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HJ 834-2017: Soil and sediment. Determination of semivolatile organic compounds. Gas chromatography /Mass spectrometry
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Soil and sediment. Determination of semivolatile organic compounds. Gas chromatography /Mass spectrometry
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HJ 834-2017
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Basic data | Standard ID | HJ 834-2017 (HJ834-2017) | | Description (Translated English) | Soil and sediment. Determination of semivolatile organic compounds. Gas chromatography /Mass spectrometry | | Sector / Industry | Environmental Protection Industry Standard | | Classification of Chinese Standard | Z18 | | Classification of International Standard | 13.080 | | Word Count Estimation | 30,322 | | Date of Issue | 2017-07-18 | | Date of Implementation | 2017-09-01 | | Quoted Standard | GB 17378.3; GB 17378.5; HJ 613; HJ 783; HJ/T 166 | | Regulation (derived from) | MEP Announcement 2017 No. 31 | | Issuing agency(ies) | Ministry of Ecology and Environment | | Summary | This standard specifies the determination of semi-volatile organic compounds in soil and sediment by gas chromatography - mass spectrometry. This method is suitable for the treatment of chlorinated hydrocarbons, phthalates, nitrosamines, ethers, haloethers, ketones, anilines, pyridines, quinolines, nitroaromatic hydrocarbons in soils and sediments Class, phenols (including nitrophenols), organochlorine pesticides, polycyclic aromatic hydrocarbons and other semi-volatile organic compounds screening and quantitative analysis, for a particular class of compounds, should be selected based on the screening of proprietary analysis Method determination. The detection limit was 0.06 ~ 0.3 mg/kg and the lower limit of determination was 0.24 ~ 1.20 mg/kg when the volume of sample was 20.0 g and the volume of constant volume was 1.0 ml. See Appendix A for details. | HJ 834-2017: Soil and sediment. Determination of semivolatile organic compounds. Gas chromatography /Mass spectrometry
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(Soil and sediment - Determination of semi - volatile organic compounds - Gas chromatographic - mass spectrometry)
National Environmental Protection Standard of the People 's Republic of China
Determination of semi - volatile organic compounds in soil and sediments
Gas chromatography - mass spectrometry
Soil and sediment - Determination of semivolatile organic compounds
- Gas chromatography/Mass spectrometry
2017-07-18 released
2017-09-01 implementation
Issued by the Ministry of Environmental Protection
i directory
Preface .ii
1 Scope of application
2 normative reference documents
3 Principle of the method
4 reagents and materials 1
5 instruments and equipment 3
6 Sample 3
7 Analysis steps
8 results are calculated and expressed
9 Precision and Accuracy
Quality Assurance and Quality Control
11 Waste disposal 10
12 Note ..10
Appendix A (normative) method detection limit and lower limit of measurement
Appendix B (informative) Methods for purification of magnesium silicate and silica gel column
Appendix C (informative) Determination of the target compound Reference parameter 17
Appendix D (informative) method of precision and accuracy
Foreword
For the implementation of the "People's Republic of China Environmental Protection Law" to protect the environment, protect human health, regulate soil and sediment
Semi-volatile organic compounds in the determination of the development of this standard.
This standard specifies the determination of semi-volatile organic compounds in soil and sediments by gas chromatography-mass spectrometry.
This standard is the first release.
Appendix A to this standard is a normative appendix, Appendix B to Appendix D are informative appendices.
This standard is organized by the Environmental Monitoring Department of the Ministry of Environmental Protection, the Secretary for Science and Technology Standards.
The main drafting of this standard. Henan Province Environmental Monitoring Center.
The standard verification unit. Xinxiang City, Henan Province Environmental Monitoring Station, Henan Province Environmental Science Research Institute, Henan Entry and Exit Inspection
Quarantine Bureau Technology Center, Kaifeng City Environmental Monitoring Station, Institute of Hydrogeology and Geology, Chinese Academy of Geological Sciences, Henan Province
Environment monitoring center.
The Environmental Protection Department of this standard approved on July 18,.2017.
This standard has been implemented since September 1,.2017.
This standard is explained by the Ministry of Environmental Protection.
Determination of semi - volatile organic compounds in soil and sediments - Gas chromatographic - mass spectrometry
Warning. The organic solvents and reference materials used in the test are toxic and hazardous substances, standard solution preparation and sample pretreatment
Should be carried out in the fume hood; operation should be required to wear protective equipment, to avoid organic solvents and reference materials directly contact the skin
Skin and clothing.
1 Scope of application
This standard specifies the determination of semi-volatile organic compounds in soil and sediments by gas chromatography-mass spectrometry.
