Some standard content:
ICS 65. 100. 20
National Standard of the People's Republic of China
CB12686--2004
Replaces GH【2686-1990
Glyphosate technical
Issued on December 6, 2004
General Administration of Quality Supervision, Inspection and Quarantine of the People's Republic of China Administration of Standardization of the People's Republic of China
Implementation on October 1, 2005
Chapter 3 and Chapter 5 of this standard are mandatory, and the rest are recommended. GB12686-2004
This standard is modified to adopt the technical requirements of FAO specification 284/TC (2000/2001) for N-phosphine carboxymethylglycine (glyphosate technical)》GLYPHOSAIEACID'FECHNICAL
The main difference between this standard and FAO specification 284/TC (2000/2001) is that the formaldehyde index of this standard is ≤0.8g/kg, while the formaldehyde index of FAO specification 284/TC (2000/2001) is ≤1.2g/kg. This index of this standard is stricter than that of FAO specification 284/TC (2000/2001). This standard is a revision of G12686-2004. The main differences between this standard and GB 12686-1990 are that the appearance is changed from white or slightly yellow powder to white powder; - the classification and grading are cancelled; - the mass fraction of glyphosate is changed to ≥95.0%; - the determination method of glyphosate is added with high performance liquid chromatography and used as arbitration method; - the control item of loss on drying is cancelled; - the control item of formaldehyde is added; - the control item of nitrosoglyphosate is added; - the control item of water insoluble matter is changed to the control item of sodium hydroxide insoluble matter; the guarantee period is changed to the acceptance period. This standard replaces GB 12686-1990 from the date of implementation. This standard is proposed by China Petroleum and Chemical Industry Association. This standard is under the jurisdiction of the National Pesticide Standardization Promotion Technical Committee (CSBTS/TC133). The responsible drafting unit of this standard is Shenyang Chemical Research Institute. The drafting organizations of this standard include Jianjiang Xin'an Chemical Co., Ltd., Haishenglian Chemical Co., Ltd., Fujian Sannong Group Co., Ltd., and Jiangnan Chemical Plant in Zhenjiang, Jiangsu. The main drafters of this standard include Mei Baogui, Li Xiujie, Chen Genliang, Yu Xiangfa, Zhang Xiuzhen, Jiang Fangqiang, Shuai Jianduo, and Xiao Huazhou. This standard was first published in December 1990. This is the first revision of glyphosate technical
Other names, structural formulas, and basic physicochemical parameters of glyphosate, the active ingredient of this product, are as follows: ISO common name: glyphosate
CIPAC digital code: 284
Chemical name; N-phosphinothricin carboxymethylglycine
Structural formula:
HO-P---CH---NH--CH.-
Empirical formula ：C,H.NO.P
Relative molecular weight: 169.07 (according to 2001 international relative atomic mass) Biological activity: Eliminates Sa
Melting point: 189℃～190℃
Vapor pressure (20℃): Negligible
GB12686--2004
Dissolution: Water 11.5g/1.(25℃), insoluble in common organic reagents such as acetone, ethanol and xylene, easy to react with alkaline solution to form water-soluble salts.
Stability: Good stability, no photochemical degradation, stable in air. Scope
This standard specifies the requirements, test methods, marking labels, packaging and storage of glyphosate source drugs. This standard is applicable to glyphosate technical drugs composed of glyphosate and impurities generated in its production. 2 Normative references
The clauses in the following documents become the clauses of this standard through reference in this standard. For any referenced document with a date, all subsequent amendments (excluding errata) or revisions are not applicable to this standard. However, parties that reach an agreement based on this standard are encouraged to study whether the latest versions of these documents can be used. For any undated referenced document, the latest version shall be used for this standard. GB602-1988 Preparation of standard solutions for determination of impurities in chemical reagents GB/T1604 Acceptance rules for commercial pesticides
GB/T1605:2001 Sampling methods for commercial pesticides GB3796 General rules for pesticide packaging
3 Requirements
3.1 Appearance: white powder.
3.2 Glyphosate technical shall meet the requirements of Table 1, GB 12686—2004
Mass fraction of glyceryl film/%
Mass fraction of formaldehyde/(g/kg）
Mass fraction of nitrosoglycin/(ng/kg)Mass fraction of sodium hydroxide insoluble matter?/(mg/kg ... Under the chromatographic operating conditions, the relative difference between the retention time of the main chromatographic peak in the sample solution and the retention time of the glyphosate chromatographic peak in the standard solution should be within 1.5 cm. Infrared spectroscopy - there should be no obvious difference between the infrared absorption spectra of the sample and the standard in the range of 0.90 tm-10 cm-1. The infrared spectrum of the standard sample is shown in Figure 1.
