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Basic dataStandard ID: HJ 1070-2019 (HJ1070-2019)Description (Translated English): Water quality--Determination of 15 chlorinated herbicides--Gas chromatography Sector / Industry: Environmental Protection Industry Standard Classification of Chinese Standard: Z16 Classification of International Standard: 13.060 Word Count Estimation: 23,272 Date of Issue: 2019 Date of Implementation: 2020-06-30 Issuing agency(ies): Ministry of Ecology and Environment HJ 1070-2019: Water quality--Determination of 15 chlorinated herbicides--Gas chromatography---This is a DRAFT version for illustration, not a final translation. Full copy of true-PDF in English version (including equations, symbols, images, flow-chart, tables, and figures etc.) will be manually/carefully translated upon your order.Water quality--Determination of 15 chlorinated herbicides--Gas chromatography National Environmental Protection Standard of the People's Republic of China Determination of 15 chlorinated herbicides in water quality Gas chromatography Water quality-Determination of 15 chlorinated herbicides -Gas chromatography 2019-12-31 released 2020-06-30 implementation Released by the Ministry of Ecology and Environment ContentsForeword ... ii 1 Scope ... 1 2 Normative references ... 1 3 Methodology ... 1 4 Reagents and materials ... 1 5 Instruments and equipment ... 2 6 Sample ... 3 7 Analysis steps ... 4 8 Calculation and Representation of Results ... 5 9 Precision and accuracy ... 6 10 Quality Assurance and Quality Control ... 7 11 Waste disposal ... 7 Appendix A (Normative) Method detection limit and lower detection limit ... 8 Appendix B (informative) Method precision and accuracy ... 9ForewordIn order to implement the "Environmental Protection Law of the People's Republic of China" and the "Law of the People's Republic of China on Water Pollution Control", protect the ecology Environment, protect human health, standardize the determination method of 15 chlorinated herbicides in water, and formulate this standard. This standard specifies the determination of 15 kinds of chlorinated herbicides in surface water, groundwater, seawater, domestic sewage and industrial wastewater. Phase chromatography. Appendix A of this standard is a normative appendix, and Appendix B is an informative appendix. 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, Shanghai Environmental Monitoring Center, Nanjing Environmental Monitoring Center, Jiangsu Province Xin, Changzhou Environmental Monitoring Center of Jiangsu Province, Jiangyin Environmental Monitoring Center of Jiangsu Province and Zhangjiagang Environmental Monitoring Center of Jiangsu Province. This standard was approved by the Ministry of Ecology and Environment on December 31,.2019. This standard will be implemented from June 30, 2020. This standard is explained by the Ministry of Ecology and Environment. Water quality-Determination of 15 chlorinated herbicides by gas chromatography Warning. The reagents and standard solutions used in the experiment are corrosive, irritating and toxic. Before reagent preparation and sample preparation The treatment process should be carried out in a fume hood; wear protective equipment as required to avoid breathing into the respiratory tract or touching the skin and Clothing.1 ScopeThis standard specifies gas chromatography for the determination of 15 chlorinated herbicides in water. This standard applies to 2,2-dichloropropionic acid, 3,5-dichlorobenzoic acid, 2- (4-chloro-2-methylphenoxy) propionic acid, and 3,6-dichloro 2-methoxybenzoic acid, 2-methyl-4-chlorophenoxyacetic acid, 2,4-dipropionic acid, 2,4-dichlorophenoxyacetic acid, 2,4,5-trichlorophenoxyethyl Acid, pentachlorophenol, 2,4,5-lanthionic acid, 3-amino-2,5-dichlorobenzoic acid, 2,4-dichlorophenoxybutyric acid, 4-amino-3,5,6- three Determination of 15 kinds of chlorinated herbicides of