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HJ 1189-2021: (Water quality Determination of 28 organophosphorus pesticides Gas chromatography-mass spectrometry)
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(Water quality Determination of 28 organophosphorus pesticides Gas chromatography-mass spectrometry)
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HJ 1189-2021
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Standard similar to HJ 1189-2021 HJ 1346.1 HJ 1199 HJ 1198 Basic data | Standard ID | HJ 1189-2021 (HJ1189-2021) | | Description (Translated English) | (Water quality Determination of 28 organophosphorus pesticides Gas chromatography-mass spectrometry) | | Sector / Industry | Environmental Protection Industry Standard | | Word Count Estimation | 25,225 | | Issuing agency(ies) | Ministry of Ecology and Environment | HJ 1189-2021: (Water quality Determination of 28 organophosphorus pesticides Gas chromatography-mass spectrometry)
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(Water quality Determination of 28 organophosphorus pesticides Gas chromatography-mass spectrometry)
National Ecological Environment Standard of the People's Republic of China
Determination of 28 Organophosphorus Pesticides in Water Quality
gas chromatography-mass spectrometry
Water quality-Determination of 28 organophosphorus pesticides
-Gas chromatography mass spectrometry
This electronic version is the official standard text, which is reviewed and typeset by the Environmental Standards Institute of the Ministry of Ecology and Environment.
Posted on 2021-09-17
2022-04-01 Implementation
Released by the Ministry of Ecology and Environment
directory
Foreword...ii
1 Scope...1
2 Normative references...1
3 Principles of the method...1
4 Reagents and materials...1
5 Instruments and equipment...2
6 Samples...3
7 Analysis steps...4
8 Result calculation and representation...6
9 Accuracy...9
10 Quality Assurance and Quality Control...10
11 Waste Disposal...10
12 Precautions...10
Appendix A (normative appendix) Method detection limit and lower limit of determination...11
Appendix B (Informative Appendix) Determination reference parameters of target compounds...12
Appendix C (informative) Accuracy of the method...13
Determination of 28 Organophosphorus Pesticides in Water Quality by Gas Chromatography-Mass Spectrometry
Warning. The organic reagents and standard materials used in the experiment are toxic compounds. The preparation of reagents and sample preparation should be kept in a fume hood.
When operating, wear protective equipment as required to avoid contact with skin and clothing.
1 Scope of application
This standard specifies the gas chromatography-mass spectrometry method for the determination of organophosphorus pesticides in water.
This standard is applicable to dichlorvos, rapid phosphorus elimination, systemic phosphorus absorption, linear phosphorus elimination,
Phorphos, Phorate, Terbuthion, Diazinon, Difenthion, Isobath, Dimethoate, Chlorazophos, Chlorpyrifos Methyl, Phosphatamine, Methyl
Parathion, Chlorpyrifos, Phosphos, Malathion, Parathion, Bromthion, Methyl isofosphos, Aminophos, Daofengsan, Profenofos,
Determination of 28 kinds of organophosphorus pesticides, such as fenamiphos, triazophos, fenamiphos, and trichlorfon.
When the sampling volume of surface water, groundwater and seawater is 1 L and the constant volume is 1.0 ml, the detection limits of 28 organophosphorus pesticides are
0.3 μg/L～0.6 μg/L, the lower limit of determination is 1.2 μg/L～2.4 μg/L; when the sampling volume of domestic sewage and industrial wastewater is 100 ml, the constant volume
When the concentration was 1.0 ml, the detection limits of the 28 organophosphorus pesticides were 4 μg/L～7 μg/L, and the lower determination limits were 16 μg/L～28 μg/L.
Please refer to Appendix A for the detection limit and lower limit of determination of this standard for the determination of target compounds.
2 Normative references
This standard refers to the following documents or clauses thereof. For dated references, only the dated version applies to this standard.
For undated references, the latest edition (including all amendments) applies to this standard.