4.3 Determination of glyphosate mass fraction
4.3.1 High performance liquid chromatography (adjudication method)
4.3.1.1 Method summary
Figure 1 Infrared spectrum of glyphosate standard sample
The sample was dissolved in a mobile phase, potassium dihydrogen phosphate aqueous solution at pH 2.0 and methanol were used as the mobile phase, and a stainless steel column (strong ion exchange column) filled with Agilent ZORBAX SAX and a UV detector (l95 nm), and the glyphosate in the sample was separated and determined by high-efficiency phase negative spectrum.
4.3.1.2 Reagents and solutions
Methanol chromatographic grade;
Potassium dihydrogen phosphate:
Water: freshly distilled water;
Phosphoric acid solution: P(H,PO,)=50%;
Glyphosate standard sample: glyphosate mass fraction ≥99.0%, 4.3.1.3 Instruments
High-performance liquid chromatograph: variable wavelength ultraviolet detector; Chromatographic data processor:
GB 12686--2004
Chromatographic column: 250mm×4.6mm inner diameter) Ailent ZORBAX SAX stainless steel column (or other strong anion exchange column equivalent thereto)
Filter: membrane pore size about 0.45um;
Micro-injector: 100μL*
Quantitative injection tube: 20μL;
Use ultrasonic cleaner,
4.3.1.4 High performance liquid chromatography operating conditions
Mobile phase Weigh 13.6 potassium dihydrogen phosphate, dissolve in 850mL water, add 150mL methanol, adjust pH to 2.0 with phosphoric acid solution, ultrasonic oscillate for 10min:
Flow rate, 1. 5 ml/minl
Column temperature, room temperature (temperature difference should not be greater than 2); Detection wavelength: 195 nm
Injection volume: 20m.
Retention time, glyphosate is about 5.7muin.
The above operating parameters are typical. According to the characteristics of different instruments, the given operating parameters can be appropriately adjusted to obtain the best effect. The typical HPLC chromatogram of glyphosate technical is shown in Figure 2.1-Glyphosate.
Figure 2 HPLC chromatogram of glyphosate technical 4.3.1.5 Determination steps
4.3.1.5. Preparation of standard solution
Weigh 0.1g glyphosate standard solution (accurate to 0.0002g), put it in a 50mL container, dilute to the scale with mobile phase, and ultrasonically vibrate for 10 min to dissolve the sample. Cool to room temperature and shake well. 4.3.1.5.2 Preparation of sample solution
Weigh 0.1g of sample containing glyphosate (accurate to 0.0002g), place in a 50mm container, dilute to scale with mobile phase, ultrasonically oscillate for 10 minutes to dissolve the sample, cool to room temperature, and shake. 4.3.1.5, 3 Determination
Under the above operating conditions, after the instrument is stable, continuously inject several injections of standard sample solution until the relative area of two adjacent injections of glyphosate peaks is less than 1.2%, then the determination is carried out in the order of standard solution, sample solution, sample solution, and standard solution. 4.3.1.6 Calculate the mass fraction of glyphosate in the sample (%) according to formula (1): A+m+w
W where:
A1——the average value of the glyphosate peak area in the standard solution; A.--the average value of the glyphosate peak area in the sample solution; m1——the mass of the standard sample, in grams (g); m2——the mass of the sample, in grams (g); L——the mass fraction of glyphosate in the standard sample, %. 4.3.1.7 Allowable difference
The difference between the two parallel determination results of glyphosate mass fraction shall not be greater than 1.2%, and the arithmetic mean shall be taken as the determination result. 4.3.2 Spectrophotometric method
4.3.2.1 Summary of method
After the sample is dissolved in water, it reacts with sodium nitrite in an acidic medium to form nitrosoglyphosate. The absorbance is measured at a wavelength of 2421 nm to calculate the instantaneous mass fraction of glyphosate.
