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Food safety national standard -- Determination of 440 pesticides and related chemical residues in edible fungi by liquid chromatography-mass spectrometry
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GB 23200.12-2016
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Basic data | Standard ID | GB 23200.12-2016 (GB23200.12-2016) | | Description (Translated English) | Food safety national standard -- Determination of 440 pesticides and related chemical residues in edible fungi by liquid chromatography-mass spectrometry | | Sector / Industry | National Standard | | Classification of Chinese Standard | G25 | | Word Count Estimation | 58,583 | | Date of Issue | 2016-12-18 | | Date of Implementation | 2017-06-18 | | Older Standard (superseded by this standard) | GB/T 23202-2008 | | Regulation (derived from) | State Health Commission, Ministry of Agriculture, Food and Drug Administration Notice No.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 23200.12-2016: Food safety national standard -- Determination of 440 pesticides and related chemical residues in edible fungi 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 440 pesticides and related chemical residues in edible fungi by liquid chromatography - mass spectrometry
ICS
National Standards of People's Republic of China
Replace GB/T 23202-2008
National standards for food safety
Edible fungi in 440 kinds of pesticides and related chemicals
Determination of residual amount
Liquid chromatography - mass spectrometry
National Food Safety Standards-
Determination of 440 pesticides and related chemicals residues in mushrooms
Liquid chromatography - mass spectrometry
2016-12-18 Release.2017-06-18 Implementation
Directory
Preface II
1 Scope 1
2 normative reference document 1
Principle 1
4 reagents and materials 1
5 instruments and equipment 2
6 Preparation of sample 2
7 Analysis Step 2
Calculation and presentation of results 4
9 precision 4
10% limit and recovery rate 4
Appendix A (informative appendix) 440 pesticides and related chemicals, English name, method of quantitative limit, grouping, solvent selection and mixing
Standard solution concentration Table 5
Appendix B (informative) 440 retention time for pesticides and related chemicals, monitoring of ion pairs, source fragmentation and collision gas
Amount 1 4
Appendix C (informative) 440 Pesticides and Related Chemicals Multiple Reaction Monitoring (MRM) Chromatogram 23
Appendix D (informative) Relative standard deviation in laboratory
Appendix E (informative appendix) Relative standard deviation between laboratories
Appendix F (informative) Experimental data on the concentration and recovery of samples
Foreword
This standard replaces GB/T 23202-2008 "Determination of 440 pesticides and related chemical residues in edible fungi Liquid Chromatography - Series
Mass spectrometry ".
This standard compared with GB/T 23202-2008, the main changes are as follows.
- Standard text format is modified to national standard text format for food safety;
- increase the "other edible fungi can refer to the implementation" in the standard range.
This standard replaced the previous version of the standard release.
-GB/T 23202-2008.
National standards for food safety
Determination of 440 pesticides and related chemical residues in edible fungi
Liquid chromatography - mass spectrometry
1 Scope
This standard specifies the amount of 440 pesticides and related chemicals (see Appendix A) Residual Liquids
Determination of Chromatography - Mass Spectrometry.
This standard applies to the qualitative identification of 440 pesticides and related chemicals in the mushroom, mushroom, black fungus and mushrooms, 364 pesticides and
Quantitative determination of related chemicals, other edible fungi 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 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 homogenate, salted out by centrifugation, solid-phase extraction column, eluted with acetonitrile-toluene solution (3 1) and related chemistry
Determination of the product by liquid chromatography - tandem mass spectrometry and 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 Acetonitrile (CH3CN, 75-05-8). Chromatographic Purification.
4.1.2 Acetone (CH3COCH3, 67-64-1). Chromatographic Purification.
4.1.3 Toluene (C7H8, 108-88-3). Chromatographic pure.
4.1.4 Isooctane (C8H18,540-84-1). Chromatographic pure.
4.1.5 dichloromethane (CH2Cl2, 75-09-2). chromatographic purity.
4.1.6 n-hexane (C6H14,110-54-3). pure chromatography.