clopidic acid, triflufenacil and tetrachloroterephthalic acid. The pretreatment methods of this standard are divided into liquid-liquid extraction and solid-phase extraction. Liquid-liquid extraction is suitable for surface water, groundwater, Domestic sewage, industrial wastewater and seawater; solid phase extraction is suitable for cleaner surface water and groundwater. When the sampling volume is 500 ml, the constant volume is 10 ml, and the injection volume is 1.0 µl, the method detection limit is 0.1 ～ 0.2 µg/L, the lower limit of determination is 0.4 ～ 0.8 µg/L, see Appendix A for details.2 Normative referencesThis 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 HJ 91.1 Technical Specifications for Sewage Monitoring HJ 442 Specifications for Environmental Monitoring in Coastal Waters HJ/T 91 Technical specifications for surface water and sewage monitoring 3 HJ/T 164 Groundwater Environmental Monitoring Technical Specification Method Principle The sample is hydrolyzed under alkaline conditions (pH ≥ 12), and then at pH ≤ 2 using dichloromethane or a solid-phase extraction column Chlorinated herbicides were extracted from the sample. After the extract was concentrated and the solvent was converted, it was derivatized with pentafluorobenzyl bromide. It was then separated by gas chromatography and detected by an electron capture detector. Qualitative according to retention time, quantified by external standard method.4 Reagents and materialsUnless otherwise stated, analytical reagents that meet national standards are used in the analysis. The test water is free of target compounds. Pure water. 4.1 Phosphoric acid. ρ (H3PO4) = 1.69 g/ml, excellent purity. 4.2 Hydrochloric acid. ρ (HCl) = 1.19 g/ml. 4.3 Anhydrous sodium sulfate (Na2SO4). Burn at 400 ° C for 2 h before use. After cooling, place it in a ground glass bottle and store in a desiccator. 4.4 Sodium chloride (NaCl). Burn at 400 ° C for 2 h before use. After cooling, place it in a ground glass bottle and store in a desiccator. 4.5 n-hexane (C6H14). pesticide residue grade. 4.6 Dichloromethane (CH2Cl2). pesticide residue level. 4.7 Acetone (C3H6O). pesticide residue level. 4.8 Methanol (CH4O). pesticide residue level. 4.9 Toluene (C7H8). pesticide residue grade. 4.10 Toluene-n-hexane mixed solvent. 16. 4.11 N-hexane-toluene mixed solvent. 1 9. 4.12 Sodium hydroxide solution. c (NaOH) = 6 mol/L. Weigh 24.0 g of sodium hydroxide in water and dilute to 100 ml. 4.13 Hydrochloric acid solution. 1 1. 4.14 Potassium carbonate solution. ρ (K2CO3) = 100 g/L. Weigh 10.0 g of potassium carbonate in water and make up to 100 ml. 4.15 Pentafluorobenzyl bromide (C7H2BrF5). 4.16 Pentafluorobenzyl bromide solution. ρ (C7H2BrF5) = 30 g/L. Weigh 3.0 g of pentafluorobenzyl bromide (4.15) in acetone and make up to 100 ml. 4.17 Standard stock solution of chlorinated herbicides. ρ = 100 mg/L Commercially available certified standard solutions can be purchased directly. The standard solution after opening is sealed and stored under frozen and protected from light, effective 1 year. Alternatively, the standard chlorinated herbicide can be placed in a desiccator containing silica gel for 48 h, then weighed with acetone (4.7) Formulated for solvents. 4.18 Mixed standard chlorinated herbicide use solution. ρ = 10.0 mg/L Pipette 10.00 ml of standard chloro herbicide stock solution (4.17) into a 100 ml volumetric flask, dilute with acetone (4.7) and Make up to the mark. The standard use solution is refrigerated at 4 ° C and stored in the dark, and the shelf life is two months. Should be returned to room temperature during use, and Shake well. 4.19 Solid-phase extraction column. 500 mg/6 ml, packed with divinylbenzene and N-vinylpyrrolidone copolymer or equivalent Extraction column. 4.20 Silica gel column. 500 mg/6 ml, packed with chromatography silica gel of 40 μm ～ 75 μm. 4.21 Nitrogen. Purity ≥99.999%.5 Instruments and equipment5.1 Gas chromatograph. with electronic capture detector (ECD). 