4.3.2.2 Reagents and solutions
Sulfuric acid solution: ΦHSO）-60%:
Potassium bromide solution: 0KBr）=250g/L
Sodium nitrite solution + p(VaNO2)14g/I., prepare when using; Glycyrrhizin standard sample: glycyrrhizin mass fraction ≥99.0%: 4.3.2.3 Apparatus and equipment
Ultraviolet spectrophotometer;
Stone fluorescence color spot: 1 4:tn
4.3.2.4 Determination steps
4.3.2.4.7 Preparation of solution
4.3.2.4.1.1 Preparation of blank solution
Pipette with a pipette? 1. Add 0.5 ml of sulfuric acid solution, 0.1 ml of boiling potassium bromide solution, and 1.5 ml of sodium nitrite solution in a 100 ml volumetric flask, then plug the flask tightly and shake thoroughly. After leaving it for 20 minutes, dilute it with water to the mark and shake thoroughly. Open the flask and leave it for 15 minutes.
4.3.2.4.1.2 Preparation of standard solution
Weigh 0.1 ml of glycyrrhizic acid standard (accurate to 0.0002 g), place it in a 100 ml volumetric flask, dilute it with water to the mark, ultrasonically shake for 10 minutes to dissolve the sample, cool it to room temperature, and shake thoroughly. Use a pipette to transfer 2 ml of the above solution to a 100 ml volumetric flask, add 5 ml of water, 0.5 ml of sulfuric acid solution, 0.1 ml of potassium bromide solution, and 0.5 ml of sodium nitrite solution in turn, plug the flask tightly and shake thoroughly. After 20 minutes, dilute with water to the mark, shake, open the stopper, and place for 15 minutes. 4.3.2.4.1.3 Preparation of sample solution
Weigh a sample containing 0.1g of chloranthate (accurate to 0.0002g) and place it in a 100ml volumetric flask. Dilute with water to the mark, vibrate with an ultrasonic wave GB 12686--2004 for 10 minutes to dissolve the sample, cool to room temperature, mix well, and use a pipette to transfer 2ml of the above solution to a 100ml volumetric flask. Add 5mJ of water, 0.5mL of sulfuric acid solution, 0.1mL of potassium bromide solution, and 0.5ml of sodium nitrite solution in sequence, then plug the stopper tightly and mix well. After 20 minutes, dilute with water to the mark. Shake well. Open the stopper and place for 15 minutes. Note: The nitrosylation reaction temperature cannot be lower than 15℃. 4.3.2.4.2 Determination
Use the convex solution as reference and determine the absorbance of the standard solution and the sample solution at 242nm by quartz colorimetry. 4.3.2.5 Calculate
the glyphosate mass fraction w2 (%) according to formula (2): miA,u
mz·A,
wherein;
A, absorbance of the standard solution;
42——absorbance of the sample solution;
mt—mass of the standard sample, in grams (g); m2—mass of the sample, in grams (g);
-mass fraction of glyphosate in the standard sample, %. 4.3.2,6 Allowable difference
The difference between the results of two parallel determinations of the glyphosate mass fraction shall not be greater than 1.0%. The arithmetic mean shall be taken as the determination result. 4.4 Determination of formaldehyde mass fraction
4.4.1 Method summary
The sample is dissolved in hot water, developed with acetylacetone, and spectrophotometric determination is performed at a wavelength of 412nm. 4.4.2 Reagents and solutions
Acetylacetone: redistilled,
Ammonium acetate;
Glacial acetic acid:
Formaldehyde solution: (formaldehyde) = 0.4. Determine the accurate mass fraction according to Appendix A2 of GBG02-1988; Acetyl lactone solution: weigh 25g of ammonium acetate in a 100ml brown volumetric flask, add 50mL of water to dissolve, add 3mL of glacial acetic acid and 0.5mL of acetylacetone reagent, dilute with water to the scale, shake well: Formaldehyde standard solution: about 10μg/mL Weigh about 2.7g of formaldehyde solution (accurate to 0.0002g), dilute with water to 1000ml, shake well: Use a pipette to take 10 ml of the above solution, dilute it to 1000 ml with water, and stir evenly. 4.4.3 Instruments and equipment
Spectrophotometer
Glass bottle with stopper: 25 ml;
Colorimetric blood; (m
Water bath.