GB 17378.3 Marine Monitoring Specification Part 3.Sample Collection, Storage and Transportation
HJ/T 91 Technical Specification for Surface Water and Sewage Monitoring
HJ 91.1 Technical Specification for Wastewater Monitoring
HJ 164 Technical Specification for Groundwater Environmental Monitoring
HJ 442.3 Technical Specifications for Environmental Monitoring in Offshore Seas Part III Water Quality Monitoring in Offshore Seas
3 Principles of the method
The organophosphorus pesticides in the water samples were extracted with chloroform, concentrated and fixed to volume, then separated by gas chromatography and detected by mass spectrometry. by retention time and
Characteristic ion abundance ratios were used for quantification and internal standard method for quantification. Trichlorfon in water samples was determined after being converted into dichlorvos by alkaline hydrolysis.
4 Reagents and Materials
Unless otherwise stated, analytical reagents that meet national standards were used in the analysis, and the experimental water was newly prepared pure water without target substances.
4.1 Trichloromethane (CHCl3). chromatographically pure.
4.2 Acetone (CH3COCH3). chromatographically pure.
4.3 n-hexane (C6H14). chromatographically pure.
4.4 Concentrated sulfuric acid (H2SO4). =1.84 g/ml.
4.5 Sodium Hydroxide (NaOH).
4.6 Sodium chloride (NaCl). After burning at 450 ℃ for 4 h, put it in a desiccator to cool to room temperature, then put it in a reagent bottle and seal it for storage.
4.7 Anhydrous sodium sulfate (Na2SO4). calcined at 450 ℃ for 4 h, placed in a desiccator and cooled to room temperature, then placed in a reagent bottle and sealed for storage.
4.8 Sulfuric acid solution. φ=50%.
Mix concentrated sulfuric acid (4.4) and water in a volume ratio of 1.1.
4.9 Sulfuric acid solution. φ=9.1%.
Mix concentrated sulfuric acid (4.4) and water in a volume ratio of 1.10.
4.10 Acetone-n-hexane mixed solution. φ=50%.
Mix acetone (4.2) and n-hexane (4.3) in a 1.1 volume ratio.
4.11 Sodium hydroxide solution. (NaOH)=10 g/L.
Weigh 1.0 g of sodium hydroxide (4.5), dissolve it in 100 ml of water, mix well, and store it in a plastic reagent bottle with a screw mouth.
4.12 Sodium hydroxide solution. (NaOH) =1.0 g/L.
Weigh 1.0 g of sodium hydroxide (4.5), dissolve it in 1 L of water, mix well, and store it in a plastic reagent bottle with a screw mouth.
4.13 Organophosphorus pesticide standard stock solution (without trichlorfon). =2000 g/ml.
Purchase commercially available certified standard solutions directly, or prepare them in acetone (4.2). See Appendix A for the components of organophosphorus pesticides (excluding trichlorfon
insect). Commercially available certified reference materials should be stored in accordance with the instructions; self-prepared standard stock solutions should be stored frozen at -18 ℃, which can be stable
Save 6 months.
Note. The sum of the concentrations of (E)-Furfenac and (Z)-Framfenox is.2000 g/ml; the sum of the concentrations of Systemic Phosphorus-S and Systemic Phosphorus-O is.2000 g/ml; (E))-
The sum of the concentrations of phosphatamine and (Z)-phosphatamine is.2000 g/ml.
4.14 Standard stock solution of trichlorfon. =2000 g/ml.
Purchase commercially available certified standard solutions directly, or prepare them in acetone (4.2). Commercially available certified reference materials are prepared according to the instructions
The standard stock solution prepared by yourself can be stored at -18 ℃, and it can be stored stably for 6 months.
Note. Trichlorfon standard stock solution is only used when spiking samples.
