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Basic dataStandard ID: HJ 997-2018 (HJ997-2018)Description (Translated English): Soil and sediment - Determination of carbonyl compounds - High performance liquid chromatography Sector / Industry: Environmental Protection Industry Standard Classification of Chinese Standard: Z18 Word Count Estimation: 20,216 Date of Issue: 12/26/2018 Date of Implementation: 6/1/2019 Issuing agency(ies): Ministry of Ecology and Environment HJ 997-2018: Soil and sediment - Determination of carbonyl compounds - High performance liquid 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. Soil and sediment - Determination of carbonyl compounds - High performance liquid chromatography National Environmental Protection Standard of the People's Republic Determination of aldehydes and ketones in soils and sediments High performance liquid chromatography Soil and sediment-Determination of carbonyl compounds -High performance liquid chromatography Published on.2018-12-26 2019-06-01 Implementation Ministry of Ecology and Environment released i 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 Calculation and representation of results...5 9 Precision and Accuracy...6 10 Quality Assurance and Quality Control...7 11 Waste treatment...7 12 Notes...7 The detection limit and lower limit of determination of Appendix A (normative appendix) method...8 Appendix B (informative) Reference chromatograms of 15 aldehyde and ketone anthracene derivatives...9 Appendix C (informative) method for precision and accuracy...10 Appendix D (informative) Purification and blank test of 2,4-dinitrophenylhydrazine (DNPH)...16 ForewordTo protect the "Environmental Protection Law of the People's Republic of China" and the Law of the People's Republic of China on Soil Pollution Prevention This standard is formulated to ensure human health and to regulate the determination of aldehydes and ketones in soils and sediments. This standard specifies high performance liquid chromatography for the determination of aldehydes and ketones in soils and sediments. Appendix A of this standard is a normative appendix, and Appendix B to Appendix D are informative appendices. This standard is the first release. This standard is formulated by the Department of Eco-Environmental Monitoring, the Department of Regulations and Standards of the Ministry of Ecology and Environment. This standard was drafted. Tianjin Ecological Environment Monitoring Center. This standard is verified by the National Environmental Analysis and Testing Center, Shanghai Environmental Monitoring Center, and Shenyang Environmental Monitoring Center. Station, Qingdao Environmental Monitoring Center Station, Tianjin Product Quality Supervision and Inspection Technology Research Institute and Tianjin Binhai New Area Environmental Protection Protection station. This standard is approved by the Ministry of Ecology and Environment on December 26,.2018. This standard has been implemented since June 1,.2019. This standard is explained by the Ministry of Ecology and Environment. 1 Determination of aldehydes and ketones in soils and sediments - High performance liquid chromatography Warning. The organic solvents and reference materials used in the experiment are toxic and hazardous substances, standard solution preparation and sample preparation. The process should be carried out in a fume hood; protective equipment should be worn as required to avoid direct contact with skin and clothing.1 Scope of applicationThis standard specifies high performance liquid chromatography for the determination of aldehydes and ketones in soils and sediments. This standard applies to soil, sediment, formaldehyde, acetaldehyde, acrolein, acetone, propionaldehyde, crotonaldehyde, butyraldehyde, benzene Aldehyde, isovaleraldehyde, n-pentanal, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, n-hexanal, 2,5-dimethyl