4.1.7 Methanol (CH3OH, 67-56-1/170082-17-4). Chromatographic Purification.
4.1.8 sodium chloride (NaCl, 7647-14-5). excellent grade pure.
4.1.9 anhydrous sodium sulfate (Na2SO4,7757-82-6). analytical grade. 650 ℃ burning 4h, stored in a dryer, cooling and standby.
4.2 solution preparation
4.2.1 acetonitrile - toluene solution (3 1). take 300 mL of acetonitrile, add 100 mL of toluene, shake back.
4.2.2 Formic acid solution (0.1%). take 1000 mL of water, add 1 mL of formic acid, shake back.
4.2.3 ammonium acetate solution (5mmol/L). Weigh 0.385 g ammonium acetate, dissolved in 1000 mL of aqueous solution, shake back.
4.2.4 acetonitrile - water solution (3 2). take 300 mL of acetonitrile, add.200 mL of water, shake back.
4.3 standards
Pesticide and Related Chemical Reference Material. Purity ≥95%, see Appendix A.
4.4 standard solution preparation
4.4.1 Standard stock solution
Respectively, weighing 5mg ~ 10mg (accurate to 0.1mg) pesticides and related chemicals in the standard 10mL volumetric flask, according to the standard
The solubility of the quasi-solution is methanol, n-hexane, acetone, acetonitrile or isooctane dissolved and constant volume to the scale (solvent options see Appendix A). standard
The stock solution is stored at 4 ° C for 1 year.
4.4.2 Mixing standard solutions (mixed standard solutions A, B, C, D, E, F and G)
According to the retention time of pesticides and related chemicals, 440 kinds of pesticides and related chemicals are divided into A, B, C, D, E, F and G
And the concentration of each pesticide and associated chemical in the instrument to determine the concentration in the mixed standard solution. This standard
For the classification of 440 pesticide and related chemicals and their mixed standard solution concentrations, see Appendix A.
Depending on the grouping of each pesticide and associated chemical, the concentration of the standard solution and the concentration of the standard stock solution, the amount of individual
Pesticide and related chemicals Standard stock solution in 100mL volumetric flask, with a fixed volume of methanol to the scale. Mixed standard solution stored at 4 ° C,
The shelf life is one month.
4.4.3 Substrate mixed standard working solution
Pesticide and related chemicals Substrate mixed standard working solution is prepared by mixing the sample with different concentrations of the substrate mixed with standard working solution
Liquid A, B, C, D, E, F and G are used for standard working curves. Matrix mixed standard working solution should be used with the current distribution.
4.5 Materials
4.5.1 Solid Phase Extraction Column. Sep-Pak CarbonNH2
1), 6 mL, 1 g or equivalent.
4.5.2 Microporous membrane (nylon). 13mm × 0.2μm.
5 instruments and equipment
5.1 Liquid Chromatography - Tandem Mass Spectrometer. Equipped with electrospray ion source.
5.2 Analyze the balance. 0.01 g and 0.0001 g.
5.3 Centrifuge tube. 80 mL.
5.4 Pipettes. 1 mL and 10 mL.
5.5 chicken heart bottle. 100 mL.
5.6 high-speed organization homogenizer. the minimum speed of not less than 15 000 r/min.
5.7 Centrifuge. not less than 4 500r/min.
5.8 Rotary evaporator.
5.9 nitrogen dryers.
5.10 Vial. 2 mL, with Teflon capping.
6 sample preparation
Edible fungus sample sampling site according to GB 2763 Appendix A, the sample chopped and homogenized homogenized homogenized, the prepared samples were
Divided into two, packed into a clean sample container, sealed and marked. The samples were cryopreserved at -18 ° C.
7 Analysis steps
7.1 Extraction
Weigh 20g sample (accurate to 0.01g) in 80mL centrifuge tube, add 40mL acetonitrile, 15000r/min homogenate extraction 1min,
Add 5g sodium chloride, and then homogenate extraction 1min, 4200 r/min centrifugal 5min, take supernatant 20mL (equivalent to 10g sample volume), 40 ℃
Water bath rotation concentrated to about 1mL, to be purified.