4.15 Organophosphorus pesticide standard solution (without trichlorfon). =50.0 g/ml.
Accurately pipette 25 μl of the organophosphorus pesticide standard stock solution (4.13) into 975 μl of the acetone-n-hexane mixed solution (4.10).
match.
4.16 Internal standard standard stock solution. =2000 g/ml.
Naphthalene-d8, acenaphthene-d10, phenanthrene-d10 and Qi-d12 should be selected as internal standards. Commercially available certified standard solutions can be purchased directly, or prepared by themselves. Commercially available
The certified reference materials are stored in accordance with the requirements of the instructions; the internal standard standard stock solution prepared by yourself is frozen and stored at -18 ℃, and 12 samples can be stored stably.
moon.
4.17 Substitute standard stock solution. =1000 g/ml.
It is advisable to use tributyl phosphate-d27 as a substitute. Commercially available certified standard solutions can be purchased directly, or prepared by themselves. Commercially available certified standards
The quality of the product is stored in accordance with the requirements of the instructions; the standard stock solution of the self-prepared substitute is stored frozen at -18 ℃, and it can be stored stably for 6 months.
4.18 Substitute standard solution. =50.0 g/ml.
Accurately pipette 50 μl of the surrogate standard stock solution (4.17) into 950 μl of the acetone-n-hexane mixed solution (4.10), and prepare it for immediate use.
4.19 Decafluorotriphenylphosphine (DFTPP) solution. =50.0 g/ml.
Commercially available certified standard solutions can be purchased directly, or prepared by themselves. Self-prepared standard solutions were stored frozen at -18 °C.
4.20 Helium. purity ≥99.999%.
5 Instruments and equipment
5.1 Vials. Amber ground stoppered glass vials or amber screw top glass vials with Teflon-lined caps.
5.2 Gas chromatograph. with split/splitless inlet.
5.3 Mass Spectrometer. Electron Impact (EI) ion source.
5.4 Capillary column. 30 m × 0.25 mm × 0.25 m, the stationary phase is 50% phenyl/50% methyl polysiloxane, or use other equivalents
capable capillary column.
5.5 Concentrating device. KD concentrator or other concentrating device.
5.6 Graphitized carbon black cartridge. 250 mg/3 ml.
5.7 Microsyringes. 5 l, 10 l, 50 l, 100 l and 1000 l.
5.8 Common laboratory instruments and equipment.
6 samples
6.1 Sample Collection
Sample collection shall be carried out in accordance with the requirements of GB 17378.3, HJ/T 91, HJ 91.1, HJ 164 and HJ 442.3.
After collecting the sample, if the pH value of the water sample is not within the range of 5 to 8, use sulfuric acid solution (4.8) or sodium hydroxide solution (4.11) to collect the water.
Adjust the pH value of the water sample to 5~8 in the device and transfer it to the sample bottle (5.1).
6.2 Storage of samples
After collection, samples should be refrigerated at 4 °C, transported away from light, and analyzed in time. If it cannot be analyzed in time, it should be stored in the refrigerator at 4°C away from light.
The shelf life is 3 days. The extract can be stored frozen at -18 °C with a storage period of 30 d.
6.3 Preparation of samples
6.3.1 Extraction and concentration
6.3.1.1 Surface water, groundwater and seawater
Measure 1 L of water sample into a separatory funnel, add 10.0 μl of the surrogate standard stock solution (4.17), and mix well. Add 30 g chlorine to the water sample
Sodium chloride (4.6), shake until completely dissolved, add 25 ml of chloroform (4.1), shake for 2 min, and be careful to release gas. Set aside for stratification, extract
Transfer the liquid to a conical flask. The extraction was repeated twice, and the extracts were combined, while retaining the trichlorfon to be tested in the aqueous layer. The extract was purified by anhydrous sodium sulfate (4.7)
After dehydration, collect it in a concentration bottle, concentrate it to about 1.0 ml, and then add 3 ml to 5 ml of acetone-n-hexane mixed solution (4.10) to wash the concentrated solution.
shrink the bottle, continue to concentrate until the volume of the extract is less than 0.5 ml, dilute to 1.0 ml with acetone-n-hexane mixed solution (4.10), add 5.0 μl
Internal standard standard stock solution (4.16), to be tested.
