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HJ 1055-2019Soil and sediment -- Determination of glyphosate -- High performance liquid chromatography (English PDF)

土壤和沉积物草甘膦的测定高效液相色谱法

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Issued by

Ministry of Ecology and Environment

Level / Type

National · Mandatory

Issue date

January 1, 1970

Implementation date

April 24, 2020

Scope

HJ 1055-2019 is the English-translated version of 土壤和沉积物草甘膦的测定高效液相色谱法.

HJ 1055-2019 — This standard specifies HPLC for the determination of glyphosate in soil and sediment. This standard applies to the determination of glyphosate in soil and sediment.

When the sample size is 10 g (dry weight), the detection limit of this method is 0.02 mg/kg, and the lower detection limit is 0.08 mg/kg.

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Document preview — HJ 1055-2019

National Standard of the People's Republic of China

ICS: 13.080
Classification: Z 18

Issued by: Ministry of Ecology and Environment

Foreword
1 Scope
2 Normative references
3 Methodology
4 Reagents and materials
5 Instruments and equipment
6 Sample
7 Analysis steps
8 Calculation and Representation of Results
9 Precision and accuracy
10 Quality Assurance and Quality Control
11 Waste disposal
Appendix A (informative) Precision and accuracy of the method

Foreword

In order to implement the "Environmental Protection Law of the People's Republic of China" Environment, protect human health, standardize the determination of glyphosate in soil and sediment, and formulate this standard.

This standard specifies HPLC for the determination of glyphosate in soil and sediment.

This standard is issued for the first time.

This standard is formulated by the Department of Eco-Environmental Monitoring, Laws and Standards Department of the Ministry of Ecology and Environment.

This standard was drafted. Nanjing Institute of Environmental Sciences, Ministry of Ecology and Environment.

Verification units of this standard. Jiangsu Environmental Monitoring Center, Jiangsu Environmental Monitoring Center, Changzhou Environmental Monitoring Center, Jiangsu Province Measurement Center, Zhenjiang Environmental Monitoring Center, Jiangsu Province, Hulunbuir Environmental Monitoring Center Station, Nanning Ecology, Guangxi Zhuang Autonomous Region Environmental Monitoring Center.

This standard was approved by the Ministry of Ecology and Environment on October 24, 2019.

This standard will be implemented from April 24, 2020.

This standard is explained by the Ministry of Ecology and Environment.

Determination of glyphosate in soil and sediment by high performance liquid chromatography Warning. The solvents and standard solutions used in the experiment are toxic and hazardous substances. Solution preparation and sample preparation should be performed in it should be carried out in a fume hood. Protective equipment should be worn during operation to avoid contact with skin and clothing.

1 Scope

This standard specifies HPLC for the determination of glyphosate in soil and sediment.

This standard applies to the determination of glyphosate in soil and sediment.

When the sample size is 10 g (dry weight), the detection limit of this method is 0.02 mg/kg, and the lower detection limit is 0.08 mg/kg.

2 Normative references

This standard refers to the following documents or clauses therein. For undated references, the valid version applies to this standard.

GB 17378.3 Marine Monitoring Code Part 3. Sample Collection, Storage and Transportation GB 17378.5 Code for Marine Monitoring Part 5. Sediment Analysis HJ 494 Water Quality Sampling Technical Guide HJ 495 Water Quality Sampling Scheme Design Technical Regulations HJ 613 Soil dry matter and moisture determination by gravimetric method HJ/T 91 Technical specifications for surface water and sewage monitoring HJ/T 166 Technical Specifications for Soil Environmental Monitoring

3 Method principle

Glyphosate in soil and sediment was extracted with a mixed aqueous solution of sodium phosphate and sodium citrate.

Extracted and purified by n-hexane under weak alkaline conditions. The aqueous phase was derivatized with 9-fluorenylmethylchloroformate (FMOC-Cl), and then Separation and Detection of Glyphosate-FMOC Derivatives by High Performance Liquid Chromatography with Fluorescence Detector Between qualitative and external standard method.

