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HJ 914-2017Water quality--Determination of paraquat and diquat--Solid phase extraction high performance liquid chromatography (English PDF)

水质百草枯和杀草快的测定固相萃取-高效液相色谱法

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Issued by

Ministry of Ecology and Environment

Level / Type

National · Mandatory

Issue date

December 28, 2017

Implementation date

April 1, 2018

Scope

HJ 914-2017 is the English-translated version of 水质百草枯和杀草快的测定固相萃取-高效液相色谱法.

HJ 914-2017 — This standard specifies the determination of paraquat in water and herbicides fast solid phase extraction - high performance liquid chromatography.

This standard applies to the surface water, groundwater and waste water paraquat and grass quick determination.

When the sample volume is 500 ml, the sample volume is 1.0 ml and the injection volume is 50 µl, the detection limit of paraquat is 0.3 µg/L, the lower limit of determination was 1.2 µg/L; the fast limit of detection was 0.4 µg/L and the lower limit of determination was 1.6 µg/L.

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Document preview — HJ 914-2017

National Standard of the People's Republic of China

Classification: Z 16

Issued by: Ministry of Ecology and Environment

Foreword .ii
1 Scope of application .1
2 Normative references .1
3 Method principle .1
4 Interference and elimination .1
5 Reagents and materials .1
6 Instruments and equipment .2
7 Samples .3
8 Analysis steps .3
9 Results Calculation and Presentation .4
10 Precision and accuracy
11 Quality Assurance and Quality Control .5
12 Waste treatment
13 Matters needing attention
Appendix A (informative) method of precision and accuracy
Appendix B (Informative) Direct injection - HPLC Determination of water quality paraquat and grass fast

Foreword

In order to implement the "Law of the People's Republic of China on Environmental Protection" and the "Law of the People's Republic of China on Prevention and Control of Water Pollution", protect the environment, Protection of human health, regulating paraquat and grass quick determination of water methods, the development of this standard.

This standard specifies the determination of surface water, groundwater and wastewater paraquat and grass fast solid phase extraction - high performance liquid chromatography.

This standard Appendix A, Appendix B is an informative annex.

This standard is released for the first time.

This standard by the Environmental Protection Department of Environmental Monitoring Division and Science and Technology Standards Division to develop.

This standard was drafted. Zhejiang Provincial Environmental Monitoring Center.

This standard verification unit. Jiangsu Provincial Environmental Monitoring Center, Zhejiang Marine Environmental Monitoring Station in Zhoushan, Hangzhou City Environment Monitoring Center Station, Suzhou City Environmental Monitoring Center, Shaoxing City Environmental Monitoring Center Station and Jiaxing City Environmental Protection Monitoring Station.

This standard MEP approved on December 28, this standard since April 1, 2018 come into operation.

This standard is interpreted by the MEP.

Water quality - Determination of paraquat and benzalkonium bromide - Solid phase extraction - High performance liquid chromatography Warning. The solvents and standard solutions used in the experiment are harmful to human health. Solution preparation and sample preparation should be performed at Fume hood, and wear protective equipment as required to avoid contact with skin and clothing.

1 Scope of application

This standard specifies the determination of paraquat in water and herbicides fast solid phase extraction - high performance liquid chromatography.

This standard applies to the surface water, groundwater and waste water paraquat and grass quick determination.

2 Normative references

This standard references the following documents or the terms. For undated references, the effective version applies to this standard.

HJ/T 91 Technical Specifications for Surface Water and Wastewater Monitoring HJ/T 164 Groundwater Environmental Monitoring Technical Specifications

3 Method principle

Paraquat and herbicides in water samples are enriched in weak cation-exchange SPE cartridges and eluted with formic acid in acetonitrile After separation by liquid chromatography, UV detector detection, according to retention time qualitative, external standard method.

4 Interference and elimination

4.1 For water samples with high salinity, in order to avoid penetration of solid phase extraction column, the sampling volume can be reduced, and the water samples can be diluted or collected Enrich with larger capacity solid phase extraction cartridge.

4.2 Determination of material interference with similar retention time, by changing the mobile phase to improve the resolution; can also be used standard solution Liquid addition method, the absorption ratio under different wavelengths, UV absorption spectroscopy to assist the qualitative comparison.

5 Reagents and materials

Unless otherwise specified, the analysis of the use of analytical reagents in line with national standards, experimental water for the absence of the target Ionized water.

5.1 Acetonitrile (CH3CN). Liquid chromatography pure.

5.2 methanol (CH3OH). liquid chromatography pure.