Determination of 15 kinds of aldehydes and ketones such as benzaldehyde. When the sample volume is 10 g and the volume is 10 ml, the detection limit of 15 aldehydes and ketones is 0.02. Mg/kg~0.06 mg/kg, the lower limit of determination is 0.08 mg/kg~0.24 mg/kg. See Appendix A for details.2 Normative referencesThe contents of this standard refer to the following documents or their terms. For undated references, the valid version applies. In this standard. GB 17378.3 Marine monitoring specification Part 3 Sample collection, storage and transportation 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/T 166 Technical Specifications for Soil Environmental Monitoring3 Principle of the methodSoil and sediment samples were extracted by shaking with acetic acid-sodium acetate solution. The aldehydes and ketones in the extract were at a certain temperature. And derivatization with 2,4-dinitrophenylhydrazine (DNPH) at pH to form stable terpenoids, extracted After concentration, it is separated by high performance liquid chromatography, detected by a UV detector, and quantified according to the retention time and external standard method.4 reagents and materialsUnless otherwise stated, analytically pure reagents that meet national standards were used for the analysis. Experimental water is double distilled water or pure The water prepared by the water equipment shall be subjected to blank inspection before use to confirm that the target compound concentration is lower than the method detection limit. 4.1 Sodium chloride (NaCl). After burning at 400 °C for 4 h, it is cooled slightly, placed in a desiccator, cooled to room temperature, transferred to a ground glass bottle, and kept in a desiccator. Save. 4.2 anhydrous sodium sulfate (Na2SO4). After burning at 400 °C for 4 h, it is cooled slightly, placed in a desiccator, cooled to room temperature, transferred to a ground glass bottle, and kept in a desiccator. 2 save. 4.3 Sodium acetate (CH3COONa). 4.4 Glacial acetic acid (CH3COOH). content ≥ 98%. 4.5 Citric acid (C6H8O7). 4.6 Sodium citrate (C6H5Na3O7·2H2O). 4.7 2,4-Dinitrophenylhydrazine [NH2NHC6H3(NO2)2, DNPH]. purity ≥99%. 4.8 Acetonitrile (CH3CN). Pure by liquid chromatography. 4.9 Dichloromethane (CH2Cl2). Pure by liquid chromatography. 4.10 Sodium chloride solution. ρ(NaCl) = 0.365 g/ml. Weigh 36.5 g of sodium chloride (4.1) and dissolve to 100 ml with water. 4.11 Extractant. Acetic acid-sodium acetate solution. Weigh 5.3 g of sodium acetate (4.3), dissolve in water, add 2.0 ml of glacial acetic acid (4.4), and dilute to 1 L with water. 4.12 Buffer solution. pH ≈3. 84.0 g of citric acid (4.5) and 29.4 g of sodium citrate (4.6) were weighed and dissolved in water to a volume of 500 ml. 4.13 Derivatizing agent. ρ (DNPH) = 3.00 mg/ml. 3.00 g of 2,4-dinitrophenylhydrazine (4.7) was weighed into acetonitrile (4.8) and dissolved to 1 L with acetonitrile. 4.14 Aldehyde, ketone-DNPH standard solution. ρ = 100 μg/ml (based on aldehydes, ketones). Including formaldehyde-DNPH, acetaldehyde-DNPH, acrolein-DNPH, acetone-DNPH, propionaldehyde-DNPH, crotonaldehyde-DNPH, Butyraldehyde-DNPH, benzaldehyde-DNPH, isovaleraldehyde-DNPH, n-pentanal-DNPH, o-methylbenzaldehyde-DNPH, inter- Methyl benzaldehyde-DNPH, p-methylbenzaldehyde-DNPH, n-hexanal-DNPH, 2,5-dimethylbenzaldehyde-DNPH. Dissolve The agent is acetonitrile (4.8). A commercially available certified standard solution can be purchased. 4.15 Standard stock solution of aldehyde and ketone. ρ=1000 μg/ml. Including formaldehyde, acetaldehyde, acrolein, acetone, propionaldehyde, crotonaldehyde, butyraldehyde, benzaldehyde, isovaleraldehyde, n-pentanal, ortho -Methyl benzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, n-hexanal, 2,5-dimethylbenzaldehyde. The solvent was acetonitrile (4.8). A commercially available certified standard solution can be purchased. 