5.2 Chromatographic column. Quartz capillary column, 30 m in length, 0.25 mm in inner diameter, 0.25 μm in thickness, 5% phenyl-95% in stationary phase Methyl polysiloxane, or other equivalent columns. 5.3 Concentration device. Nitrogen blowing concentrator, rotary evaporator or KD concentrator, etc. 5.4 Water bath. 5.5 Solid phase extraction device. 5.6 Scale concentration bottle. 5.7 General laboratory instruments and equipment.6 samples6.1 Sample collection and storage Samples were collected in accordance with the requirements of HJ 91.1, HJ/T 91, HJ/T 164, HJ 442 and GB 17378.3. Immediately after the sample was collected, adjust the pH ≤ 2 with hydrochloric acid solution (4.13), refrigerate at 4 ° C and store in the dark, and extract within 7 days. The extract was analyzed within 30 days. 6.2 Preparation of test specimens 6.2.1 Hydrolysis Measure 500 ml of sample into a separatory funnel, adjust the pH of the solution to ≥12 with sodium hydroxide solution (4.12), and let stand for 1 h. The sample volume is recorded as V. Note. For high concentration samples, reduce the sample size. For samples containing only phenoxycarboxylic acid herbicides, no hydrolysis is required. 6.2.2 Extraction 6.2.2.1 Liquid-liquid extraction method Clean samples such as surface water and groundwater can be directly extracted without purification. For samples with complex matrices, The sample (6.2.1) is decontaminated. Purification. Add 30 ml of dichloromethane (4.6) to the hydrolyzed sample (6.2.1), shake and deflate, and shake to extract After 15 minutes, let stand for 15 minutes. After the two phases are separated, the lower organic phase is discarded. Add another 30 ml of dichloromethane and repeat the extraction. Next, the lower organic phase was discarded. Extraction. Use phosphoric acid (4.1) to adjust the hydrolyzed sample (6.2.1) or purified sample to pH ≤ 2 and add 10 g of chlorinated Sodium (4.4), shake to dissolve. Add 30 ml of dichloromethane (4.6), shake and deflate, shake for 15 min, and let stand 15 minutes, after the two phases were separated, the organic phase dehydrated by anhydrous sodium sulfate was collected in a graduated concentration flask (5.6). Reuse 30 ml of dichloromethane were repeatedly extracted twice. Combine the organic phases dehydrated with anhydrous sodium sulfate and concentrate with a concentration device (5.3) Nearly dry. Dissolve in 5 ml of acetone (4.7) and wait for derivatization. 6.2.2.2 Solid-phase extraction Column activation. Place the solid-phase extraction column (4.19) on the solid-phase extraction device (5.5). 10 ml of dichloromethane (4.6), 10 ml of methanol (4.8) is passed through the solid-phase extraction column at a rate of about 5 ml/min. Add 20 ml of water. When about 2 ml of water remain, close the valve. Enrichment. The pH of the hydrolyzed sample (6.2.1) was adjusted to ≤ 2 with phosphoric acid (4.1). Pass the sample at a flow rate of 10 ml/min. Pass the activated solid phase extraction column. After the sample is completely enriched, continue to pump for 10 min or purge with nitrogen (4.21) to make the extraction. The column was dried. Then add 20 ml of methanol (4.8) to elute and collect the eluate into a graduated concentration flask (5.6). With concentration device (5.3) Concentrate to near dryness and dissolve in 5 ml of acetone (4.7) until derivatized. 