The method is applicable to the soil and sediments of chlorinated hydrocarbons, phthalates, nitrosamines, ethers, halogen ethers,
Ketones, anilines, pyridines, quinolines, nitroaromatic hydrocarbons, phenols including nitrophenols, organochlorine pesticides, polycyclic
Aromatic hydrocarbons and other semi-volatile organic matter screening and quantitative analysis, for a particular class of compounds, should be selected in this foundation
On the use of proprietary analytical methods.
The sampling volume was 20.0 g, the volume of volume was 1.0 ml. When the total scanning method was used, the detection limit was 0.06 mg/kg ~
0.3 mg/kg, the determination of the lower limit of 0.24 mg/kg ~ 1.20 mg/kg. See Appendix A.
2 normative reference documents
The contents of this standard refer to the following documents or their terms. Those who do not specify the date of the reference file, the effective version of the appropriate
For this standard.
Specification for ocean monitoring - Part 3. Sample collection, storage and transport
Specification for marine monitoring - Part 5. Sediment analysis
Determination of Dry Matter and Moisture in Soil
Extraction of pressurized fluid from soil and sediment organic matter
Technical specification for soil environmental monitoring
3 Principle of the method
The semi-volatile organic compounds in soil or sediments are extracted by suitable extraction methods (Soxhlet extraction, pressurized fluid extraction, etc.)
Take the appropriate cleaning method (gel permeation chromatography or column purification) according to the sample matrix interference to purify the extract,
Concentrated, constant volume, separated by gas chromatography, mass spectrometry. According to the retention time, fragment ion mass ratio and its abundance qualitative,
Internal standard method.
4 reagents and materials
Unless otherwise stated, analytical reagents conforming to national standards are used for analysis. Experimental water for the new preparation of ultra-pure water
Or distilled water.
4.1 acetone (C3H6O). pesticide residues.
4.2 dichloromethane (CH2Cl2). pesticide residues.
4.3 Ethyl acetate (C4H8O2). pesticide residues.
4.4 Cyclohexane (C6H12). Pesticide level.
4.5 dichloromethane - acetone mixed solvent. 1 1.
2 were mixed at a 1. 1 by volume ratio with dichloromethane (4.2) and acetone (4.1).
4.6 Gel Permeation Chromatography Mobile phase. mixed with 1 1 volume ratio with ethyl acetate (4.3) and cyclohexane (4.4), or by instrument
The preparation of other solvent system.
4.7 nitric acid. ρ (HNO3) = 1.42 g/ml, excellent grade pure.
4.8 nitric acid solution. 1 1.
With excellent grade pure nitric acid (4.7) and experimental water by 1. 1 volume ratio.
4.9 Copper powder (Cu). purity 99.5%
Use the nitric acid solution (4.8) to remove the oxide on the surface of the copper powder before use, rinse off the acid with experimental water, and use acetone (4.1)
After cleaning, and then use high-purity nitrogen slowly dry standby, each temporary treatment, to keep the copper powder surface bright.
4.10 semi-volatile organic standard stock solution. ρ = 1000 mg/L ~ 5000 mg/L, commercially available standard solution.
4.11 semi-volatile organic standard intermediate liquid. ρ =.200 μg/ml ~ 500 μg/ml.
The semi-volatile organic standard stock solution (4.10) was diluted with dichloromethane-acetone mixed solvent (4.5).
4.12 Internal standard stock solution. ρ = 5000 mg/L
1,4-dichlorobenzene-d4, naphthalene-d8, acenaphthene-d10, phenanthrene-d10, 䓛-d12 and perylene-d12, commercially available standard solutions. You can also use other
Nature of semi-volatile organic matter similar to the internal standard.
4.13 internal standard liquid. ρ =.200 μg/ml ~ 500 μg/ml.
The internal standard stock solution (4.12) was diluted with dichloromethane-acetone mixed solvent (4.5) and mixed.
4.14 Substitute stock solution. ρ = 1000 mg/L to 4000 mg/L.
Phenol-d6,2-fluorophenol, 2,4,6-tribromophenol, nitrobenzene-d5,2-fluorobiphenyl, 4'4-terphenyl-d14 and other commercially available
Quasi solution.
4.15 Substitute intermediate. ρ =.200 μg/ml to 500 μg/ml.
The stock solution (4.14) was diluted with dichloromethane-acetone mixed solvent (4.5) and mixed.
4.16 decafluorotriphenylphosphine (DFTPP). ρ = 50 mg/L, commercially available standard solution.
The other concentrations were diluted with dichloromethane (4.2) to 50 mg/L and mixed.
