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HJ 960-2018: Soil and sediment - Determination of carbamate pesticides - Post-column derivatization- high performance liquid chromatography
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Soil and sediment - Determination of carbamate pesticides - Post-column derivatization- high performance liquid chromatography
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HJ 960-2018
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Basic data | Standard ID | HJ 960-2018 (HJ960-2018) | | Description (Translated English) | Soil and sediment - Determination of carbamate pesticides - Post-column derivatization- high performance liquid chromatography | | Sector / Industry | Environmental Protection Industry Standard | | Classification of Chinese Standard | Z18 | | Word Count Estimation | 14,188 | | Date of Issue | 2018-07-29 | | Date of Implementation | 2019-01-01 | | Regulation (derived from) | Ministry of Ecology and Environment Announcement No. 27 of 2018 | | Issuing agency(ies) | Ministry of Ecology and Environment | HJ 960-2018: Soil and sediment - Determination of carbamate pesticides - Post-column derivatization- high performance liquid chromatography
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Soil and sediment - Determination of carbamate pesticides - Post-column derivatization- high performance liquid chromatography
National Environmental Protection Standard of the People's Republic
Soil and sediment carbamate pesticides
Determination of post-column derivatization-high performance liquid chromatography
Soil and sediment- Determination of carbamate pesticides-
Post-column derivatization- high performance liquid chromatography
Published on.2018-07-29
2019-01-01 Implementation
Ministry of Ecology and Environment released
i directory
Foreword.ii
1 Scope 1
2 Normative references 1
3 Principle of the method 1
4 interference and elimination..2
5 reagents and materials..2
6 instruments and equipment..3
7 samples..3
8 Analysis step 4
9 Calculation and representation of results 5
10 Precision and Accuracy.7
11 Quality Assurance and Quality Control..7
12 Waste treatment.7
Appendix A (Normative Appendix) Method Detection Limit and Lower Measurement Limit.8
Appendix B (informative) Method Precision and Accuracy..9
Foreword
To implement the "Environmental Protection Law of the People's Republic of China", protect the ecological environment, protect human health, regulate soil and sink
This standard is established for the measurement method of carbamate pesticides in the product.
This standard specifies post-column derivatization-high performance liquid chromatography for the determination of 10 carbamate pesticides in soil and sediment.
law.
Appendix A of this standard is a normative appendix, and Appendix B is an informative appendix.
This standard is the first release.
This standard is formulated by the Environmental Monitoring Department and the Science and Technology Standards Department.
This standard was drafted. Zhejiang Environmental Monitoring Center.
This standard is verified by. Jiangsu Environmental Monitoring Center, Hangzhou Environmental Monitoring Center Station, Shaoxing Environmental Monitoring Center
Station, Suzhou Environmental Monitoring Center Station, Zhejiang Environmental Monitoring Engineering Co., Ltd. and China Inspection Group Physical and Chemical Testing Co., Ltd.
This standard is approved by the Ministry of Ecology and Environment on July 29,.2018.
This standard has been implemented since January 1,.2019.
This standard is explained by the Ministry of Ecology and Environment.
1 Determination of soil and sediment carbamate pesticides
Post-column derivatization-high performance liquid chromatography
Warning. The solvents and standard solutions used in the experiment are harmful to human health. The solution preparation and sample preparation process should be
Wear in a fume hood; wear protective equipment as required to avoid direct contact with skin and clothing.
1 Scope of application
This standard specifies post-column derivatization-high performance liquid chromatography for the determination of 10 carbamate pesticides in soils and sediments.
law.
This standard applies to soil and sediments of aldicarb sulfoxide, aldicarb sulfone, methomyl, 3-hydroxy carbofur, aldicarb,
Determination of 10 carbamate pesticides such as propoxur, carbofuran, carbaryl, isoprocarb and methylthiocarb.
When the sample volume is 10 g, the sample volume is 1.0 ml, and the injection volume is 15 μl, 10 carbamate farmers
The detection limit of the drug is 1 to 3 μg/kg, and the lower limit of determination is 4 to 12 μg/kg. See Appendix A for details.
2 Normative references
This standard refers to the following documents or their terms. For undated references, the valid version applies to this
standard.
GB 17378.3 Marine monitoring specification Part 3. Sample collection, storage and transport
GB 17378.5 Marine monitoring specification Part 5. Sediment analysis
HJ 494 Water Quality Sampling Technical Guidance
HJ 613 Determination of dry matter and moisture in soils - Gravimetric method
HJ 783 Extraction of soil and sediment organic matter by pressurized fluid extraction
HJ/T 166 Technical Specifications for Soil Environmental Monitoring
3 Principle of the method
Carbamate pesticides in soil or sediment are extracted by organic solvent, solid phase extraction column purification, concentration, constant volume,
After separation by liquid chromatography column, it is hydrolyzed under basic conditions to form methylamine (Formula 1), which reacts with the derivatizing reagent to form a strong
The fluorescent substance (formula 2) was measured by a fluorescence detector. According to the retention time qualitative, the external standard method is quantitative.
