.4 to 105.00 10.15 oxadiazone 5 83.20 to 109.40 9.23 10 75.90 ~ 94.10 6.76 10 80.60 ~ 104.80 10.02 50 73.24 ~ 94.58 9.73 50 80.44 ~ 100.32 8.26 Dilute pyridine 5 84.00 ~ 103.60 6.19 diltthlor 5 82.60 ~ 104.80 7.77 10 88.20 ~ 103.20 5.14 10 75.30 ~ 98.10 7.22 50 82.06 ~ 104.34 8.30 50 82.70 ~ 104.26 8.20

Table C.1 (continued)

Butoxfen 5 83.12 ~ 105.60 6.19 Butanone 5 77.40 to 103.20 10.02 10 80.00 ~ 98.40 5.14 10 76.90 ~ 97.30 8.31 50 79.46 ~ 100.62 8.30 50 77.42 ~ 102.86 10.22 Trimesterone 5 78.60 ~ 102.20 8.20 Trimethoproxone 5 76.20 ~ 107.00 7.90 10 81.20 ~ 104.20 7.84 10 80.50 to 101.70 10.39 50 87.12 ~ 103.76 5.94 50 80.86 ~ 99.56 6.14 Cyclohexanone 5 82.20 to 104.20 8.47 Cyclohexanone 5 81.60 ~ 108.60 8.58 10 74.20 ~ 101.00 8.24 10 77.60 ~ 98.70 5.89 50 78.76 ~ 94.84 6.45 50 78.94 ~ 98.34 8.31 Pyrrione 5 74.60 ~ 103.80 9.82 Pyrrione 5 78.40 ~ 99.60 7.97 10 79.10 ~ 97.30 6.58 10 78.10 ~ 102.10 11.19 50 75.80 ~ 98.76 7.93 50 83.12 ~ 100.64 7.69 Herbs off 5 76.80 ~ 101.40 7.12 Herbs off 5 73.60 ~ 98.40 5.67 10 81.50 to 101.10 6.53 10 78.40 to 100.70 7.61 50 77.66 ~ 96.88 7.43 50 80.22 ~ 99.34 8.32 Thiabendone 5 76.40 ~ 108.60 10.22 Thiomethoxone 5 76.40 ~ 101.20 6.33 10 78.90 ~ 101.70 9.00 10 76.70 ~ 101.30 9.71 50 78.28 ~ 102.12 8.96 50 83.36 ~ 104.20 7.91

Table C.1 (continued)

Oxadiazone 5 79.40 to 100.80 8.33 Oxadiazone 5 76.20 to 103.20 9.43 10 75.90 ~ 105.70 10.18 10 79.40 ~ 97.30 7.77 50 76.66 ~ 96.88 7.60 50 78.88 ~ 99.24 7.88 Dilute pyridine 5 77.20 ~ 103.60 8.87 diltthlor 5 75.80 ~ 106.40 10.24 10 76.40 ~ 104.70 10.47 10 78.50 ~ 103.50 9.25 50 79.52 ~ 101.46 7.74 50 78.86 ~ 97.00 6.68 Butroxydim ~ 5 74.40 99.40 76.00 5 8.34 butroxydim - 105.40 10.05 10 78.40 ~ 96.20 7.31 10 76.10 ~ 102.60 9.23 50 77.08 to 102.06 10.38 50 79.46 to 102.72 8.36 Trimethoproxone 5 74.20 to 103.40 9.66 Trimethylpenone 5 78.20 to 98.40 7.80 10 75.40 to 98.40 7.79 10 79.50 to 105.80 10.04 50 81.74 ~ 102.54 8.07 50 80.72 ~ 103.36 6.61 Cyclohexanone 5 77.40 ~ 103.80 9.48 Cyclohexanone 5 82.00 ~ 109.40 9.99 10 78.60 ~ 106.70 7.70 10 81.60 ~ 104.80 6.99 50 77.14 ~ 96.54 8.34 50 82.04 ~ 97.94 6.54 Pyrione 5 80.20 ~ 103.60 7.99 Spinach Pyranone 5 81.20 to 106.80 8.60 10 79.40 to 103.20 9.10 10 78.90 to 101.60 8.33 50 84.12 ~ 102.84 6.79 50 80.22 ~ 99.24 7.57

Table C.1 (continued)