Note 1.Sodium chloride may not be added to seawater samples.
Note 2.The temperature during the concentration process cannot be higher than 40 ℃.
Note 3.If the concentration of organophosphorus pesticides in the sample exceeds the highest point of the curve, the sampling amount of the sample can be reduced.
6.3.1.2 Domestic and industrial wastewater
Measure 100 ml of the water sample into a separatory funnel, add 10.0 μl of the surrogate standard stock solution (4.17), and mix well. Add 3 g to the water sample
Sodium chloride (4.6), shake until completely dissolved, add 10 ml of chloroform (4.1), shake for 2 min, and be careful to release gas. stand for stratification,
The extract was transferred to a conical flask. Repeat the extraction twice, and combine the extracts, while retaining the aqueous layer of trichlorfon to be tested. The extract was purified by anhydrous sodium sulfate
(4.7) After dehydration, collect it in a concentration bottle, concentrate it to about 1.0 ml, then add 3 ml to 5 ml of acetone-n-hexane mixed solution (4.10) and shake it.
Wash the concentration bottle, continue to concentrate until the volume of the extract is less than 0.5 ml, dilute to 1.0 ml with acetone-n-hexane mixed solution (4.10), add 5.0 μl
Internal standard standard stock solution (4.16), to be tested.
Note. If the concentration of organophosphorus pesticides in the sample exceeds the highest point of the curve, the sampling amount of the sample can be reduced.
6.3.2 Purification and concentration
When the color of the chloroform extract is darker, the extract should be purified.
Use 5 ml of acetone-n-hexane mixed solution (4.10) to activate the graphitized carbon black cartridge (5.6) in advance, and then concentrate the chloroform extract
To about 1.0 ml, the extract was added to the activated graphitized carbon black column, followed by 10 ml of acetone-n-hexane mixed solution (4.10)
Elution, collect all the eluates, continue to concentrate to about 1.0 ml, then add 3 ml to 5 ml of acetone-n-hexane mixed solution (4.10) and shake
Wash the concentration bottle, continue to concentrate until the volume of the extract is less than 0.5 ml, dilute to 1.0 ml with acetone-n-hexane mixed solution (4.10), add 5.0 μl
Internal standard standard stock solution (4.16), to be tested.
6.3.3 Preparation of Trichlorfon Samples
Adjust the pH value of the aqueous phase collected in 6.3.1.1 or 6.3.1.2 to 9-10 with sodium hydroxide solution (4.12), pour it into a conical flask, cover
Remove the cap, place it in a water bath at 50 °C for alkaline hydrolysis, and constantly shake the conical flask. After 15 minutes, take out the conical flask, cool it to room temperature, use sulfur
After adjusting the pH value of acid solution (4.9) to 5~6, transfer this solution to a separatory funnel, extract and concentrate according to 6.3.1.
6.4 Preparation of blank samples
Replace the water sample with experimental water, and prepare a blank sample according to the same steps as the sample preparation (6.3).
7 Analysis steps
7.1 Instrument reference conditions
7.1.1 Gas chromatography reference conditions
Injection port. temperature 220 °C, splitless; carrier gas. helium; column flow. 1.0 ml/min (constant flow); temperature program. 40 °C (4 min)
/min 10°C 270°C (12 min).
7.1.2 Reference conditions for mass spectrometry
Transmission line temperature. 270 ℃; ion source temperature. 230 ℃; ion source electron energy. 70 eV; data acquisition method. full scan;
Scan quality range. 35 u ~ 500 u.
7.2 Calibration
7.2.1 Instrument performance check
Pipette 1 μl of decafluorotriphenylphosphine (DFTPP) solution (4.19) with a microsyringe and inject it directly into the gas chromatograph (5.2) for separation.