(1)
(2)
24 interference and elimination
Substances with similar retention times interfere with the determination and can be added by changing the mobile phase gradient elution procedure, standard addition
Method, quantitative qualitative wavelength absorption ratio and other methods to eliminate interference.
5 reagents and materials
Analytically pure reagents in accordance with national standards were used for analysis, unless otherwise stated.
The pure water of the standard.
5.1 Acetonitrile (CH3CN). liquid chromatography grade.
5.2 Methanol (CH3OH). liquid chromatography grade.
5.3 Dichloromethane (CH2Cl2). liquid chromatography grade.
5.4 Sodium hydroxide (NaOH).
5.5 Sodium tetraborate (Na2B4O7·10H2O).
5.6 2-mercaptoethanol (HSC2H4OH) or 2-dimethylaminoethanethiol hydrochloride (C4H11NS·HCl).
5.7 O-phthalaldehyde (C8H6O2).
5.8 anhydrous sodium sulfate (Na2SO4).
The muffle furnace was fired at 450 ° C for 4 h, cooled slightly, and placed in a desiccator for use.
5.9 Hydrolyzate. Sodium hydroxide solution, c (NaOH) = 0.05 mol/L.
Weigh 2.0 g of sodium hydroxide (5.4), dissolve in water and dilute to 1 L, and filter through a filter (5.19). Can also be purchased directly
Buy commercial goods.
5.10 Sodium tetraborate solution. c (Na2B4O7·10H2O) = 0.05 mol/L.
19.1 g of sodium tetraborate (5.5) was weighed, dissolved in water and diluted to 1 L, and filtered through a filter (5.19). Also directly
Buy commercial items.
5.11 Derivatization reagents.
Weigh 0.1 g of o-phthalaldehyde (5.7) and dissolve it in 10 ml of methanol (5.2). Pipette.200 μl 2-mercaptoethanol (5.6) or
Weigh 2.0 g of 2-dimethylaminoethanethiol hydrochloride (5.6) and dissolve it in 10 ml of sodium tetraborate solution (5.10). The above two kinds
The solution was mixed and diluted to 1 L with sodium tetraborate solution (5.10).
5.12 Methanol-dichloromethane mixed solvent. 12.
Mix with methanol (5.2) and dichloromethane (5.3) in a volume ratio of 1.2.
5.13 Methanol-dichloromethane mixed solvent. 19.
Mix with methanol (5.2) and dichloromethane (5.3) in a volume ratio of 1.9.
5.14 Standard stock solution of carbamate pesticide. ρ=100 mg/L.
Purchase commercially available certified standard solutions directly and store them in accordance with the standard solution certificate.
5.15 Standard use solution for carbamate pesticides. ρ=10 mg/L.
Take 500 μl of carbamate pesticide standard stock solution (5.14) in a 5 ml volumetric flask and dilute to volume with methanol (5.2).
Mix well, place in a -18 ° C refrigerator, sealed, protected from light, and the shelf life is 6 months.
5.16 Solid phase extraction column. Graphitized carbon black/N-propyl ethylene diamine composite filler column (500 mg/6 ml) or other properties
A similar solid phase extraction column.
35.17 Diatomaceous earth. 0.6 to 0.9 mm (30 mesh to 20 mesh).
5.18 Quartz sand. 150 to 830 μm (200 mesh to 100 mesh).
The muffle furnace was fired at 450 ° C for 4 h, cooled slightly, and placed in a clean dryer for later use.
5.19 Filter. 0.45 μm polyethersulfone or other equivalent material.
5.20 Filter. 0.45 μm PTFE or other equivalent material.
5.21 Nitrogen. purity ≥ 99.99%.
6 Instruments and equipment
6.1 High Performance Liquid Chromatograph.
6.1.1 with fluorescence detector, gradient elution function.
6.1.2 With post-column derivatization system, the derivatization reaction can be completed automatically.
6.1.3 Column. C8 column with a particle size of 5 μm, a column length of 25.0 cm and an inner diameter of 4.0 mm or other properties
Similar columns.
6.2 Freeze dryer.
6.3 Extraction device. pressurized fluid extractor (with extraction tank below 50 ml), Soxhlet extraction device, automatic Soxhlet extraction
Instrument or other equivalent extraction device.