4.17 Gel Permeation Chromatography Calibration Solution. Contains corn oil (25 mg/ml), di (2-diethylhexyl) phthalate
(1 mg/ml), methotrexate (200 mg/L), perylene (20 mg/L) and sulfur (80 mg/L). Commercially available.
Note. All standard stock solutions from 4.10 to 4.17 should be stored in accordance with the manufacturer's instructions. All the intermediate liquids should be at -10 ° C
Save as below. Before use should check the changes, once the evaporation or degradation should be re-preparation, should be used before the room temperature, mixing.
4.18 desiccant. excellent grade pure anhydrous sodium sulfate (Na2SO4) or granular diatomite 250 μm ~ 150 μm (60 mesh ~ 100 mesh).
Placed in muffle furnace 400 ℃ baking 4 h, after cooling into the grinding glass bottle sealed in the dryer to save.
4.19 glass column. diameter 20 mm, length 10 cm ~ 20 cm, with PTFE piston.
4.20 quartz sand. 150 μm ~ 830 μm (100 mesh to 20 mesh).
Placed in the muffle furnace at 400 ℃ baking 4 h, after cooling into a plugged glass bottle sealed sealed.
4.21 glass wool or glass fiber filter. before use with dichloromethane (4.2) immersion, to be dichloromethane (4.2) volatile dry,
Sealed in a sealed glass bottle.
4.22 Soxhlet extraction sleeve. glass fiber or natural fiber material sleeve. Before use, the glass fiber sleeve is placed in the muffle furnace
400 ℃ baking 4 h, natural fiber sleeve application and sample extraction of the same solvent purification.
4.23 High purity nitrogen. purity 99.999%.
34.24 Carrier gas. high purity helium, purity 99.999%.
5 instruments and equipment
5.1 Gas Chromatography/Mass Spectrometer. Electronically bombarded (EI) ionization source.
5.2 Column. quartz capillary column, length 30 m, inner diameter 0.25 mm, film thickness 0.25 m, stationary phase 5% - phenyl-methyl
Polysiloxane, or other equivalent capillary column.
5.3 Extraction device. Soxhlet extraction or pressurized fluid extractor and other equipment equivalent performance.
5.4 Gel Permeation Chromatography (GPC). a 254 nm fixed wavelength UV detector, filled with gel packing column.
5.5 Concentration device. rotary evaporator, nitrogen blowing instrument or other equivalent equipment.
5.6 Vacuum Freeze Dryer. No load vacuum below 13 Pa.
5.7 solid phase extraction device.
5.8 General laboratory equipment and equipment commonly used.
6 samples
6.1 Collection and storage of samples
Soil samples were collected and preserved according to the relevant requirements of HJ/T 166, and the samples of sediment were in accordance with the relevant requirements of GB 17378.3
Collection and preservation. Samples should be stored in a clean, flat-edged brown glass bottle. Transport should be sealed, dark, 4 ℃ to
Under the cold storage. Transported to the laboratory, if not timely analysis, should be below 4 ℃ cold, dark, sealed, save time
No more than 10 days.
6.2 Determination of moisture
Determination of dry matter content of soil samples According to HJ 613, the moisture content of sediment samples was measured according to GB 17378.5.
6.3 Preparation of the sample
6.3.1 Sample preparation
The sample on the enamel plate or stainless steel plate, mix, remove branches sticks, leaves, stones and other foreign bodies, according to HJ/T 166
Quadrilateral Samples for screening contaminants should be treated with fresh samples. Natural drying does not affect
For analysis purposes, the sample can also be naturally dried. Fresh soil or sediment samples can be dried using freeze-dried and desiccant methods
dry. If the moisture content of soil or sediment samples is higher (greater than 30%), the water phase should be centrifuged and the water phase
Line drying.
Method 1. freeze-drying method. Take appropriate sample after mixing, into the vacuum freeze dryer (5.6) for drying and dehydration. dry
The dried samples were milled and passed through a 0.25 mm pore size sieve and homogenized to about 250 μm (60 mesh). then
Weigh 20 g (accurate to 0.01 g) sample, all transferred to the extractor to be used.
Method 2. desiccant method. Weigh 20 g (accurate to 0.01 g) fresh sample, add a certain amount of desiccant (4.18)
Mix, dehydrate and grind into fine particles, mix well until it is scattered, all transferred to the extraction container.