5.3 Formic acid (HCOOH). liquid chromatography pure.

5.4 Formic acid ammonium (HCOONH4). excellent grade pure.

5.5 Sulfuric acid (H2SO4). p = 1.84 g/ml.

5.6 Sodium thiosulfate (Na2S2O3 · 5H2O). excellent grade pure.

5.7 Sodium hydroxide (NaOH).

5.8 sulfuric acid solution. 1 1.

Take 50 ml of sulfuric acid (5.5) and slowly add 50 ml of water.

5.9 Sodium hydroxide solution. p = 0.4 g/ml.

Weigh 40 g sodium hydroxide (5.7) dissolved in water, set the volume to 100 ml.

5.10 methanol solution. 1 1.

Separately take 50 ml of methanol (5.2) and 50 ml of water, and mix well.

5.11 ammonium formate solution. pH = 2 ~ 3.

Weigh 12.6 g of ammonium formate (5.4) dissolved in water, add 20 ml of formic acid (5.3), and dilute to 1000 ml with water.

5.12 containing 2% formic acid in acetonitrile.

Take 2 ml of formic acid (5.3) and 98 ml of acetonitrile (5.1) respectively, and mix well.

5.13 standard stock solution. rho = 100 mg/L.

Direct purchase of commercial paraquat (C12H14Cl2N2, CAS NO.1910-42-5) and quick kill grass (C12H12Br2N2, CAS NO.85-00-7) certified standard solution, according to the standard solution certificate requirements.

5.14 standard solution. rho = 10.0 mg/L.

Take 500 µl standard stock solution (5.13) in a 5 ml volumetric flask (polypropylene or polyvinyl chloride), dissolve in methanol Liquid (5.10) constant volume, mix, placed in -18 °C refrigerator, sealed, protected from light, shelf life of 6 months.

5.15 SPE Columns. Weak Cation Exchange Columns (150 mg/6.0 ml or 500 mg/6.0 ml) or other similar properties Solid phase extraction column.

5.16 Nitrogen. Purity >=99.999%.

5.17 Filter. 0.45 µm nylon membrane.

6 Instruments and equipment

6.1 liquid chromatography (HPLC).

6.1.1 tunable wavelength UV detector or diode array detector.

6.1.2 Column. Hydrophilic liquid chromatography column (HILIC) with a column length of 25 cm, an inner diameter of 4.6 mm and a particle size of 5 µm.

Or other similar performance of the column.

6.1.3 Injector. Manual or autosampler, injection volume 5 µl ~ 50 µl.

6.1.4 Oven.

6.1.5 Vials. Polyvinyl chloride or polypropylene.

6.2 solid-phase extraction device. automatic or manual, adjustable flow rate. 10 ml polyvinyl chloride or polypropylene eluent receiver tube.

6.3 pH meter. accurate to 1 decimal place.

6.4 Concentration device. nitrogen purifier or other types of performance-equivalent equipment.

6.5 General laboratory equipment and equipment.

7 Samples

7.1 Sample Collection and Storage

Samples were collected using a sample bottle of polyvinyl chloride or polypropylene according to HJ/T 91 and HJ/T 164 0 ~ 4 °C dark preservation, extraction completed within 7 d, 21 d after extraction to complete the analysis. When the water sample pH > 9, the application of sulfuric acid Liquid (5.8) Adjust the pH of the water sample to neutral. Add sodium thiosulfate (5.6) when the sample contains residual chlorine. Add 0.1 g per liter of water.

7.2 Sample Preparation

7.2.1 Filtering

The water sample is filtered with a filter (5.17) and placed in a sampling bottle.

7.2.2 Solid phase extraction

The pH of the water sample is adjusted to 6-7 with sulfuric acid solution (5.8) or sodium hydroxide solution (5.9), followed by 4 ml of methanol (5.2), Water Activate the SPE column (5.15) at a rate of 1 drop/s (~ 3 ml/min) and ensure that the column packing the surface does not reveal the liquid level. Take 500 ml filtered water sample (7.2.1) (based on the appropriate concentration of target and other cations in the water sample Reduce the sampling volume), adjust the flow so that the water sample to 2 ml/min ~ 5 ml/min speed through the extraction column, the column packing just Before exposure to air, rinse with 2 ml of water, 2 ml of methanol (5.2), and the effluent discarded. Then 5 ml containing 2% Formic acid in acetonitrile (5.12) eluted at 1 drop/s (about 3 ml/min) SPE cartridge, the eluate was collected in the wash Detach the receiver tube, constant volume, to be measured, if necessary, continue to 7.2.3.