7.2 Purification
Add about 2 cm high anhydrous sodium sulfate to the Sep-Pak CarbonNH2 solid phase extraction column and place the solid phase extraction unit
on. The column was pre-washed with 4 mL of acetonitrile-toluene solution before loading, and the sample concentrate was rapidly transferred when the liquid level reached the top of anhydrous sodium sulfate
To the purification column, and replace the heart of the bottle to receive. The vial was washed with 2 mL of acetonitrile-toluene solution and the washings were combined into the extraction column and repeated
This operation 3 times. The residual sample was transferred to an extraction column. At the top of the SPE column, connect a 50 mL reservoir with 25 mL of acetonitrile-toluene
Solution elution pesticides and related chemicals, combined in 100mL chicken heart bottle, 40 ℃ water bath spin concentrated to
Sep-Pak CarbonNH2 solid phase extraction column is the product name of Waters' products. This information is provided for the convenience of users of this standard and does not indicate the recognition of the product. If it is
His equivalent product has the same effect, you can use these equivalent.
About 0.5mL. And dried at 45 ° C under nitrogen. The residue was dissolved in 1 mL of acetonitrile-water solution and filtered through a 0.2 μm microporous membrane for liquid chromatography
Determination of Tandem Mass Spectrometer. At the same time take no pesticide and related chemicals, edible fungus samples, according to 7.1 and 7.2 steps to prepare sample blank extract,
Used to prepare matrix mixed standard working solution.
7.3 Determination
7.3.1 A, B, C, D, E, F Group Liquid Chromatography - Tandem Mass Spectrometry Reference Conditions
Column.
A) ZORBAX SB-C18, 3.5 μm, 100 mm × 2.1 mm (inner diameter) or equivalent;
B) mobile phase and gradient elution conditions in Table 1;
Table 1 Mobile phase and gradient elution conditions
Total flow/min Flow rate/(μL/min) Mobile phase A (0.1% formic acid) /% Mobile phase B (acetonitrile) /%
0 0.00 400 99.0 1.0
1 3.00 400 70.0 30.0
2 6.00 400 60.0 40.0
3 9.00 400 60.0 40.0
4 15.00 400 40.0 60.0
5 19.00 400 1.0 99.0
6 23.00 400 1.0 99.0
7 23.01 400 99.0 1.0
C) Column temperature. 40 ° C;
D) Injection volume. 10 μL;
E) ionization source mode. electrospray ionization;
F) ionization source polarity. positive mode;
G) atomization gas. nitrogen;
H) atomization gas pressure. 0.28 MPa;
I) ion spray voltage. 4000 V;
J) Dry gas temperature. 350 ° C;
K) Dry gas flow rate. 10 L/min;
L) Monitor the ion pair, the collision gas energy and the source fragmentation voltage, see Appendix B.
7.3.2 Group G Liquid Chromatography - Tandem Mass Spectrometry Reference Conditions
A) Column. ZORBAX SB-C18, 3.5 μm, 100 mm × 2.1 mm (inner diameter) or equivalent;
B) mobile phase and gradient elution conditions in Table 2;
Table 2 Mobile phase and gradient elution conditions
Total time/min Flow rate/(μL/min) Mobile phase A (5 mmol/L ammonium acetate water) /% Mobile phase B (acetonitrile) /%
0 0.00 400 99.0 1.0
1 3.00 400 70.0 30.0
2 6.00 400 60.0 40.0
3 9.00 400 60.0 40.0
4 15.00 400 40.0 60.0
5 19.00 400 1.0 99.0
6 23.00 400 1.0 99.0
7 23.01 400 99.0 1.0
C) Column temperature. 40 ° C;
D) Injection volume. 10 μL;
E) ionization source mode. electrospray ionization;
F) ionization source polarity. negative mode;
G) atomization gas. nitrogen;
H) atomization gas pressure. 0.28 MPa;
I) ion spray voltage. 4000 V;
J) Dry gas temperature. 350 ° C;
K) Dry gas flow rate. 10 L/min;
L) Monitor the ion pair, the collision gas energy and the source fragmentation voltage, see Appendix B.