Analysis, the obtained decafluorotriphenylphosphine (DFTPP) key ion abundance should meet the standards specified in Table 1, otherwise it should be mass spectrometer (5.3)
parameters to adjust or consider cleaning the ion source.
Note. When using an ion trap or other type of mass spectrometer, the decafluorotriphenylphosphine (DFTPP) key ion abundance standard can be implemented according to the instrument manufacturer's instructions.
9 Accuracy
9.1 Precision
Six laboratories carried out six repeated determinations of surface water samples spiked with concentrations of 1.0 μg/L, 10.0 μg/L and 90.0 μg/L.
The intra-laboratory relative standard deviations were 6.2%-19%, 4.9%-17% and 3.2%-14%; the inter-laboratory relative standard deviations were
0.6%～4.3%, 1.3%～4.2% and 0.5%～3.7%; the repeatability limits are 0.1 μg/L～0.4 μg/L, 1.6 μg/L～3.5 μg/L and
11 μg/L～27 μg/L; the reproducibility limits are 0.2 μg/L～0.4 μg/L, 1.8 μg/L～3.8 μg/L and 14 μg/L～32 μg/L, respectively.
Six laboratories carried out six repeated determinations of groundwater samples spiked with concentrations of 1.0 μg/L, 10.0 μg/L and 90.0 μg/L.
The intra-laboratory relative standard deviations were 6.1%-19%, 4.9%-17%, and 3.2%-14%; the inter-laboratory relative standard deviations were
0.7%～4.2%, 1.4%～4.5% and 0.5%～4.1%; the repeatability limits are 0.1 μg/L～0.4 μg/L, 1.6 μg/L～3.6 μg/L and 0.1 μg/L～0.4 μg/L, respectively.
11 μg/L～28 μg/L; the reproducibility limits are 0.2 μg/L～0.5 μg/L, 1.8 μg/L～4.2 μg/L and 15 μg/L～36 μg/L, respectively.
Six laboratories carried out six repeated determinations of the domestic sewage with the spiked concentrations of 10 μg/L, 100 μg/L and 900 μg/L respectively.
The intra-laboratory relative standard deviations were 5.2%-14%, 4.4%-10% and 0.5%-8.6%; the inter-laboratory relative standard deviations were
0.5%～2.2%, 0.2%～1.5% and 0.4%～2.6%; repeatability limits are 2 μg/L～3 μg/L, 10 μg/L～24 μg/L and 40 μg/L～
120 μg/L; the reproducibility limits are 2 μg/L～3 μg/L, 14 μg/L～38 μg/L and 140 μg/L～256 μg/L, respectively.
Six laboratories carried out six repeated determinations of industrial wastewater samples spiked with concentrations of 10 μg/L, 100 μg/L and 900 μg/L.
The intra-laboratory relative standard deviations were 4.3%-14%, 4.0%-10% and 0.5%-9.0%; the inter-laboratory relative standard deviations were
0.5%～2.2%, 0.2%～1.6% and 0.4%～2.5%; the repeatability limits are 2 μg/L～3 μg/L, 10 μg/L～28 μg/L and 51 μg/L～
141 μg/L; the reproducibility limits were 2 μg/L～3 μg/L, 14 μg/L～33 μg/L and 146 μg/L～225 μg/L, respectively.
In the laboratory, six repeated determinations were carried out on seawater samples with spiked concentrations of 1.0 μg/L, 10.0 μg/L and 90.0 μg/L.
The relative standard deviations within the laboratory were 5.0%-12%, 7.2%-12% and 5.2%-10%, respectively.
For method precision data, see Table C.1 to Table C.4.
9.2 Correctness
Six laboratories carried out six repeated determinations of surface water samples spiked with concentrations of 1.0 μg/L, 10.0 μg/L and 90.0 μg/L.