6.4 Concentrator. Nitrogen blown concentrator, rotary evaporator or other equivalent equipment.
6.5 Analytical balance. The sensitivity is 0.01 g.
6.6 Common instruments and equipment used in general laboratories.
7 samples
7.1 Sample collection and preservation
Collect and store soil samples in accordance with the relevant requirements of HJ/T 166, and collect water bodies according to the relevant requirements of HJ 494
Samples of marine sediments were collected according to the relevant requirements of GB 17378.3. After sample collection, seal and avoid at 0~4°C
Light preservation, extraction completed within 7 days.
7.2 Preparation of samples
Remove foreign matter (branches, leaves, stones, etc.) from the sample and mix the sample thoroughly. If the sample has a high moisture content,
It should be dried first with a freeze dryer (6.2). Weigh two samples of approximately 10 g (accurate to 0.01 g).
One sample of the soil sample is used to determine the dry matter content; the other is used for extraction. When using pressurized fluid extraction, add
Add appropriate amount of diatomaceous earth (5.17) and put it into the extraction tank. When using Soxhlet extraction, add an appropriate amount of anhydrous sodium sulfate (5.8) and load
Extract the tube.
One sample of the sediment is used to determine the water content; the other is used for extraction, and the extraction method is based on the soil sample.
7.3 Determination of moisture
The dry matter content of the soil samples was determined according to HJ 613, and the moisture content of the sediment samples was determined in accordance with GB 17378.5.
47.4 Preparation of samples
7.4.1 Extraction
7.4.1.1 Pressurized fluid extraction
The carbamate pesticide in the sample was extracted with a methanol-dichloromethane mixed solvent (5.12) at a pressure of 10.34 Mpa.
The extraction temperature is 80oC, the heating time is 5 min, the static extraction time is 5 min, the flushing amount is 80%, and the nitrogen is purged for 60 s after extraction.
Cycle extraction 3 times. Or set and optimize the extraction conditions according to HJ 783.
7.4.1.2 Soxhlet extraction
Place the filter cartridge in the Soxhlet extractor return tube and add.200 ml methanol-dichloromethane mixed solvent to the round bottom solvent bottle.
(5.12), extraction is 12 h, and the reflux rate is controlled at 4 to 6 times/h. After the extraction is completed, the round bottom solvent bottle is taken out and concentrated.
Note. Other equivalent extraction methods can be used if verified.
7.4.2 Concentration
The extract (7.4.1) was concentrated to nearly 1.0 ml with a concentrating device (6.4) to be purified.
7.4.3 Purification
The solid phase extraction column (5.16) was activated at a rate of 2 ml/min with 5.0 ml of a methanol-dichloromethane mixed solvent (5.13).
Transfer the concentrate (7.4.2) to the column head before the packing is about to be exposed to air, before the packing is about to be exposed to air.
The extraction column was eluted with 5.0 ml of a methanol-dichloromethane mixed solvent (5.13), and the eluate was collected in a graduated tube.
Note. When using different batches of extraction column to purify the sample, the amount of elution solvent should be determined experimentally.
7.4.4 Concentration after purification
The eluent (7.4.3) was concentrated to near dryness with a nitrogen blowing concentrator (6.4), and the volume was adjusted to 1.0 with methanol (5.2).
Ml, filter membrane (5.20), to be tested.
The treated samples should be stored frozen in a refrigerator below -18 ° C and analyzed in 30 days.
7.5 Preparation of blank samples
A blank sample was prepared by replacing the actual sample with quartz sand (5.18) in the same manner as in the preparation of the sample (7.4).
8 Analysis steps
8.1 Reference measurement conditions
8.1.1 post-column derivatization conditions
Reactor temperature. 100oC, derivatized pump flow rate. 0.3 ml/min.
8.1.2 Chromatographic conditions
Mobile phase. mobile phase A acetonitrile (5.1), mobile phase B water, gradient elution procedures are shown in Table 1. Flow rate. 0.8 ml/min;
5 injection volume. 15 μl; column temperature. 37oC; fluorescence detector. excitation wavelength 330 nm, quantitative emission wavelength 460 nm, set
The emission wavelength is 435 nm.
Table 1 Gradient elution procedure
Time (min) mobile phase A (%) mobile phase B (%)
8.2 Establishment of the standard curve
Transfer the appropriate amount of carbamate pesticide standard solution (5.15) to a 5 ml volumetric flask and dilute with methanol (5.2).
To the standard line, prepare a standard series of at least 5 concentration points. The standard series concentration is 0.05 μg/ml, 0.50 μg/ml, 1.00.