6.2.3 Derivation Add 30 μl potassium carbonate solution (4.14) to the extraction solution (6.2.2.1 or 6.2.2.2) to be derivatized, mix well and add 200 μl pentafluorobenzyl bromide solution (4.16), sealed with a stopper and derivatized in a water bath at 60 ° C ± 2 ° C for more than 3 h. After derivatization, the reaction solution was concentrated to 0.5 ml with a concentration device (5.3), and the volume was adjusted with a toluene-n-hexane mixed solvent (4.10). To 2 ml. 6.2.4 Purification after derivation The silica gel column (4.20) was packed with 0.5 g of anhydrous sodium sulfate (4.3). Rinse the silica gel column with 5 ml of n-hexane (4.5). Add the sample to a silica gel column, rinse with 10 ml toluene-n-hexane mixed solvent (4.10), and discard the eluent. With 8 ml plus The hexane-toluene mixed solvent (4.11) was used for elution. The entire eluate was received in a 10 ml stopper colorimetric tube, and the volume was adjusted with n-hexane. To the mark, to be tested. 6.3 Preparation of blank samples Use experimental water to replace the sample, and follow the same steps as in the sample preparation (6.2) to prepare a laboratory blank sample. Equipment.7 Analysis steps7.1 Chromatographic Reference Conditions Inlet temperature. 250 ° C, splitless injection. Detector. ECD. Detector temperature. 300 ° C. Heating program. keep the initial temperature at 80 ° C for 2 minutes, raise it to 170 ° C at 30 ° C/min, keep it for 5 minutes, and then keep it at 10 ° C/min The temperature was raised to.200 ° C and held for 2 minutes, and then raised to 300 ° C at 10 ° C/min for 5 minutes. Carrier gas. nitrogen (4.2.1); flow rate. 1.0 ml/min. Makeup gas flow. 30 ml/min. Injection volume. 1.0 μl. 7.2 Establishment of working curve Take 20.0 μl, 50.0 μl, 100 μl, 500 μl, and 1000 μl of the standard use solution (4.18) in the graduated concentration bottle (5.6) , Dilute to 5 ml with acetone, and prepare each target compound content as 0.50 μg, 1.00 μg, 2.50 μg, 5.00 μg and 10.0 μg (This is the reference content) standard series. Follow the same steps as 6.2.3 and 6.2.4 to perform derivatization and purification treatment, and inject samples from low concentration to high concentration in order. Using the target compound content as the abscissa and the corresponding peak area as the ordinate, a working curve was established. Under the chromatographic reference conditions (7.1) specified in this standard, the standard gas chromatograms of 15 chlorinated herbicides are shown in Figure 1. 1-2,2-dichloropropionic acid; 2-3,5-dichlorobenzoic acid; 3-2- (4-chloro-2-methylphenoxy) propionic acid; 4-3,6-dichloro -2-methoxybenzoic acid; 5 2-methyl-4-chlorophenoxyacetic acid; 6-2,4-dipropionic acid; 7-2,4-dichlorophenoxyacetic acid; 8-2,4,5-trichlorophenoxyacetic acid; 9 -Pentachlorophenol; 10 -2,4,5-Labelic acid; 11-3-amino-2,5-dichlorobenzoic acid; 12-2,4-dichlorophenoxybutyric acid; 13-4-amino-3,5,6 -Trichloropyridinecarboxylic acid; 14 -Trifluorocarboxenol; 15-tetrachloroterephthalic acid. Figure 1 Reference gas chromatograms of 15 chlorinated herbicide derivatives (ρ = 1000 μg/L) 7.3 Sample determination Test the sample (6.2.4) under the same conditions as the establishment of the working curve (7.2). If the test concentration exceeds When the working curve concentration range is obtained, the sample is diluted to the working curve concentration range, and the dilution factor is recorded as D. 7.4 Blank test The blank sample (6.3) was measured under the same conditions as the sample measurement (7.3).8 Results calculation and representation8.1 Qualitative analysis Characterized by the retention time of each target compound according to the standard chromatogram. Gas chromatography-mass spectrometry (GC-MS) Qualitative confirmation. 8.2 Calculation of results The mass concentration of the target compound in the sample is calculated according to formula (1). 𝜌𝑖 = 𝑚𝑖 𝑉 × 𝐷 (1) Where. ρi--mass concentration of target compound i in the sample, μg/L mi--the content of the target compound i obtained from the working curve, μg; V--sample volume, L; D--Dilution multiple. 