7.3.3 Qualitative determination
When the sample is measured under the same experimental conditions, if the retention time of the detected chromatographic peaks is consistent with the standard sample,
After the background of the sample mass spectrum, the selected ions are present, and the selected ion abundance ratio is proportional to the ion abundance ratio of the standard sample
(Relative abundance > 50%, allow ± 20% deviation; relative abundance > 20% to 50%, allow ± 25% deviation; relative abundance > 10% to
20%, allow ± 30% deviation; relative abundance ≤ 10%, allow ± 50% deviation), you can determine the presence of this sample pesticide or related chemistry
Goods.
7.3.4 Quantitative determination
In this standard, liquid chromatography-tandem mass spectrometry was quantitatively determined by external standard-calibration curve method. To reduce the impact of matrix on quantitative determination, quantitative use
The standard solution should be prepared using a standard solution of the matrix mixed standard solution. And to ensure that the measured samples of pesticides and related chemicals response value
Are within the linear range of the instrument. See Appendix C for more than 440 chromatograms for multi-reaction monitoring (MRM) for pesticides and related chemicals.
7.4 parallel test
Perform the parallel test of the same specimen according to the above procedure.
7.5 blank test
Unless the sample is not weighed, according to the above steps.
8 results are calculated and expressed
The results of liquid chromatography-tandem mass spectrometry were quantified by standard curve method. The quantitative results of standard curve method were calculated according to formula (1)
Xi = ci ×
V x
(1)
M 1000
Where.
Xi - Residue of test component in milligrams per kilogram (mg/kg);
Ci - the concentration of the solution to be measured from the standard curve, in micrograms per milliliter (μg/mL);
V - volume of sample solution in milliliters (mL);
M - the weight of the sample represented by the sample solution in grams (g).
The result of the calculation should be deducted from the blank value. The result of the measurement is expressed by the arithmetic mean of the parallel measurement, and the two valid digits are 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 quantitative limits of this method are given in Appendix A.
10.2 Recovery rate
When adding levels of LOQ, 4 × LOQ, add the recovery rate see Appendix F.
Appendix A
(Informative)
440 pesticides and related chemicals, English name, method Quantitative limits, grouping, solvent selection and mixing Standard solution concentration
A.1 440 kinds of pesticides and related chemicals, English name, method of quantitative limit, grouping, solvent selection and mixed standard solution concentration table
A.1.
Table A.1 440 kinds of pesticides and related chemicals, English name, method of quantitative limit, grouping, solvent selection and mixed standard solution concentration
Serial number Chinese name English name
The limit of quantitation
/ (Μg/kg)
Solvent
Mixed standard dissolved
Liquid concentration
/ (Mg/L)
Group A
1 aniline spirit propham 55.00 toluene 11.00
2 isoprocarb isoprocarb 1.16 methanol 0.23
3, 3, 4, 4, 4, 3, 3, 3, 3, 3, 5, trimethacarb 0.16 Methanol 0.03