4 Reagents and materials

Unless otherwise specified, analytical reagents that meet national standards are used in the analysis, and the experimental water is freshly prepared distillation Water or pure water without the target compound.

4.1 Acetonitrile (CH3CN). pure liquid chromatography.

4.2 n-hexane (C6H14).

4.3 Hydrochloric acid (HCl). rho (HCl) = 1.19 g/ml.

4.4 Hydrochloric acid solution. 1 1.

Hydrochloric acid (4.3) and water were mixed in a volume ratio of 1. 1.

4.5 Phosphoric acid (H3PO4). phi (H3PO4) = 85.0%.

4.6 Phosphoric acid solution. phi (H3PO4) = 0.2%.

Accurately measure 2.35 ml of phosphoric acid (4.5) into a 1 L volumetric flask, make up to volume with water, shake well, and use it immediately before use.

4.7 Sodium phosphate dodecahydrate (Na3PO4 · 12H2O).

4.8 Sodium citrate dihydrate (Na3C6H5O7 · 2H2O).

4.9 Mixed extraction solution of sodium phosphate and sodium citrate. c (Na3PO4 · 12H2O) = 0.03 mol/L, c (Na3C6H5O7 · 2H2O) = 0.01 mol/L.

Weigh accurately 11.40 g (accurate to 0.01 g) sodium phosphate dodecahydrate (4.7) and 2.94 g (accurate to 0.01 g) Hydrate trisodium citrate (4.8), dissolve in water and make up to a 1 L volumetric flask.

4.10 Sodium tetraborate decahydrate (Na2B4O7 · 10H2O).

4.11 Sodium tetraborate solution. c (Na2B4O7 · 10H2O) = 0.05 mol/L.

Accurately weigh 1.91 g (accurate to 0.01 g) sodium tetraborate decahydrate (4.10), dissolve in water and make up to 100 ml Volumetric flask.

4.12 9-fluorenyl methyl chloroformate (C15H11ClO2, FMOC-Cl). purity is not less than 99%, refrigerate below 4 °C, avoid Light save.

4.13 9-fluorenyl methyl chloroformate solution. rho (C15H11ClO2) = 1.0 mg/ml.

Accurately weigh 50.0 mg (accurate to 0.1 mg) of 9-fluorenylmethyl chloroformate (4.12), dissolve with acetonitrile (4.1) and Make up to a 50 ml volumetric flask, shake well, transfer to a compact bottle and refrigerate below 4 ° C, save from light.

4.14 Glyphosate standard stock solution. rho (C3H8NO5P) = 100 mg/L.

Commercially available certified standard solutions can be used directly or formulated with standard materials. Weigh accurately 10.0 mg (to the nearest 0.1 mg) Glyphosate standard material, dissolved in water and made up to a 100 ml volumetric flask, shake well, transfer to a compact bottle and refrigerate below 4 ° C Save for 2 months.

4.15 Glyphosate standard solution. rho (C3H8NO5P) = 10.0 mg/L.

Transfer 1.0 ml glyphosate standard stock solution (4.14) into a 10 ml volumetric flask, dilute with water and make up to volume, shake Evenly transferred to a compact bottle and stored under refrigeration at 4 ° C. The storage period is 2 months.

4.16 Quartz sand. The particle size is 0.7-0.3 mm (25-50 mesh).

4.17 Syringe filter. 0.22 µm. The material of the filter membrane is polytetrafluoroethylene or other equivalent materials.

4.18 Filter paper. medium speed filter paper, cotton fiber material.

5 Instruments and equipment

5.1 Liquid chromatograph. It has a gradient elution function, the temperature of the column oven can be controlled, and it is equipped with a fluorescence detector.

5.2 Chromatographic column. The packing is octadecylsilane bonded silica gel, the particle size is 5 µm, the column length is 250 mm, and the inner diameter is 4.6 mm.

Column or other equivalent column.