Grasses 5 77.40 ~ 103.60 8.87 Herbs off 5 80.40 ~ 104.80 9.47 10 79.50 to 103.30 8.75 10 76.20 to 103.50 9.12 50 82.90 ~ 104.62 7.50 50 8020 ~ 100.72 7.03 Thiadenone 5 82.20 ~ 105.40 8.45 Thiadenone 5 80.00 ~ 105.60 9.04 10 83.10 ~ 104.20 7.73 10 81.60 ~ 105.50 8.85 50 88.70 ~ 103.42 5.22 50 82.06 ~ 106.60 8.68 Oxadiazone 5 81.40 ~ 107.60 9.46 oxadiazone 5 82.60 ~ 100.00 7.17 10 81.60 ~ 105.40 8.16 10 84.00 ~ 105.70 7.59 50 84.70 ~ 101.94 6.71 50 83.20 ~ 108.06 6.88 Dilute pyridine 5 80.20 ~ 104.00 8.23 dilute pyridine 5 82.00 ~ 105.40 9.01 10 79.20 to 95.80 6.31 10 81.20 to 101.10 9.66 50 79.70 ~ 102.74 8.39 50 88.70 ~ 102.72 5.09 Butoxfen 5 77.60 ~ 105.60 10.55 Butanone 5 76.20 ~ 99.60 7.66 10 79.40 ~ 95.40 6.48 10 78.60 ~ 105.10 9.42 50 80.06 ~ 104.02 6.99 50 80.72 ~ 106.20 7.77 Trimesterone 5 83.20 to 108.20 8.14 Trimethoproxone 5 82.60 to 104.60 7.07 10 78.10 ~ 100.10 7.99 10 78.10 ~ 106.40 8.79 50 82.12 to 106.12 7.22 50 88.06 to 102.74 5.05

Table C.1 (continued)

Cyclohexanone

5 80.20 ~ 96.20 6.40 Spinach Cyclohexanone 5 82.00 ~ 105.60 8.48 10 79.40 to 97.30 7.39 10 79.40 to 98.50 7.72 50 77.52 ~ 98.62 8.97 50 84.06 ~ 102.72 6.24 Pyrione 5 77.00 ~ 103.40 10.57 Pyrrione 5 73.20 ~ 104.80 11.33 10 81.00 ~ 104.10 7.61 10 79.50 ~ 103.50 9.13 50 77.04 ~ 100.62 8.70 50 84.06 ~ 102.84 7.51 Herbs off 5 77.80 ~ 98.00 8.08 Herbs off 5 80.80 ~ 105.40 8.84 10 78.50 to 98.40 8.39 10 79.10 to 102.60 8.52 50 78.86 to 102.14 9.61 50 84.08 to 102.50 6.00 Thiabendone 5 76.00 ~ 103.60 9.53 Thiomethoxone 5 80.20 ~ 98.40 6.88 10 81.00 ~ 99.70 6.80 10 79.40 ~ 105.80 9.80 50 79.46 ~ 106.72 8.59 50 84.12 ~ 103.36 5.83 Oxalcone 5 78.20 to 101.20 8.30 Elicenone 5 80.60 to 109.40 10.10 10 79.50 to 106.80 11.04 10 79.30 to 104.80 9.10 50 80.42 to 104.20 9.12 50 82.02 to 106.08 8.21 Diltiazem 5 80.20 ~ 105.20 8.12 dilute pyridine 5 81.80 ~ 102.40 8.65 10 79.40 ~ 100.40 7.58 10 79.80 ~ 98.70 6.74 50 75.68 ~ 104.72 9.74 50 78.22 ~ 98.52 7.13

Table C.1 (continued)

Butoxfen 5 76.62 ~ 102.80 9.85 Butoxfen 5 80.00 ~ 107.60 9.83 10 79.10 ~ 106.80 9.09 10 79.20 ~ 103.10 8.61 50 85.02 ~ 100.48 7.07 50 80.62 ~ 106.96 7.78 Trimesterone 5 80.60 ~ 101.60 8.25 Trimethoproxone 5 74.40 ~ 104.20 9.31 10 78.50 to 103.70 9.21 10 78.30 to 97.10 7.27 50 82.72 ~ 104.76 6.65 50 78.94 ~ 100.20 8.08 Cyclohexanone 5 81.20 ~ 103.60 9.63 Cyclohexanone 5 74.20 ~ 104.60 10.39 10 80.40 ~ 106.40 8.74 10 78.10 ~ 103.10 9.15 50 82.12 ~ 100.76 7.03 50 81.74 ~ 99.24 7.01 Pyrione 4 77.20 ~ 98.20 7.70 Pyrrione 5 74.60 ~ 97.20 6.30 10 80.10 ~ 103.90 9.76 10 78.90 ~ 98.40 6.88 50 82.12 ~ 102.68 7.43 50 78.96 ~ 98.62 8.49 Grasses 5 81.60 ~ 103.20 8.11 Grasses off 5 77.80 ~ 98.40 8.14 10 79.80 to 108.10 9.45 10 78.50 to 100.30 8.11 50 80.78 ~ 97.78 6.08 50 78.86 ~ 99.24 7.74 Thiabendone 5 81.20 to 99.60 6.60 Thiadenone 5 79.40 to 103.20 9.37 10 78.60 ~ 102.70 7.49 10 76.10 ~ 96.40 7.14 50 82.62 ~ 106.20 7.41 50 78.46 ~ 96.12 6.77