Gg/ml, 2.50 μg/ml and 5.00 μg/ml (this is the reference concentration). Standard series solution from low to high concentration
Inject, according to the measurement conditions (8.1), the concentration of each carbamate pesticide in the standard series solution is plotted on the abscissa.
A standard curve is established with its corresponding peak area (or peak height) as the ordinate.
8.3 Sample determination
The measurement of the sample (7.4) was carried out in the same manner as the establishment of the standard curve (8.2).
8.4 Blank test
The blank sample (7.5) was measured in the same manner as in the sample measurement (8.3).
9 Calculation and representation of results
9.1 Qualitative analysis
Qualitative according to the retention time of the target in the sample and the target in the standard solution. Standard additions can be used if necessary
Method, quantitative and qualitative wavelength absorption ratio and other methods to assist qualitative.
Under the measurement conditions (8.1) specified in this standard, the standard solution chromatogram is shown in Figure 1.
6Figure 1 Standard solution chromatogram
9.2 Calculation of results
The mass concentration of the target in the soil sample is calculated according to formula (3).
Dm
i wm
w
1000
(3)
Where. iw 1 - the concentration of the i-th target in the soil sample, μg/kg;
I1 - the concentration of the i-th target in the soil sample, mg/L;
1V - soil sample volume, ml;
1m - soil sample wet weight, g;
Dmw - soil dry matter content, %;
The mass concentration of the target in the sediment sample is calculated according to formula (4).
)1(
I2
OH
Wm
w
(4)
Where. iw 2 - the concentration of the i-th target in the sediment sample, μg/kg;
I2 - concentration of the i-th target in the sediment sample, mg/L;
2V - sediment volume constant volume, ml;
2m - sediment sample wet weight, g;
OHw 2 - sediment moisture content, %.
9.3 Result representation
The number of decimal places in the measurement result is consistent with the method detection limit, and up to 3 significant digits are reserved.
Min0 5 10 15 20 25 30 35
LU
1-anthracene sulfoxide; 2-oxadicarb sulfone; 3-nordovir; 4-3-hydroxy carbofur; 5-aldoxime;
6-killer; 7-carbocarb; 8-carbinavir; 9-isopropion; 10-methylthiocarb.
710 precision and accuracy
10.1 Precision
Unified sediments at 500 μg/kg and 5 μg/kg for carbamate-containing pesticides in six laboratories
The sample was tested in 6 replicates. The relative standard deviations in the laboratory ranged from 1.6% to 7.6% and 2.4% to 13%.
The relative standard deviations between laboratories are. 4.1%~12%, 4.9%~19%; the repeatability limits are. 56~
73 μg/kg, 1-2 μg/kg; the reproducibility limits ranged from 79 to 161 μg/kg and 2 to 3 μg/kg.
See Appendix B for precision results.
10.2 Accuracy
Six laboratories calibrated uniform sediment samples containing carbamate pesticides that were less than the method detection limit.
The analytical standards were 500 μg/kg and 5 μg/kg, respectively. The recoveries ranged from 78.7% to 106% and 82.6%.
141%; the final values of the spiked recovery were. (86.7 ± 20)% ~ (102 ± 8.2)%, (93.8 ± 10)% ~ (111 ± 28)%.
See Appendix B for accuracy results.
11 Quality Assurance and Quality Control
11.1 Blank test
Analyze at least 1 laboratory blank for every 20 samples or batches (less than 20 samples/batch), blank test results
Should be below the method detection limit.
11.2 Calibration
The correlation coefficient of the standard curve is r ≥ 0.995.
Select the intermediate concentration point of the standard curve for continuous calibration, 20 samples per batch or each batch (less than 20 samples)
/ batch) 1 continuous calibration, the relative deviation of the measurement results should be ≤ 20%, otherwise the standard curve needs to be re-established.
11.3 Parallel samples
Analyze at least 1 parallel sample for every 20 samples or batches (less than 20 samples/batch), parallel sample relative deviation ≤
30%.
11.4 Matrix addition
Analyze at least 1 matrix plus standard for every 20 samples or batches (less than 20 samples/batch).
Between 60% and 145%.
12 Waste treatment
The waste liquid and waste generated in the experiment should be collected centrally and properly marked, and entrusted by qualified units for processing.
8 Appendix A
(normative appendix)
Method detection limit and lower limit of measurement
When the sample volume is 10 g, the sample volume is 1.0 ml, and the injection volume is 15 μl, 10 carbamate farmers
The detection limit and lower limit of the method of the drug are shown in Table A.1.
Table A.1 Method detection limits and lower limit of measurement
No. Compound English name CAS No.