5.3 Centrifuge tube. polypropylene (PP) material, 50 ml.

5.4 Ultrasonic cleaner. The ultrasonic power is 500 ~ 700 W.

5.5 High-speed centrifuge. Speed range is 8000 ~ 12000 r/min.

5.6 Analytical balance. The sensitivity is 0.1 mg.

5.7 Mixer.

5.8 General laboratory instruments and equipment.

6 Samples

6.1 Sample collection and storage

Collect and store soil samples in accordance with the relevant requirements of HJ/T 166, in accordance with GB 17378.3, GB 17378.5, HJ 494, HJ 495 and HJ/T 91 require the collection and storage of sediment samples.

The samples should be sealed, protected from light, refrigerated, transported and stored below 4 ° C. Soil samples should be pre-treated and deposited within 7 days Samples should be pre-treated within 3 days.

6.2 Preparation of samples

Soil samples. Weigh two fresh samples, one for dry matter content and one for dry matter the amount should be greater than 10 g) for the determination of the target glyphosate.

Sediment samples. Centrifuge for 10 minutes with a high-speed centrifuge (5.5) to remove interstitial water, and then weigh two fresh samples.

One sample is used to determine the moisture content, and the other sample (the dry matter content should be greater than 10 g) is used to determine the target glyphosate.

6.3 Determination of moisture

The dry matter content of soil samples was measured according to HJ 613, and the moisture content of sediment samples was measured according to GB 17378.5.

set.

6.4 Preparation of test specimens

6.4.1 Extraction

Transfer the entire sample (6.2) to a 50 ml centrifuge tube and add 50.0 ml of a mixed extract of sodium phosphate and sodium citrate (4.9), ultrasonic extraction for 30 min, centrifugation with high-speed centrifuge (5.5) for 5 min, take the supernatant and filter with filter paper (4.18), to be purified.

6.4.2 Purification

The extraction solution (6.4.1) was first adjusted to pH 9 with a hydrochloric acid solution (4.4), and allowed to stand for 10 minutes, then filtered through filter paper (4.18) Add 50 ml of n-hexane (4.2), leave it to stand after shaking, discard the organic phase, and use 50 ml of n-hexane (4.2) for the water phase.

Extract once.

6.4.3 Derivation

Take 1.00 ml of purified water solution (6.4.2) into a 1.5 ml polyethylene plastic tube and add 0.12 ml of sodium tetraborate Solution (4.11) and 0.2 ml 9-fluorenyl methyl chloroformate solution (4.13), derivatized with a mixer (5.7) at room temperature for 4 h, Filtered with a needle filter (4.17) before testing.

6.5 Preparation of blank sample

Use quartz sand (4.16) instead of the sample, and follow the same steps as the sample preparation (6.4) to prepare a blank sample.

7 Analysis steps

7.1 Measurement reference conditions

Mobile phase A. acetonitrile; mobile phase B. phosphoric acid solution (4.6);

Flow rate. 1.0 ml/min.

Column temperature. 35 ° C.

Injection volume. 20 µl.

Excitation wavelength. 254 nm; emission wavelength. 301 nm.

Table 1 Gradient elution procedure

Time (min) Mobile phase A (%) Mobile phase B (%)

7.2 Establishment of working curve

Pipette different volumes of standard use solution (4.15) and dilute with water to prepare a standard series of at least 5 concentration points, grass Glyphosate has a mass concentration of 10.0 µg/L, 20.0 µg/L, 50.0 µg/L, 100 µg/L,.200 µg/L, and 500 µg/L (see Test concentration). Derivation according to step 6.4.3, to be tested.

According to the instrument measurement reference conditions (7.1), the samples were injected in order from low to high, with the glyphosate concentration as the abscissa and the peak area (peak height) is the ordinate, and a working curve is established. The reference chromatogram of the glyphosate derivative is shown in Figure 1.

Figure 1 Reference chromatogram of glyphosate derivative

7.3 Sample determination

Test the sample (6.4) under the same conditions (7.2) as the working curve.

7.4 Blank test

The blank sample (6.5) was measured under the same conditions as the sample measurement (7.3).