The recovery rates of standard additions ranged from 36.1% to 99.2%, 52.5% to 100% and 57.2% to 110%, respectively, and the final values of the standard addition recoveries were (37.4
±2.0)%～(95.5±5.0)%, (54.3±2.9)%～(96.7±5.2)% and (59.1±3.2)%～(106±5.6)%.
Six laboratories carried out six repeated determinations of groundwater samples spiked with concentrations of 1.0 μg/L, 10.0 μg/L and 90.0 μg/L.
The recovery rates of standard additions ranged from 35.1% to 97.2%, 50.9% to 98.3% and 55.5% to 107%, respectively, and the final values of the standard addition recoveries were (36.4
±2.0)%～(93.5±5.1)%, (52.7±2.8)%～(94.7±5.1)% and (57.5±3.0)%～(103±5.6)%.
Six laboratories carried out six repeated determinations on domestic sewage samples with spiked concentrations of 10 μg/L, 100 μg/L and 900 μg/L.
The recovery rates of standard additions ranged from 43.6% to 98.6%, 59.1% to 108%, and 59.3% to 109%, respectively, and the final values of the standard addition recoveries were (49.5
±10.7)%～(97.0±2.3)%, (60.0±1.3)%～(107±2.5)% and (60.2±1.3)%～(107±2.5)%.
Six laboratories carried out six repeated determinations of industrial wastewater samples spiked with concentrations of 10 μg/L, 100 μg/L and 900 μg/L.
The recovery rates of standard additions ranged from 45.3% to 93.9%, 60.0% to 107% and 61.1% to 104%, respectively, and the final values of the standard addition recoveries were (51.2
±10.7)%～(92.4±2.2)%, (60.9±1.3)%～(104±6.5)% and (62.0±1.4)%～(102±2.3)%.
Six replicate determinations were performed in the laboratory on seawater samples spiked at concentrations of 1.0 μg/L, 10.0 μg/L and 90.0 μg/L.
The yields ranged from 37.5% to 98.1%, 43.1% to 99.3% and 59.4% to 107%.
The method accuracy data are shown in Table C.5 to Table C.7.
10 Quality Assurance and Quality Control
10.1 Blank test
At least one blank test should be done for every 20 samples or each batch (≤20 samples), and the determination result should be lower than the detection limit of the method.
10.2 Calibration
10.2.1 The relative standard deviation (RSD) of the target relative response factor (RRF) should be ≤ 20%, or the correlation of the target standard curve
Number r≥0.99, otherwise the standard curve should be redrawn;
10.2.2 Every 20 samples or each batch (≤20) samples should be measured at an intermediate check point of the curve, and the measurement result should be consistent with the standard curve.
The relative error of the concentration should be within ±20%, otherwise, a new standard curve should be established.
10.3 Parallel samples
At least one parallel sample should be determined for every 20 samples or each batch (≤20 samples). The relative deviation of the parallel sample determination results should be within ±20%
within.
10.4 Matrix spikes
10.4.1 Every 20 samples or each batch (≤ 20) samples should be tested for at least one matrix spiked sample, trichlorfon, dichlorvos, dichlorvos
The recovery rate of standard addition of phosphorus and systemic phosphorus should be greater than 30%, and the recovery rate of other target compounds should be between 60% and 120%.
Note. Trichlorfon standard stock solution (4.14) and organophosphorus pesticide standard solution (4.15) should be added to the sample at the same time.
10.4.2 The recovery rate of substitutes should be between 60% and 120%.
10.5 Internal Standard
The deviation between the retention time of the internal standard in the sample and the retention time of the internal standard in the calibration of the day or the most recently drawn standard curve should not exceed 0.5 min.
The variation of the quantitative ion peak area should be between 50% and 150%.
11 Waste Disposal
The waste liquid and waste generated during the experiment should be collected by classification, stored in a centralized manner, and entrusted with qualified personnel according to law.
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