Note 1. Penetrating experiments should be performed on unknown samples of the same matrix to determine the appropriate sampling volume. The method is as follows. Use solid Phase extraction cartridges (150 mg/6.0 ml) are enriched with the same water sample of different volumes (eg 100 ml,.200 ml and 400 ml) as in the latter assay Fruit less than 30% of the former, indicating that the latter is too large volume of water-rich samples, solid-phase extraction column has penetrated, should be appropriate to reduce the sampling volume, the water sample dilution or use a larger SPE column (eg 500 mg/6.0 ml) to enrich the sample.

Note 2. For samples with high target content ( > 0.1mg/L), the sample can be directly injected into the filter after filtration.

7.2.3 Concentration

Concentrate the eluate to a volume of 1.0 ml with a concentrating device (6.4) and transfer to a vial (6.1.5) to be tested.

7.3 Blank sample preparation

Replace the sample with experimental water, and follow the same procedure as sample preparation (7.2) to prepare laboratory blank samples.

8 Analysis steps

8.1 Measurement conditions

Mobile phase. ammonium formate solution (5.11)/acetonitrile (5.1) = 6/4 (V/V); flow rate. 1.0 ml/min;

Injection volume. 50 µl; detection wavelength. Paraquat quantitative wavelength of 257 nm, auxiliary qualitative wavelength of 290 nm;

The amount of wavelength is 309 nm, the auxiliary qualitative wavelength is 290 nm.

8.2 Calibration curve establishment

Pipette a certain amount of standard solution (5.14), with 2% formic acid in acetonitrile (5.12) diluted to volume in polyvinyl chloride or polypropylene volumetric flask, a standard series of at least 5 concentration points is prepared, the standard series concentrations are 0.5 mg/L, 1.0 mg/L, 2.0 mg/L, 5.0 mg/L and 10.0 mg/L (this is the reference concentration). From low concentration to high concentration in turn on the standard line Column solution injection, according to the measurement conditions (8.1) analysis. The standard series of solutions in the concentration of the target as abscissa, with its corresponding the peak height or peak area for the vertical axis, the establishment of the calibration curve.

Note. The standard series of solutions by sub-placed in -18 °C refrigerator, sealed, protected from light, can be stored for 6 months.

8.3 Sample Determination

The same procedure as used in the calibration curve (8.2) was used to determine the sample (7.2).

8.4 Blank test

The blank sample (7.3) was measured according to the same procedure as the sample measurement (8.3).

9 Results calculated and expressed

9.1 Qualitative analysis

According to the retention time of the target qualitative. Under the same chromatographic conditions, the sample in the target retention time and standard solution the relative retention time of this component should be less than 2.5%. If necessary, the standard solution to add law, the absorption of different wavelengths Income ratio and UV absorption spectra to help qualitative.

In the standard conditions of measurement (8.1), 1.0 mg/L paraquat and herbicide fast standard solution chromatogram shown in Figure 1.

1 - herbicide fast, absorption wavelength of 309nm; 2 paraquat, absorption wavelength of 257nm

Figure 1 standard solution chromatogram

9.2 Results Calculation

The mass concentration of the target in the sample is calculated according to equation (1).

2 V - sample volume, ml;

1 V - volume of water-rich sample, ml.

9.3 Results show

When the test result is less than 10 µg/L, keep 1 decimal place; when the test result is greater than or equal to 10 µg/L, Leave 3 significant digits.

10 Precision and accuracy

10.1 Precision

In six laboratories, groundwater, surface water, wastewater containing paraquat concentrations of 2.5 µg/L, 20.0 µg/L and 100 µg/L the samples were measured 6 times repeatedly, and the relative standard deviations in the laboratory were 6.2% ~ 14%, 4.3% ~ 12%, 1.7% ~ the relative standard deviations (RSDs) were 9.8%, 8.9% and 6.1% respectively. The repeatability limits were 0.6 µg/L, 5.0 µg/L, 17 µg/L; reproducibility limits. 0.7 µg/L, 6.5 µg/L, 23 µg/L.

In six laboratories, groundwater, surface water, wastewater containing 2.5 g/L, 20.0 µg/L and 100 µg/L the samples were measured 6 times repeatedly, the relative standard deviations in the laboratory were 7.2% ~ 12%, 5.0% ~ 15%, 2.7% ~ the relative standard deviations (RSDs) were 8.8%, 9.8% and 5.2%, respectively. The repeatability limits were 0.6 µg/L, 4.7 µg/L, 17 µg/L; reproducibility limits. 0.8 µg/L, 6.8 µg/L, 19 µg/L.

The result of precision is shown in Appendix A.

10.2 Accuracy

Six laboratories spiked actual samples of groundwater, surface water, and wastewater that contained less than the detection limit of paraquat the recoveries were in the range of 70.4% -90.7%, respectively, with the spiked concentrations of 2.5 µg/L, 20.0 µg/L and 100 µg/L, respectively.