8 Results calculation and representation

8.1 Qualitative analysis

Characterized by the retention time (RT) of the target compound in the sample. Retention times and expectations of target compounds in samples the relative deviation of the retention time (ie the average relative retention time in the standard solution) should be controlled within ± 5%. If necessary the method of adding the target compound to the sample is used to assist the characterization.

8.2 Calculation of results

8.2.1 Calculation of results in soil samples

The moisture content of fresh soil samples is calculated according to formula (1).

1 (1) dm

Where. Vs--water content of fresh soil sample, ml;

m1--sample mass (wet weight), g;

wdm-dry matter content in soil sample,%;

rhoH2O-density of water at -20 ° C, g/ml.

The glyphosate concentration (mg/kg) in the soil sample is calculated according to formula (2).

× × 1000

rho VV

In the formula. w1-target concentration in soil sample, mg/kg;

rho1--the concentration of glyphosate calculated from the working curve, µg/L;

Vs--water content of fresh soil sample, ml;

V1--extract volume, ml;

m1--sample mass (wet weight), g;

wdm-dry matter content in soil sample,%.

8.2.2 Calculation of results in sediment samples

The water content of the fresh sediment sample is calculated according to formula (3).

2 HO

Where. Vsd--water content of fresh sediment sample, ml;

M2-- sample mass (wet weight), g;

wH2O--water content of sediment sample,%;

rhoH2O-density of water at -20 ° C, g/ml.

The concentration of glyphosate (mg/kg) in the sediment sample is calculated according to formula (4).

twenty two

(1) 1000

rho VV

Where. w2-- concentration of glyphosate in sediment sample, mg/kg;

rho2--concentration of glyphosate calculated from the working curve, µg/L;

Vsd--water content of sediment sample, ml;

V2-extraction volume, ml;

m2-sample weight (wet weight), g;

wH2O--Moisture content of sediment sample,%.

8.3 Representation of results

The number of digits after the decimal point in the measurement result is the same as the detection limit of the method. A maximum of three significant digits are retained.

9 Precision and accuracy

9.1 Precision

Six laboratories performed uniform samples with glyphosate concentrations of 0.100 mg/kg, 0.500 mg/kg, and 1.00 mg/kg Measurement. The relative standard deviations in the laboratory were 3.3% ~ 12%, 1.6% ~ 11%, and 2.7% ~ 12%, respectively.

The quasi deviations were 3.4% ~ 7.8%, 3.4% ~ 12%, and 4.0% ~ 11%, respectively; the repeatability limits were 0.014 ~ 0.019 mg/kg, 0.066 ~ 0.094 mg/kg and 0.11 ~ 0.17 mg/kg; the reproducibility limits are 0.018 ~ 0.026 mg/kg, 0.076 ~ 0.17 mg/kg and 0.17 ~ 0.29 mg/kg.

See Appendix A for method precision data.

9.2 Accuracy

Six laboratories have performed unified sampling of glyphosate at concentrations of 0.100 mg/kg, 0.500 mg/kg and 1.00 mg/kg Analytical determination. The spiked recovery ranges were 71.0% ~ 109%, 73.6% ~ 106%, and 68.3% ~ 109%. Mark back the final yields are. 79.6% ± 12% ~ 102% ± 13%, 77.3% ± 5.6% ~ 100% ± 8.6%, and 75.5% ± 9.4% ~ 100% ± 12%.

See Appendix A for method accuracy summary data.

10 Quality Assurance and Quality Control

10.1 Blank test

At least one blank test shall be performed for each batch of samples, and the blank value shall not exceed the detection limit of the method.

10.2 Calibration

When the instrument is used for the first time or when the instrument is repaired, the column is replaced, or the calibration is not qualified, a working curve and correlation coefficient should be established.

Should be >=0.995. Every 20 samples or each batch of samples (<= 20 samples/batch) should be measured in the middle concentration point of a working curve the relative error between the measurement result and the concentration of the quasi-solution should be within ± 20%.