6.3.2 Extraction
Extraction method can choose Soxhlet extraction, pressurized fluid extraction and other equivalent extraction method.
a) Soxhlet extraction. Transfer the prepared soil or sediment sample to the Soxhlet extraction sleeve (4.22)
The quasi-curve above the intermediate point of the concentration of the intermediate (4.15), carefully placed in the Soxhlet extractor tube, in the round bottom solvent
The mixture was added with 100 ml of dichloromethane-acetone mixed solvent (4.5) for 16 h to 18 h, and the reflux rate was controlled at 4
Times ~ 6 times. Then stop heating the reflux, remove the round bottom solvent bottle, to be concentrated.
4b) Pressurized fluid extraction. Follow HJ 783.
Note. If there is significant moisture in the above extract, further filtration and dehydration are required. Place a layer of glass wool or glass fiber on the glass funnel
Filter (4.21), add about 5 g of anhydrous sodium sulfate (4.18) and filter the extract into the concentrate vessel. And then mixed with a small amount of dichloromethane - acetone dissolved
(4.5) to wash the container 3 times, the washing liquid into the funnel to filter, and finally a small amount of dichloromethane - acetone mixed solvent (4.5) rinse the leak
Bucket, all collected to the concentration of utensils, to be concentrated.
6.3.3 Concentration
Concentration method recommended the use of the following two ways, other methods can be verified when the effect is better or equivalent.
a) Nitrogen blowing
At room temperature, open the nitrogen to the solvent surface with gas flow fluctuations (to avoid the formation of gas vortex), with dichloromethane (4.2)
Repeatedly washed the nitrogen blowing process has been exposed during the condenser wall. Concentrate to about 2 ml to stop the concentration.
When purified by gel permeation chromatography, add about 5 ml gel permeation chromatography mobile phase (4.6) for solvent conversion,
And then concentrated to about 1 ml, to be purified.
When a specific type of semi-volatile organic compounds is to be purified, the solvent can be converted according to the method of Appendix B and concentrated
To about 1 ml to be purified.
b) Rotate Evaporation Concentration
The heating temperature was set at about 40 ° C, and the extract (6.3.2) was concentrated to about 2 ml to stop the concentration. With disposable dropper
The concentrated solution was transferred to a graduated concentrator and the bottom of the rotary vial was mixed with a small amount of dichloromethane-acetone mixed solvent (4.5)
Rinse 2 times, merge all the concentrate, and then boil to about 1 ml with nitrogen to be purified.
When purged with gel permeation chromatography, when the above-mentioned concentrate nitrogen was blown to 2 ml, about 5 ml gel permeation chromatography
The mobile phase (4.6) is solvent converted and concentrated to about 1 ml to be purified.
When a specific type of semi-volatile organic compounds is to be purified, the solvent can be converted according to the method of Appendix B and concentrated
To about 1 ml to be purified.
6.3.4 Purification
6.3.4.1 Gel permeation chromatography purification
When the purpose of the analysis is to screen all semi-volatile organic compounds, gel permeation chromatography should be used.
a) Gel permeation column calibration
The gel permeation column was calibrated according to the instrument brochure, and the chromatogram was calibrated by gel permeation chromatography (4.17)
The peak should meet the following conditions. all peaks are symmetrical; the chromatographic peaks of corn oil and bis (2-diethylhexyl) phthalate
Between the resolution greater than 85%; phthalic acid bis (2-diethylhexyl) ester and methanol droplets between the peaks of the large resolution
At 85%; the resolution between methotrexate and perylene peaks is greater than 85%; the peaks of perylene and sulfur can not overlap,
From more than 90%.
b) Determine the collection time
The collection time of semi-volatile organic matter is initially determined before the peak of the corn oil reaches the peak of the sulfur, and the perylene is eluted
That is to stop collecting. And then using semi-volatile organic standard intermediate (4.11) injection to form a standard spectrum, according to the standard substance
The spectra further determine the start and stop collection times and determine their recovery rates. Low boiling point of semi-volatile organic compounds
The rate of recovery and other factors led to the recovery rate decreased, when the majority of the target recovery rate is greater than 90%, you can click here
Set the time and instrument conditions to purify the sample, otherwise you will need to adjust the collection time and other conditions.
c) Extraction of the extract
5 Flow chromatographic mobile phase with gel permeation (4.6) The concentrated extract (6.3.3) was added to the gel permeation chromatograph dosing loop
The volume required is automatically purified according to the determined collection time, and the effluent is collected until it is concentrated again (6.3.5).
6.3.4.2 column purification
When the analysis is concerned only with certain compounds in semi-volatile organic compounds, chromatography with different adsorbents can be used
Column for purification.
The recommended purification methods for different target items are shown in Table 1. See Appendix B for specific operating procedures. Other methods to verify the effect of excellent
Equivalent to or when used.