83.0% ~ 105% and 91.3% ~ 107%, respectively. The final recoveries were 76.1% ± 15%, 90.9% ± 16% and 99.5% ± 12%.

Six laboratories spiked actual samples of groundwater, surface water and waste water containing less than the detection limit the recoveries were 2.5%, 20.0% and 100%, respectively. The recoveries were 82.0% -104% 82.0% ~ 111% and 74.1% ~ 83.3%, respectively. The final recoveries were 89.5% ± 16%, 95.5% ± 19% and 77.7% ± 8.0%.

The result of accuracy is shown in Appendix A.

11 Quality Assurance and Quality Control

11.1 Blank test

Analyze at least 1 lab blank every 20 samples or batches (less than 20), blank test results should be less than square Law detection limit.

11.2 Calibration

Correlation coefficient calibration curve >= 0.955, or re-calibration.

Select the calibration curve of the intermediate concentration point for continuous calibration, each analysis of 20 samples or batches (less than 20 samples) Perform a continuous calibration, the relative deviation of the measurement results should be <= 20%, otherwise re-establish the calibration curve.

11.3 Parallel samples

At least 1 parallel sample was analyzed for every 20 samples or batches (less than 20) with a relative bias of <=30% for parallel samples.

11.4 Substrate spiking

Analyze at least 1 matrix spike sample every 20 samples or batches (less than 20) with a recovery of 60% -120% between.

12 Waste treatment

The waste liquid generated in the experiment should be collected intensively and correspondingly identified, commissioned by a qualified unit for processing.

13 Precautions

Do not use glassware and consumables during sample collection, pre-treatment and analysis.

Appendix A.

(Informative)

Method precision and accuracy Using solid-phase extraction enrichment, determination of the precision and accuracy of the three types of spiked water samples, precision results are shown in the table A.1, method accuracy results in Table A.2.

Table A.1 Six laboratories by solid phase extraction precision (n = 6)

Sample type target

average value

(Mg/L)

Laboratory relative

standard deviation(%) Relative between laboratories standard deviation(%) Repeatability r (Mg/L) Reproducibility limit R (Mg/L) groundwater Paraquat 1.9 6.2 ~ 14 9.8 0.6 0.7 Quick kill 2.2 7.2 ~ 12 8.8 0.6 0.8 Surface water Paraquat 18.2 4.3 ~ 12 8.9 5.0 6.5 Grass quick 19.1 5.0 ~ 15 9.8 4.7 6.8 Wastewater Paraquat 99.5 1.7 ~ 11 6.1 17 23 Grass quick 77.7 2.7 ~ 12 5.2 17 19 Note. The sample volume is.200ml, the sample volume is 1.0ml.

Table A.2 Six laboratories SPE accuracy (n = 6)

Sample type target

Paraquat not detected 2.5 70.4 ~ 90.7 76.1 ± 15 Kill grass was not detected 2.5 82.0 ~ 104 89.5 ± 16 Surface water Paraquat was not detected 20.0 83.0 ~ 105 90.9 ± 16 Grass kill fast not detected 20.0 82.0 ~ 111 95.5 ± 19 Wastewater Paraquat not detected 100 91.3 ~ 107 99.5 ± 12 Kill quickly not detected 100 74.1 ~ 83.3 77.7 ± 8.0 Note. The sample volume is.200ml, the sample volume is 1.0ml.

Appendix B

(Informative)

Direct Injection - HPLC Determination of Paraquat and Quicksilver Water High-concentration samples can be 0.45 µm nylon filter (5.17) filtered, placed in polyvinyl chloride or polypropylene vials (6.1.5), measured directly on the machine. Measurement conditions see 8.1.

Pipette a certain amount of standard use solution (5.14), prepared with water at least five concentration point of the standard series, the standard series of thick Degrees were 0.05 mg/L, 0.5 mg/L, 1.0 mg/L, 2.0 mg/L and 5.0 mg/L respectively, which is the reference concentration. By low concentration to a high concentration in order to standard series of sample injection, according to the measurement conditions (8.1) analysis. The standard series of solutions in the target concentration Degree of abscissa, with its corresponding peak height or peak area for the vertical axis, the establishment of the calibration curve.

The mass concentration of the target in the sample is calculated according to the following formula.

- mass concentration of the target in the sample, mg/L;

A - the peak area or peak height of the target;

a - the intercept of the calibration curve;

b - the slope of the calibration curve;

f - the dilution of the sample.

When the injection volume was 50 µl, the detection limit of paraquat was 0.01 mg/L, the lower limit of determination was 0.04 mg/L;

The limit was 0.01 mg/L and the limit of determination was 0.04 mg/L.

......
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