4 ring curmitine cycluron 0.10 methanol 0.02
5 Carbaryl carbaryl 5.16 Methanol 1.03
6 Toxicant propachlor 0.16 Methanol 0.03
7 pimidazole raenzazole 0.66 methanol 0.13
8 ocher net simetryn 0.06 methanol 0.01
9 Green Valley Long monolinuron 1.80 Methanol 0.36
10 times out of phosphorus mevinphos 0.80 toluene 0.16
11 azepine aziprotryne 0.70 methanol 0.14
12 Micronautics Secbumeton 0.06 Methanol 0.01
13 Azathione Sulfonamide cyprodinil 0.36 Methanol 0.07
14 sulton buturon 4.50 methanol 0.90
15 bisacyl chloride carbetamide 1.80 methanol 0.36
16 pirimicar pirmicarb 0.08 methanol 0.02
17 Isosubicin clomazone 0.20 Methanol 0.04
18 cyanocobalt cyanazine 0.10 methanol 0.02
19 promised net prometryne 0.10 methanol 0.02
20 methyl paraoxon methyl 0.40 methanol 0.08
21 4,4-dichlorobenzophenone 4,4-dichlorobenzophenone 6.80 Methanol 1.36
22 thiacloprid thiacloprid 0.20 methanol 0.04
23 imidacloprid 11.00 Methanol 2.20
24 sulfothiazide ethidimuron 0.76 methanol 0.15
25 Butoxalone isomethiozin 0.56 Methanol 0.11
Potatoes cis and trans diallate 44.60 Methanol 8.92
27 acetochlor acetochlor 23.70 methanol 4.74
28 nitrilpyram 8.56 methanol 1.71
29 Methoxypropine methoprotryne 0.10 Methanol 0.02
30 Dimethylphenols dimethhenamid 2.16 Methanol 0.43
31 Terracuria terrbucarb 1.06 Methanol 0.21
32 tebuconazole penconazole 1.00 methanol 0.20
33 myclobutamycin myclobutanil 0.50 methanol 0.10
34 Paclobutrazole paclobutrazol 0.30 Methanol 0.06
35 times thiophosphor sulfoxide fenthion sulfoxide 0.16 methanol 0.03
36 triazole alcohol triadimenol 5.30 methanol 1.06
37 Zhong Ding Ling butralin 0.96 Methanol 0.19
38 Spiroxamine 0.06 Methanol 0.01
39 Methylphenol tolclofos methyl 33.30 Methanol 6.66
40 beetachin a desmedipham 2.00 methanol 0.40
41 Methanol 1.06 Methanol 1.07
42 allyl alcohol allethrin 30.20 methanol 6.04
43 diazinon 0.36 Toluene 0.07
44 Paralyzed Phosphorus edifenphos 0.40 Methanol 0.08
45 Propoxamine pretilachlor 0.16 Methanol 0.03
Table A.1 (continued)
Serial number Chinese name English name
The limit of quantitation
/ (Μg/kg)
Solvent
Mixed standard dissolved
Liquid concentration
/ (Mg/L)
Fluorotiazole flusilazole 0.30 Methanol 0.06
47 Propane Zinc iprovalicarb 1.16 Methanol 0.23
48 wheat rust Ling benodanil 1.76 methanol 0.35
49 fluoroamide flutolanil 0.56 methanol 0.11
50 Sulfonamph famphur 1.80 Methanol 0.36
51 benzoprene benalyxyl 0.60 methanol 0.12
52 benzyl chlorotriazole alcohol diclobutrazole 0.26 methanol 0.05
53 Acetiazole etaconazole 0.90 Methanol 0.18
54 Chlorophenylpyrimidinol fenarimol 0.30 Methanol 0.06
55 phthalic acid phthalic acid, dicyclobexyl ester 1.00 methanol 0.20
56 Tetramethrin tetramethrin 0.90 Methanol 0.18
57 antibacterial spirit dichlofluanid 1.30 toluene 0.26
58 solution grass cloquintocet mexyl 0.96 methanol 0.19
59 Biphenyl triazole alcohol bitertanol 16.70 Methanol 3.34
Potassium Phosphorus Azinphos ethyl 54.46 Methanol 10.89
Methanol a clodinafop propargyl 1.20 Methanol 0.24
62 Suzumaru triflumuron 1.96 Methanol 0.39
63 isoxazolone a isoxaflutole 1.96 methanol 0.39
64 paclitaxel a anilofos 0.36 Methanol 0.07
65 Thiabendazole a thiophanat ethyl 10.10 Methanol 2.02
66 Quizalofop-ethyl 0.36 Methanol 0.07
67 Fiprofenoxylate Haloxyfop-methyl 1.30 Methanol 0.26