4.4.4 Determination steps
4. 4. 4. 1 Drawing of standard curve
Preparation of blank solution: Use a pipette to take 10 ml of water and 2 Tml of acetylacetone solution in turn into a glass bottle with a stopper, and heat it in boiling water at 100°C for 3 min, take out and cool to room temperature, shake. For the drawing of the standard curve: use a pipette to draw 1mL. 2ml., 6ml., 10ml, 20nl of formaldehyde standard solution and place them in 5 100tnL volumetric flasks, dilute with water to the scale, and shake well. Use a pipette to draw 10ml..L: of the above solution and 2mL of acetyl lactone solution in turn, place them in a cold glass bottle. Heat in boiling water at 100℃ for 3min. Take out and cool to room temperature. Take the blank solution as a reference and measure the absorbance at a wavelength of 412nm. Draw a standard curve with the volume of the fermentation standard solution as the horizontal axis and the absorbance as the vertical axis. GB12686—2004
4. 4. 4. 2 Determination
Weigh 0.1g of glycyrrhizic acid sample (accurate to 0.0002g), cover it in a 100mL volumetric flask, dilute with water to the scale, cover the bottom of the cover and oscillate ultrasonically for 10 1. Dissolve the sample, take it out and cool it to room temperature. Use a pipette to take 10 ml of the above solution and 2 mL of acetylacetone solution, place them in a stoppered glass bottle, heat them in boiling water at 100℃ for 3 minutes, take them out and cool them to room temperature. Take the blank solution as a reference, measure the absorbance of the sample solution at a wavelength of 412nm, and find the corresponding volume of formaldehyde standard solution on the standard curve. 4. 4. 4. 3 Calculate the mass fraction of formaldehyde in the sample (g/kg) according to formula (3): wm.V
Where:
The mass of the formaldehyde solution weighed to prepare the formaldehyde standard solution, in grams (g): V—The volume value of the formaldehyde standard solution corresponding to the measured sample absorbance, in milliliters (mL), which means the mass fraction of dissolved formaldehyde, %;
n——The mass of the sample, in grams (g), 4. 5. Determination of the mass fraction of nitrosoglyphosate 4.5.1 Method summary
The sample was dissolved in a mobile phase, and a pH 2.0 potassium dioxygen phosphate aqueous solution and methanol were used as the mobile phase. Agilent ZORBAX SAX is used as a filler stainless steel column (strong anion exchange column) and a UV detector (242nm) to perform anion exchange liquid chromatography separation and determination of nitrosoglyphosate in the sample.
4.5.2 Reagents and solutionsWww.bzxZ.net
Methanol: color grade;
Potassium dihydrogen phosphate;
Water, freshly distilled and double distilled water:
Phosphoric acid solution: P(H.PO,)-50%:
Nitrosoglyphosate standard sample: known nitrosoglyphosate mass fraction. 4.5.3 Instruments
High performance liquid chromatograph: with variable wavelength UV detector: Chromatographic data processor;
Chromatographic column: 250mm×4.6mm (inner diameter) Agilent ZORBAX SAX stainless steel column (or other strong anion exchange sample equivalent thereto)
Filter, filter membrane diameter is about 0.45μm;
Injector: 1 mL;
Stationary mixing tube: 200μL;
Ultrasonic cleaner.
4.5.4 High performance subtraction chromatography operating conditions
Mobile phase: Weigh 27.2α potassium dihydrogen phosphate, dissolve it in 850ml of water, add 150ml of methanol, adjust the pH to 2.0 with phosphoric acid solution, and oscillate ultrasonically for 10 min;
Flow rate: 1.5 mL/min;
Overflow: room temperature (temperature difference should not exceed 2°C); detection wavelength: 242nm;
Injection volume: 200μL:
Retention time: about 9 min for nitrosoglycin. The above operating parameters are typical. According to the characteristics of different instruments, the given operating parameters can be appropriately adjusted to obtain the best effect. A typical nitrosoglycin HPLC chromatogram is shown in Figure 3. \Nitrosoglycin.
Figure 3 High performance liquid chromatography of nitroso glyphosate 4.5.5 Determination steps
4.5.5.1 Preparation of standard sample
GB12686—2004
Weigh 0.04 μg of nitroso glyphosate standard sample (accurate to 0.000 2g), place it in a 50mL volumetric flask, dilute to scale with water, ultrasonically oscillate for 10min to dissolve the sample, cool to room temperature, and shake well. Use a pipette to draw 1ml of the above solution into a 1000ml volumetric flask, dilute to scale with water, and pipette.