8.3 Representation of results The number of digits after the decimal point of the measurement result is kept consistent with the detection limit of the method, and a maximum of three significant digits are retained.9 Precision and accuracy9.1 Precision 9.1.1 Liquid-liquid extraction Six laboratories performed 6 replicates of blank spiked samples with chlorinated herbicide concentrations of 0.500 μg/L and 10.0 μg/L Re-assay. the relative standard deviations in the laboratory were 1.6% to 9.5% and 0.9% to 7.8%; the relative standard deviations between laboratories 2.1% to 5.8% and 1.6% to 4.5%, respectively; repeatability limits are 0.02 to 0.08 μg/L and 0.14 to 0.74 μg/L, respectively; The performance limits were 0.04 to 0.14 μg/L and 0.54 to 1.3 μg/L, respectively. Six laboratories conducted 6 spiked samples of surface water with chlorinated herbicide concentrations of 0.500 μg/L and 10.0 μg/L Repeated determination. the relative standard deviations in the laboratory were 2.0% to 13% and 2.0% to 8.8%; the relative standard deviations between laboratories The differences are 1.6% to 5.4% and 1.2% to 3.5%, respectively; the repeatability limits are 0.02 to 0.06 μg/L and 0.50 to 0.54 μg/L, respectively; Reproducibility limits are 0.04 to 0.10 μg/L and 0.38 to 1.1 μg/L, respectively. Six laboratories conducted six replicates of domestic sewage samples containing chlorinated herbicides at 1.00 μg/L and 18.0 μg/L Re-assay. the relative standard deviations in the laboratory are 4.4% -18% and 2.6% -10%, respectively; the relative standard deviations between laboratories 3.1% to 7.7% and 1.3% to 5.3%, respectively; the repeatability limits are 0.02 to 0.10 μg/L and 0.28 to 1.0 μg/L, respectively; The performance limits were 0.12 ～ 0.24 μg/L and 0.82 ～ 2.8 μg/L, respectively. Six laboratories carry out spiked samples of uniform industrial wastewater containing chlorinated herbicides at 1.00 μg/L and 18.0 μg/L Six repeated determinations. the relative standard deviations in the laboratory were 3.8% to 19% and 2.7% to 11%, respectively; Standard deviations are 3.5% to 7.4% and 1.2% to 4.5%, respectively; repeatability limits are 0.04 to 0.12 μg/L and 0.28 to 1.0 μg/L; the reproducibility limits are 0.12 ～ 0.24 μg/L and 0.96 ～ 2.4 μg/L, respectively. Six laboratories performed six replicates of seawater spiked samples containing chlorinated herbicides at 1.00 μg/L and 18.0 μg/L Repeat determination. the relative standard deviations in the laboratory are 3.9% to 15% and 2.6% to 11%, respectively; 0.8% to 5.6% and 1.5% to 4.0%, respectively; the repeatability limits are 0.04 to 0.10 μg/L and 0.32 to 1.1 μg/L, respectively; The performance limits were 0.08 to 0.16 μg/L and 1.0 to 2.2 μg/L, respectively. 9.1.2 Solid Phase Extraction Six laboratories performed 6 blank spiked samples with chlorinated herbicide concentrations of 0.500 μg/L and 10.0 μg/L Repeated determination. the relative standard deviations in the laboratory were 2.5% to 9.2% and 0.8% to 2.3%; the relative standard deviations between laboratories The differences are 14% to 27% and 1.8% to 4.1%, respectively; the repeatability limits are 0.02 to 0.04 μg/L and 0.04 to 0.16 μg/L, respectively; Reproducibility limits are 0.20 to 0.36 μg/L and 0.52 to 1.2 μg/L, respectively. Six laboratories performed spiked samples of surface water with chlorinated herbicide concentrations of 0.500 μg/L and 10.0 μg/L. 6 Repeated determinations. Relative standard deviations in the laboratory are 4.7% to 19% and 2.4% to 11%, respectively; The deviations are 7.5% to 16% and 2.9% to 11%, respectively; the repeatability limits are 0.02 to 0.06 μg/L and 0.20 to 0.70 μg/L, respectively; Reproducibility limits are 0.12 to 0.24 μg/L and 0.92 to 3.0 μg/L, respectively. 9.2 Accuracy 9.2.1 Liquid-liquid extraction Six laboratories carried out spiking recovery measurements on surface water samples containing chlorinated herbicides, and the spiking concentrations were 0.500 μg/L and 10.0 μg/L. Spike recovery rates are 72% to 102% and 79% to 102%, respectively. Final recovery rates They were 81% ± 10% ～ 89% ± 10% and 86% ± 9% ～ 92% ± 9%. 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