The detection limit
(μg/kg)
Lower limit of measurement
(μg/kg)
1 Aldicarb Sulfoxide 1646-87-3 2 8
2 Aldicarb Sulfone 1646-88-4 2 8
3 Methomyl 16752-77-5 2 8
4 3-hydroxy carbofur 3-Hydroxycarbofuran 16655-82-6 2 8
5 Aldicarb 116-06-3 2 8
6 Killer Propoxur 114-26-1 2 8
7 Carbofuran 1563-66-2 1 4
8 Carbaryl Carbaryl 63-25-2 3 12
9 Isoprocarb 2631-40-5 2 8
10 Mercury dimethur 2032-65-7 2 8
9 Appendix B
(informative appendix)
Method precision and accuracy
The precision and accuracy of the actual spiked samples were determined by pressurized fluid extraction and solid phase extraction purification. Table B.1 gives
The method precision index, Table B.2 gives the method accuracy index.
Table B.1 Method precision
Serial number compound
average value
(μg/kg)
Experimental room relative
standard deviation(%)
Interlaboratory
standard deviation(%)
Reproducibility limit r
(μg/kg)
Reproducibility limit R
(μg/kg)
Standard concentration. 500 μg/kg
1 涕 威 威 sulfoxide 510 1.7 ~ 7.6 4.1 73 88
2 aldicarb sulfone 452 3.0~5.4 7.0 60 104
3 灭多威448 2.5～6.2 6.2 56 93
4 3-hydroxy carbofuran 446 3.2~6.2 4.5 66 83
5 Aldicarb 449 2.0～6.5 12 67 161
6 杀杀威442 2.9～7.5 8.2 64 117
7 grams of Budweiser 445 1.6 to 6.0 7.7 57 109
8 carbaryl 444 2.9 to 5.5 4.7 59 79
9 Isopro 433 2.3 to 7.6 11 68 152
10 methylthiocarb 447 2.5-6.2 5.4 58 86
Standard concentration. 5 μg/kg
1 Aldicarb sulfoxide 6 4.4~12 13 1 3
2 aldicarb sulfone 5 4.2～8.1 10 1 2
3 灭多威 5 3.6～9.0 10 1 2
4 3-hydroxy carbofur 5 4.0～8.5 19 1 3
5 Aldicarb 5 2.9~7.2 11 1 2
6 Killer 5 5 to 6.3 9.1 1 2
7 grams of Budweiser 5 3.8 ~ 6.5 11 1 2
8 carbaryl 5 3.8 to 9.3 8.0 1 2
9 Iso Wei 5 3.5～6.9 17 1 3
10 methylthiocarba 5.6~13 4.9 2 2
Table B.2 Method accuracy
Serial number compound
Sample concentration
(μg/kg)
Spike recovery range
P (%) P (%) P
(%)
Scaling recovery final value
PSP 2 (%)
Standard concentration. 500 μg/kg
1 aldicarb sulfoxide < 2 94.1～106 102 4.1 102±8.2
2 aldicarb sulfone < 2 84.9 ~ 101 90.3 6.3 90.3 ± 13
3 灭多威 < 2 84.3～97.1 89.5 5.5 89.5±11
4 3-hydroxy carbofuran < 2 85.0~93.0 89.2 4.0 89.2±8.0
5 涕威威< 2 79.8～104 89.8 11 89.8±22
6 杀杀威< 2 80.4～97.7 88.4 7.3 88.4±15
7 grams of Budweiser < 1 82.3 ~ 102 89.0 6.9 89.0 ± 14
8 carbaryl < 3 84.6～93.8 88.7 4.2 88.7±8.4
9 Iso Wei < 2 78.7～105 86.7 10 86.7±20
10 methylthiocarb< 2 84.8～97.9 89.5 4.9 89.5±9.8
Standard concentration. 5 μg/kg
1 aldicarb sulfoxide < 2 99.4～139 111 14 111±28
2 aldicarb sulfone < 2 90.9~119 100 10 100±20
3 灭多威 < 2 90.7～115 98.3 9.1 98.3±18
4 3-hydroxy carbofuran < 2 88.6~141 103 19 103±38
5 涕威威< 2 82.7～106 94.8 10 94.8±20
6 杀杀威< 2 86.0～110 96.6 8.9 96.6±18
7 grams of Budweiser < 1 87.4 ~ 118 98.4 11 98.4 ± 22
8 carbaryl < 3 88.2～109 98.0 7.9 98.0±16
9 Iso Wei < 2 82.6～128 98.7 17 98.7±34
10 methylthiocarb< 2 85.0～100 93.8 5.0 93.8±10
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