10.3 Parallel samples

At least 10% of the duplicate samples should be measured for each batch of samples. When the number of samples is less than 10, at least one parallel sample should be measured.

The relative deviation of the measurement results of the sample shall be <=20%.

10.4 Matrix Spiking

Every 20 samples or each batch (<=20 samples/batch) should be spiked with a matrix, and the recovery range of the spike should be within 60% ~ 120%.

11 Waste treatment

All waste liquid and waste generated in the experiment should be collected separately, placed in a closed container for centralized storage, and marked with obvious signs.

Entrust a qualified unit for disposal.

Appendix A

(Informative appendix) Method precision and accuracy the precision and accuracy of the methods are listed in Tables A.1 and A.2.

Table A.1 Summary of method precision

Matrix type

Spiked concentration (Mg/kg) average value (Mg/kg) Relative in the laboratory standard deviation(%) Interlaboratory standard deviation(%) Repeatability limit r (Mg/kg) Reproducibility limit R (Mg/kg) Red soil 0.10 0.10 3.4 ~ 8.4 7.8 0.016 0.026 0.50 0.47 1.8 ~ 8.7 7.4 0.073 0.12 1.00 0.94 2.7 ~ 6.5 11 0.11 0.29 Paddy soil 0.10 0.091 3.6 ~ 7.8 4.9 0.014 0.018 0.50 0.46 1.6 ~ 8.3 12 0.086 0.17 1.00 0.90 2.7 ~ 9 7.7 0.14 0.23 Black soil 0.10 0.085 5.5 ~ 8.6 7.4 0.017 0.023 0.50 0.42 3.8 ~ 7.6 3.7 0.069 0.076 1.00 0.83 3.2 ~ 9.3 4.0 0.16 0.17 Lake sink Accumulation 0.10 0.081 5.7 ~ 10 7.7 0.019 0.025 0.50 0.39 5.9 ~ 11 3.4 0.094 0.094 1.00 0.76 2.7 ~ 8 6.2 0.13 0.18 River sink Accumulation 0.10 0.084 3.3 ~ 12 3.4 0.018 0.018 0.50 0.40 4.4 ~ 6.9 5.7 0.066 0.12 1.00 0.80 3.4 ~ 12 5.7 0.17 0.20

Table A.2 Summary of method accuracy

Matrix type

Spiked concentration (Mg/kg) Spike recovery range Around (%) Spike recovery Mean P (%) Spike recovery standard deviation S (%) Final spike recovery SP 2+/- (%) Red soil 0.10 91.9 ~ 109 102 6.3 102 ± 13 0.50 93.1 ~ 106 100 4.3 100 ± 8.6 1.00 90.6 ~ 109 100 5.8 100 ± 12 Paddy soil 0.10 87.5 ~ 92.3 89.0 1.8 89.0 ± 3.7 0.50 84.0 ~ 93.3 87.9 3.6 87.9 ± 7.3 1.00 81.3 ~ 86.5 84.3 2.0 84.3 ± 4.0 Black soil 0.10 76.5 ~ 85.1 82.2 3.1 82.2 ± 6.2 0.50 73.6 ~ 84.4 79.5 3.9 79.5 ± 7.8 1.00 74.3 ~ 86.0 78.5 4.2 78.5 ± 8.5 Lake sink Accumulation 0.10 71.0 ~ 88.9 79.6 6.2 79.6 ± 12 0.50 74.1 ~ 81.1 77.3 2.8 77.3 ± 5.6 1.00 68.3 ~ 80.6 75.5 4.7 75.5 ± 9.4 River sink Accumulation 0.10 77.6 ~ 87.5 84.2 3.8 84.2 ± 7.6 0.50 75.6 ~ 89.3 80.9 4.9 80.9 ± 9.8 1.00 75.3 ~ 88.4 79.7 4.9 79.7 ± 9.8

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This preview omits tables, figures, formulas and parts of the technical clauses. The complete document — 9 pages — is available in the English PDF.

Referenced standards

Normative references

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