Table 1 Target analyte categories and applicable purification methods
Target compound alumina column magnesium silicate column silica gel column gel permeation chromatography
Aniline and aniline derivatives
Phenol
Phthalates Pec
Nitrosamines P
Organochlorine pesticides Phip
Nitroaromatic and cyclic ketones
Polycyclic Aromatic Hydrocarbons Phip
Halogenated Ethers
Chlorinated hydrocarbons
Other semi - volatile organic compounds
6.3.5 Concentration, plus internal standard
The purified test solution (6.3.4) was concentrated again by the step of nitrogen concentration or rotary evaporation (6.3.3)
Into the amount of internal standard liquid (4.13), and set to 1.0 ml, after mixing transferred to 2 ml vials, to be tested.
6.4 Preparation of blank samples
The blank sample was prepared in the same manner as in the preparation (6.3) of the sample using quartz sand (4.20) instead of the actual sample.
7 Analysis steps
7.1 Instrument reference conditions
7.1.1 Gas Chromatographic Reference Conditions
Inlet temperature. 280 ° C, splitless;
Injection volume. 1.0 μl, column flow. 1.0 ml/min (constant current);
Column temperature. 35 ℃ start to keep 2 min; at 15 ℃/min temperature to 150 ℃, keep 5 min; at 3 ℃/min temperature
To 290 ° C for 2.0 min.
Note. Hold to the last target after benzo (ghi) perylene peaks.
7.1.2 Mass spectrometry reference conditions
Electron bombardment source (EI);
Ion source temperature. 230 ° C;
Ionization energy. 70 eV;
6 Interface temperature. 280 ° C;
Four pole temperature. 150 ℃
Quality scanning range. 35 amu ~ 450 amu;
Solvent delay time. 5 min.
Data acquisition mode. full scan (Scan) or select the ion mode (SIM) mode.
7.2 Calibration
7.2.1 Mass spectrometry performance check
Before each analysis, mass spectrometry should be automatically tuned, and then the gas chromatography and mass spectrometer set to the analytical method required instrument
Condition and in a standstill state, directly injected into the 1.0 μl defluorotriphenylphosphine (DFTPP) (4.16) by gas chromatography inlet.
Solution to obtain a deca-fluorotriphenylphosphine spectrum, and the ion abundance of its mass debris should all meet the requirements in Table 2. Otherwise be required
Clean the mass spectrometer ion source.
Table 2 Deafluorotriphenylphosphine (DFTPP) ion abundance specification requirements
Mass - to - charge ratio (m/z) relative abundance specification mass - to - charge ratio (m/z) relative abundance specification
51 198 peaks (base) 30-60%.199 198 peaks 5-9%
68 2% less than 69 peaks 275% of peak 10-30%
70 less than 69 peaks of 2% 365 greater than 1% of peak
127 & lt;/RTI & gt; & lt;/RTI & gt;
197 less than 198 peaks 1% 442 base or more than 198 peaks of 40%
198 base peak, abundance 100% 443 442 peak 17-23%
7.2.2 Drawing of calibration curves
Take 5 5 ml volumetric flask, add 2 ml of dichloromethane solvent (4.2), take appropriate amount of semi-volatile organic
(4.11), the intermediate intermediate (4.15) and the internal standard intermediate (4.13) were treated with methylene chloride solvent (4.2)
Set the volume after mixing, prepared at least 5 concentration points of the standard series. The concentration of semi-volatile organic compounds and substitutes is different
And the concentration of the internal standard was 40.0 μg/ml, which was 1.0 μg/ml, 5.0 μg/ml, 10.0 μg/ml, 20.0 μg/ml and 50.0 μg/ml.
It can also be calibrated according to the instrument sensitivity or the concentration of the target in the sample to other gas chromatography-mass spectrometers for the appropriate concentration level
series.
According to the instrument reference conditions (7.1), from low to high concentrations of sequential injection analysis. With the target compound concentration for sitting
The ratio of the ratio of the quantitated ion response of the target compound to the internal standard compound and the product of the mass concentration of the internal standard compound
Standard, draw the calibration curve.
7.2.3 Chromatography/Mass Spectrometry of Standard Samples
The total ion chromatogram of the target is shown in Fig. 1 under the reference conditions recommended by this standard.
(Phenol), phenol, dibromo-2- (2-chloroethyl) ether, 6.2-chlorophenol, ; 1,1,2-dichlorophenyl; 8.14-dichlorobenzene-d4 (internal standard); 9.1,4-dichlorobenzene; 10.1,2-dichlorobenzene; 11.2-methylphenol;
(2-chloroisopropy...
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