4.16 Standard use solution of aldehyde and ketone. ρ=100 μg/ml. Pipette 1.00 ml of aldehyde and ketone standard stock solution (4.15) in a 10 ml volumetric flask and dilute to volume with acetonitrile (4.8). It can be stored in cold storage for 2 months below 4 °C. 4.17 Quartz sand. The particle size is 0.297 mm~0.84 mm (50 mesh to 20 mesh). After burning at 400 °C for 4 h, it is cooled slightly, placed in a desiccator, cooled to room temperature, transferred to a ground glass bottle, and kept in a desiccator. Save. 4.18 Glass fiber membrane. pore size 0.45 μm. 4.19 Nitrogen. purity ≥ 99.9%.5 instruments and equipment5.1 High Performance Liquid Chromatograph. UV detector or diode array detector. 5.2 Column. octadecylsilane bonded silica gel column (C18), packing particle size 5.0 μm, column length 250 mm, inner diameter 4.6 mm, Or other equivalent column. 35.3 Vials. Not less than 60 ml brown wide-mouthed glass bottles with Teflon-silica-lined screw caps. 5.4 Oscillator. Horizontal oscillator or flip oscillator. 5.5 Constant Temperature Oscillator. Temperature accuracy is ±2 °C. 5.6 Extraction equipment. solid phase extraction unit or liquid-liquid extraction unit. 5.7 Concentration equipment. Equipment with comparable performance such as rotary evaporator, KD concentrator or nitrogen blow concentrator. 5.8 Balance. The sensitivity is 0.01 g. 5.9 Solid phase extraction column. C18 column or other equivalent solid phase extraction column, the specification is 1000 mg/6 ml or more. 5.10 Separating funnel. 250 ml, Teflon piston or glass piston without oil. 5.11 Extraction bottle..200 ml glass bottle with Teflon-silica liner screw cap. 5.12 Flat-bottomed flask..200 ml, with a flat-bottomed glass flask. 5.13 Common instruments and equipment used in general laboratories.6 samples6.1 Sample collection and preservation Soil samples were collected and stored in accordance with the relevant regulations of HJ/T 166. Water according to the relevant regulations of HJ 494 Collection of bulk sediment samples. The collection of marine sediment samples is carried out in accordance with the relevant provisions of GB 17378.3. Use a shovel or stainless steel scoop to collect the sample into the vial (5.3) as soon as possible and fill it up. Quickly remove the sample vial The sample adhered to the grain and the outer surface, sealed the sample bottle, and stored in the dark. If not analyzed in time, refrigerate below 4 ° C, 5 d Derivatization and extraction were completed, and the derivatized extract was analyzed within 7 days. 6.2 Preparation of samples Remove foreign matter (stones, leaves, etc.) from the sample and weigh 10 g (accurate to 0.01 g) of the sample in the extraction bottle (5.11) in. Another sample was weighed to determine the dry matter content or moisture content. 6.3 Determination of moisture The dry matter content of the soil sample was measured according to HJ 613, and the moisture content of the sediment sample was determined in accordance with GB 17378.5. 6.4 Preparation of samples 6.4.1 Extraction In the extraction vial containing the sample (6.2), add.200 ml of extractant (4.11), sealed, in the shaker (5.4) The mixture was shaken for not less than 18 h, filtered through a glass fiber filter (4.18), and the extract was collected for derivatization. 6.4.2 Derivative Take 100 ml of extract (6.4.1) in a flat-bottomed flask (5.12), add 4 ml of buffer solution (4.12), 6 ml The biocide (4.13) was placed in a constant temperature oscillator (5.5) and shaken at 40 ° C for 1 h. Note. You can use a temperature-controlled ultrasonic cleaner or ultrasonic extractor instead of a constant temperature oscillator. The ultrasonic time is not less than 30 min, and the ultrasonic temperature is not exceeded. Over 40 ° C ± 2 ° C. 46.4.3 Extraction and concentration 6.4.3.1 Solid phase extraction The solid phase extraction column (5.9) was fixed on a solid phase extraction apparatus (5.6) with 10 