Table C.1 (continued)

Oxadiazone 5 83.20 to 104.60 7.61 Oxadiazone 5 81.20 to 104.80 9.26 10 78.10 ~ 106.40 8.80 10 79.60 ~ 100.10 8.05 50 80.06 to 99.24 6.98 50 80.60 to 100.12 7.59 Diltiazem 5 81.20 ~ 104.20 8.18 diltthlor 5 77.60 ~ 103.40 9.35 10 79.90 ~ 98.30 6.43 10 78.80 ~ 98.90 7.62 50 80.38 ~ 106.12 9.22 50 78.96 ~ 102.72 10.01 Butoxfen 5 74.80 to 107.20 11.15 Butoxfen 5 81.00 to 102.80 8.44 10 80.20 to 104.60 7.32 10 79.10 to 106.30 9.57 50 80.18 ~ 98.36 8.09 50 84.12 ~ 104.08 5.97 Trimesterone 5 77.20 to 105.40 9.29 Trimethoprostenone 5 77.40 to 103.20 8.18 10 78.40 ~ 106.70 9.75 10 79.50 ~ 103.70 9.17 50 76.92 ~ 99.24 8.32 50 82.72 ~ 102.84 7.86 Cyclohexanone 5 83.20 to 109.20 8.07 Cyclohexanone 5 76.40 ~ 105.40 10.17 10 79.50 to 103.00 8.93 10 83.10 to 106.40 8.60 50 76.98 ~ 99.76 9.13 50 82.12 ~ 100.10 6.59 Pyranone 5 83.80 to 100.20 6.53 Pyrrione 5 74.20 ~ 103.60 9.74 10 81.60 ~ 104.70 9.22 10 86.10 ~ 103.70 6.48 50 79.52 ~ 102.68 8.53 50 82.90 ~ 103.36 7.23

Table C.1 (continued)

Herbs off 5 74.40 ~ 103.20 9.40 Herbicide 5 85.20 ~ 109.40 9.02 10 81.20 to 108.10 8.99 10 79.50 to 104.20 8.09 50 78.94 ~ 98.48 6.74 50 84.26 ~ 106.08 Thiabendone 5 74.20 ~ 100.40 9.01 Thiadenone 5 82.20 ~ 100.00 5.97 10 78.60 ~ 98.40 7.79 10 79.80 ~ 98.70 6.37 50 83.16 ~ 106.20 7.27 50 82.06 ~ 99.04 9.02 Oxadiazone 5 77.40 ~ 104.60 10.34 oxadione 5 80.40 ~ 100.20 7.48 10 78.10 ~ 106.40 9.71 10 79.20 ~ 94.20 5.49 50 78.82 ~ 99.24 7.49 50 79.70 ~ 98.22 7.53 Diltiazem 5 82.00 ~ 104.80 9.25 dilute pyridine 5 78.40 ~ 100.60 8.40 10 79.60 ~ 96.20 5.68 10 82.60 ~ 105.20 7.69 50 81.94 ~ 99.34 5.95 50 79.02 ~ 97.52 6.55 Butenone 5 80.20 to 103.40 8.39 Butanone 5 81.40 to 104.80 8.50 10 79.10 ~ 95.60 6.29 10 78.10 ~ 102.60 9.74 50 79.70 ~ 99.30 7.61 50 80.44 ~ 107.76 7.94 Trimesterone 5 77.00 ~ 100.60 8.25 Trimethoproxone 5 83.20 ~ 106.80 8.70 10 79.40 ~ 96.70 7.01 10 80.30 ~ 101.20 10.70 50 82.06 ~ 99.24 7.09 50 80.72 ~ 98.04 7.64 Cyclohexanone 5 80.40 ~ 98.40 7.74 Cyclohexanone 5 82.00 ~ 106.00 9.41 10 78.10 ~ 103.50 9.17 10 81.60 ~ 102.60 9.27 50 82.12 ~ 98.74 6.85 50 80.12 ~ 98.50 6.71 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