68 Fluorinated chlorpyrifos butyl 0.16 Methanol 0.03
69 Ethyl bromothiophosphorus bromophos-ethyl 283.86 Methanol 56.77
70 Scavenging bensulide 17.10 Methanol 3.42
71 bromophenylene phosphate bromfenvinfos 1.50 methanol 0.30
Potassium azoxystrobin 0.26 Methanol 0.05
73 Pyridobacillus pyrazophos 0.80 Methanol 0.16
74 Fluorfins flufenoxuron 1.60 Methanol 0.32
75 indoxacarb 3.76 methanol 0.75
76 Amino-avermectin benzoate emamectin benzoate 0.16 Methanol 0.03
Group B
77 cotton Long a dazomet 63.50 methanol 12.70
78 nicotine a nicotine 1.10 methanol 0.22
79 non-grass long fenuron 0.50 methanol 0.10
80 Methotrexate a cyromazine 3.60 Methanol 0.72
81 rats died crimidine 0.80 methanol 0.16
82 Acephate A acephate 6.66 Methanol 1.33
Mushi enemy molinate 1.06 Methanol 0.21
84 carbendazim carbendazim 0.26 methanol 0.05
Chloro-4-hydroxy-3-phenylpyridazine
6-chloro-4-hydroxy-3-phenyl-pyridazi
0.86 Methanol 0.17
86 Propoxur propoxur 12.20 Methanol 2.44
87 isazolone isouron 0.20 methanol 0.04
88 chlormopron a chlorotoluron 0.30 methanol 0.06
89 long-acting force thiofanox 78.50 methanol 15.70
90 Chlorobenzene chlorbufam 91.50 Methanol 18.30
91 Wicked Viola bendiocarb 1.60 Methanol 0.32
92 Fighting Chin propazine 0.16 Methanol 0.03
93 terbutaline terbuthylazine 0.26 methanol 0.05
94 diuron diuron 0.80 methanol 0.16
95 Chloromethylthiophosphate chlormephos 224.00 Methanol 44.80
96 Moisturizer Pyorin 0.30 Methanol 0.06
Table A.1 (continued)
Serial number Chinese name English name
The limit of quantitation
/ (Μg/kg)
Solvent
Mixed standard dissolved
Liquid concentration
/ (Mg/L)
97 wild Yan dry difenzoquat-methyl sulfate 0.40 methanol 0.08
98 Hexamethasone clothianidin 31.50 Methanol 6.30
99 Take the grass a pronamide 7.70 Methanol 1.54
100 dimethachlor dimethachloro 0.96 methanol 0.19
101 Bromoguron a methobromuron 8.40 Toluene 1.68
Potassium phorate
103 benzoate aclonifen 12.10 methanol 2.42
104 dean phosphorus mephosfolan 1.16 methanol 0.23
105 Benzylimidazole imibenzonazole-des-benzyl 3.10 Methanol 0.62
106 grass is not long neburon 3.56 methanol 0.71
107 Aroma cream mefenoxam 0.76 Methanol 0.15
108 ethofume sate 186.00 Methanol 37.20
109 different rice blast net iprobenfos 4.16 methanol 0.83
110 Ciproazoleazole cyproconazole 0.36 Methanol 0.07
111 thiamethoxam thiamethoxam 16.50 methanol 3.30
112 pyrimethazine etrimfos 9.40 methanol 1.88
Chlorpyrifos cythioate 40.00 Methanol 8.00
114 Phosphoramidam 1.96 Methanol 0.39
115 beetin a phenmedipham 2.26 methanol 0.45
116 Biphenyl Ester a bifenazate 11.40 Methanol 2.28
117 Cyclomide Fenhexamid 0.46 Methanol 0.09
118 benzodiazole flutriafol 4.30 methanol 0.86
119 Bacteriostatic ester furalaxyl 0.40 Methanol 0.08
120 bio-allyrin bioallethrin 99.00 methanol 19.80
121 benzonitrile cyanofenphos 10.40 Methanol 2.08
122 Methylpyrimidine Phosphorus pirimiphos methyl 0.10 Methanol 0.02
123 buprofezin buprofezin 0.46 methanol 0.09
124 Ethylenediophosulfone disulfoton sulfone 1.26 Methanol 0.25
125 Quinacid fenazaquin 0.16 Methanol 0.03
126 triazophos 0.36 Toluene 0.07
127 Flavored Phosphorus DEF 0.80 Toluene 0.16
128 Cyclohexanone pyriftalid 0.30 Methanol 0.06
129 metolazole metconazole 0.66 methanol 0.13
13...
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