ml of acetonitrile (4.8) and 10 ml, respectively. Water activated extraction column. Add 10 ml of sodium chloride solution (4.10) to the derivatized solution (6.4.2) and transfer to the extraction column. The loading speed is 3 ml/min~5 ml/min. Rinse the vessel and tubing with 10 ml of water and continue to pump for 1 min. use 9 ml of acetonitrile (4.8) was eluted from the extraction column at a flow rate of 3 ml/min to 5 ml/min, and the eluate was collected into a 10 ml volumetric flask. Dilute to the mark with acetonitrile (4.8), mix and test. 6.4.3.2 Liquid-liquid extraction Transfer the derivatized solution (6.4.2) to a separatory funnel (5.10) and add 1.5 g of NaCl (4.1), respectively. 15 ml and 10 ml of dichloromethane (4.9) were extracted twice, and the extracts were combined and the extract was dehydrated with anhydrous sodium sulfate (4.2). Concentrate to near dryness with a concentration device (5.7), change the solvent to acetonitrile (4.8), determine the volume to 10 ml with acetonitrile, and mix. To be tested. Note. High concentration samples can be appropriately added once. 6.5 Preparation of blank samples The sample was replaced with quartz sand (4.17), and the preparation of the blank sample was carried out in the same manner as in the preparation of the sample (6.4).7 Analysis steps7.1 Reference chromatographic conditions Mobile phase. 60% acetonitrile 40% water, isocratic elution, hold for 30 min; Detection wavelength. 360 nm; Mobile phase flow rate. 1.0 ml/min; Column temperature. 30 ° C; Injection volume. 10 μl. 7.2 Establishment of the standard curve Transfer an appropriate amount of aldehyde, ketone-DNPH standard solution (4.14), and make a mass concentration of 0.03 with acetonitrile (4.8). Standard series of mg/L, 0.05 mg/L, 0.10 mg/L, 0.50 mg/L, 1.00 mg/L and 1.50 mg/L. According to reference color Spectral conditions (7.1) were determined by taking the standard series target compound concentration as the abscissa and its corresponding peak area or peak height. For the ordinate, a standard curve is established. 7.3 Reference chromatogram The chromatograms of the 15 aldehyde and ketone anthracene derivatives on the C18 column (5.2) are shown in Figure 1. Note. See Appendix B for the separation of other different types of columns. 51. Formaldehyde-DNPH; 2. Acetaldehyde-DNPH; 3. Acrolein-DNPH; 4. Acetone-DNPH; 5. Propionaldehyde-DNPH; 6. Butenal-DNPH; 7. Butyraldehyde-DNPH; 8. benzaldehyde-DNPH; 9. isovaleraldehyde-DNPH; 10. n-pentanal-DNPH; 11. o-methylbenzaldehyde-DNPH; 12. m-methylbenzaldehyde-DNPH; 13. p-Methyl benzaldehyde-DNPH; 14. n-hexanal-DNPH; 15.2,5-dimethylbenzaldehyde-DNPH. Figure 1 Reference chromatogram of 15 aldehyde and ketone anthracene derivatives 7.4 Sample determination The measurement of the sample (6.4) was carried out in the same manner as the establishment of the standard curve (7.2). 7.5 Blank test The blank sample (6.5) was measured in the same manner as in the sample measurement (7.4).8 Calculation and representation of results8.1 Qualitative analysis Qualitative according to the retention time of the target compound. If necessary, use standard addition method, absorption ratio at different wavelengths, UV Methods such as spectral scanning aid the qualitative. 8.2 Calculation of results 8.2.1 Calculation of results of soil samples The target content w in the soil sample is calculated according to formula (1). 2dm V Vw m WV (1) Where. w--the content of the target compound in the sample, mg/kg; --the mass concentration of the target compound in the sample calculated from the standard curve, mg/L; V--sample volumetric volume, ml; V1--extractant volume, ml; V2--extraction sample volume, ml; m -- sample weighing, g; dmW - sample dry matter content, %. 