4.5.5.2 Preparation of sample
Weigh 25 μg of sample (accurate to 0.02g), place it in a stoppered glass bottle, add 50mL of water with a pipette, and ultrasonically oscillate for 10min. Cool to room temperature, shake well, and filter.
4.5.5.3 Determination
Under the above operating conditions, wait for the instrument to be calibrated, and continuously inject several needles of standard solution until the relative change in the area of nitrosoglycin between two adjacent needles is less than 70%. Then carry out determination in the order of standard solution, sample solution, sample solution, and standard bath solution. 4.5.6 Calculation The mass fraction of nitrosoglyphosate in the sample (mg/kg) shall be calculated according to formula (4): Where: Az.m:w×1 000 A, is the average value of the area of nitrosoglyphosate in the standard solution, A is the average value of the peak area of nitrosoglyphosate in the sample solution; m is the mass of the standard sample, in grams (g);
is the mass of the sample, in grams);
is the mass fraction of nitrosoglyphosate in the standard sample, %. 4.6 Determination of insoluble matter in sodium hydroxide 4.6.1 Reagents and instruments Sodium hydroxide solution: e(Na2O3)-40 g/L; Conical flask: 250 ml; Glass sand core crucible: G3;
GB 12686--2004
Oven: 105℃-2℃;
Suction filter bottle: 500ml.
4.6.2 Determination method
Weigh 10 g of sample (accurate to 0.01g), put it into a conical flask, add 100 ml of sodium hydroxide solution, heat it in a 90% water bath for 5 ml. Immediately filter it through a vortex filter (accurate to 0.0002g), then wash the conical flask with 61 ml of water three times and filter it by suction. Put the crucible in a drying oven to dry for 2h, take it out and put it in a desiccator to cool, and weigh it (accurate to 0.0002g). 4.6.3 Calculation:
The mass fraction of sodium hydroxide insoluble matter in the test pipe (?k) is calculated according to formula (5): wg -- =m ×1 000
Wherein:
m;—Total mass of wax crucible and sodium hydroxide insolubles after drying, in grams (g); mo-…—Mass of the sample after drying, in grams (g);
4.7 Inspection and acceptance of products
shall comply with the provisions of GB/T1604. For the processing of limit values, the rounded value comparison method shall be adopted. 5 Marking, labeling, packaging and purchase and transportation
5. 1 The marking, labeling and packaging of glyphosate technical shall comply with the provisions of GB3796. 5)
5. 2 Glyphosate technical shall be packaged in clean, dry shrink-woven bags lined with plastic bags, with a net content of 25 kg per bag. Other forms of packaging can also be used according to user requirements or order agreements, but they must comply with the provisions of GB3796. 5.3 The packaging of glyphosate technical should be stored in a ventilated and dry warehouse. 5.4 During storage and transportation, strictly prevent moisture and sunlight, do not mix with food, seeds, and feed, avoid contact with skin and eyes, and prevent inhalation from the mouth. 5.5 Safety: Glyphosate is a low-grade mold herbicide. If the skin and eyes come into contact with the drug solution, rinse with plenty of water. The flushing time should not be less than 15 minutes, and ask a doctor for diagnosis and treatment: If accidentally taken, induce vomiting immediately. 5.6 Acceptance period: The acceptance period of glyphosate technical is 1 month. From the date of delivery, the product quality acceptance shall be completed within one month, and all its indicators shall meet the standard requirements.Glyphosate is a low-grade mold-resistant herbicide. If the skin or eyes come into contact with the liquid, rinse with plenty of water. The flushing time should not be less than 15 minutes, and consult a doctor: If ingested by mistake, induce vomiting immediately. 5.6 Acceptance period: The acceptance period for glyphosate technical is 1 month. From the date of delivery, the product quality acceptance should be completed within one month, and all indicators should meet the standard requirements.Glyphosate is a low-grade mold-resistant herbicide. If the skin or eyes come into contact with the liquid, rinse with plenty of water. The flushing time should not be less than 15 minutes, and consult a doctor: If ingested by mistake, induce vomiting immediately. 5.6 Acceptance period: The acceptance period for glyphosate technical is 1 month. From the date of delivery, the product quality acceptance should be completed within one month, and all indicators should meet the standard requirements.
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