68.2.2 Calculation of results of sediment samples The target content w in the sediment sample is calculated according to formula (2). twenty one- V Vw m WV ( ) (2) Where. w--the content of the target compound in the sample, mg/kg; --the mass concentration of the target compound in the sample calculated from the standard curve, mg/L; V--sample volumetric volume, ml; V1--extractant volume, ml; V2--extraction sample volume, ml; m -- sample weighing, g; W--sample moisture content, %. 8.3 Result representation The retention of the number of digits after the decimal point is consistent with the method detection limit, and up to 3 significant digits are retained. Note. m-methylbenzaldehyde-DNPH and p-methylbenzaldehyde-DNPH are difficult to separate substances. When the column cannot separate the two, measure The result is the sum of the difficult to separate substances.9 Precision and accuracy9.1 precision Six laboratories added aldehyde and ketone compounds to soils with concentrations of 0.20 mg/kg, 0.50 mg/kg, and 2.00 mg/kg, respectively. The soil samples were subjected to 6 repeated measurements, and the relative standard deviations in the laboratory were 4.8% to 29% and 4.3% to 33%, respectively. 0.20%~29%; the relative standard deviations between laboratories are. 10%~20%, 6.4%~20%, 6.6%~20%; repeatability limit Respectively. 0.05 mg/kg to 0.09 mg/kg, 0.14 mg/kg to 0.22 mg/kg, 0.37 mg/kg to 0.72 mg/kg; reproducibility The limits are. 0.07 mg/kg ~ 0.10 mg/kg, 0.18 mg/kg ~ 0.25 mg/kg, and 0.66 mg/kg ~ 0.90 mg/kg. Six laboratories added aldehydes and ketones at concentrations of 0.20 mg/kg, 0.50 mg/kg, and 2.00 mg/kg, respectively. The samples were re-measured 6 times. The relative standard deviations in the laboratory were 2.8%~32% and 2.5%~29%, respectively. 1.7%~22%; the relative standard deviations between laboratories are. 7.9%~21%, 11%~19%, 6.7%~21%; repeatability limit Respectively. 0.05mg/kg ~0.09mg/kg, 0.10 mg/kg ~0.25 mg/kg, 0.33 mg/kg ~0.65 mg/kg; reproducibility The limits are. 0.07mg/kg ~0.11 mg/kg, 0.15 mg/kg ~0.38 mg/kg, 0.47 mg/kg ~1.02 mg/kg. See Appendix C for precision results. 9.2 Accuracy The concentration of aldehydes and ketones in the six laboratories was 0.20 mg/kg, 0.50 mg/kg, 2.00 mg/kg, respectively. The soil samples were tested six times. The recoveries ranged from 43.5% to 101% and 41.5% to 99.0%. 42.0%~104%, the final recoveries of the spiked recovery are. 56.3%±19.0%~87.0%±20.4%, 51.2% ± 21.4% ~ 77.2% ± 35.2%, 50.8% ± 26.6% ~ 88.7% ± 14.8%. The concentration of aldehydes and ketones in the six laboratories was 0.20 mg/kg, 0.50 mg/kg, 2.00 mg/kg, respectively. 7 Sediment samples were subjected to 6 replicate measurements. The recoveries ranged from 46.3% to 112% and 40.8% to 112%, respectively. 41.3%~116%, the final recoveries of the spiked recovery were. 54.5%±15.4%~91.2%±30.4%, 47.9%±22.8%~90.5%±26.2%, 45.2%±20.6%~94.7%±32.0%. See Appendix C for accuracy results. 10 Quality Assurance and Quality Control 10.1 At least one laboratory blank shall be analyzed for each batch of samples, and the target determination results shall be lower than the method detection limit. 10.2 The correlation curve of the standard curve should be ≥0.999, otherwise it should be recalibrated. 10.3 Analyze at least 1 standard curve intermediate concentration point for every 20 samples or batches (less than 20 samples/batch) The relative error between the measured value and the standard value is within ±20%, otherwise the standard curve should be redrawn. 10.4 Test at least 1 parallel sample for every 20 samples or batches (less than 20 samples/batch), parallel sample determination results The relative deviation should be ≤ 45%. 10.5 Analyze at least 1 matrix plus standard for every 20 samples or batches (less than 20 samples/batch), aldehyde compounds The recovery should be between 45% and 120%, and the acetone recovery should be between 40% and 100%. 11 Waste treatment The waste generated in the experiment should be collected and stored in a centralized manner and sent...... |
