HJ 645-2013_English: PDF (HJ645-2013)
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Ambient air. Determination of volatile halogenated hydrocarbons. Activated charcoal adsorption and carbon disulfide desorption/gas chromatographic method
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HJ 645-2013
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| Standard ID | HJ 645-2013 (HJ645-2013) | | Description (Translated English) | Ambient air. Determination of volatile halogenated hydrocarbons. Activated charcoal adsorption and carbon disulfide desorption/gas chromatographic method | | Sector / Industry | Environmental Protection Industry Standard | | Classification of Chinese Standard | Z11 | | Classification of International Standard | 13.040.20 | | Word Count Estimation | 13,186 | | Quoted Standard | HJ/T 194 | | Drafting Organization | Dalian Municipal Environmental Monitoring Center | | Administrative Organization | ?Ministry of Environmental Protection | | Regulation (derived from) | Department of Environmental Protection Notice No. 12 of 2013 | | Summary | This standard specifies the determination of volatile halogenated hydrocarbons in ambient air activated carbon adsorption carbon disulfide desorption/gas chromatography. This standard applies to the ambient air chlorobenzene, benzyl chloride, 1, 1 dichlor |
HJ 645-2013
Ambient air.Determination of volatile halogenated hydrocarbons.Activated charcoal adsorption and carbon disulfide desorption/gas chromatographic method
National Environmental Protection Standard of the People's Republic
Determination of volatile halogenated hydrocarbons in ambient air
Activated carbon adsorption-carbon disulfide desorption/gas chromatography
Ambient air - Determination of volatile halogenated hydrocarbons -
Activated charcoal adsorption and carbon disulfide desorption/gas
Chromatographic method
2 0 1 3 - 2 - 1 7 released
2 0 1 3 - 7 - 1 Implementation
release
Ministry of Environmental Protection
Content
Foreword. II
1 Scope 1
2 Normative references 1
3 Principle of the method 1
4 interference and elimination..1
5 reagents and materials..1
6 instruments and equipment..1
7 samples..2
8 Analysis step 3
9 Calculation and representation of results 4
10 precision and accuracy. 5
11 Quality Assurance and Quality Control..5
Appendix A (normative appendix) detection limit and lower limit of determination of target 6
Appendix B (informative) method of precision and accuracy..7
Foreword
To implement the Environmental Protection Law of the People's Republic of China and the Law of the People's Republic of China on the Prevention and Control of Atmospheric Pollution
This standard is formulated to ensure human health and to regulate the determination of volatile halogenated hydrocarbons in ambient air.
This standard specifies the adsorption of activated carbon for the determination of volatile halogenated hydrocarbons in ambient air - carbon disulfide desorption/gas chromatography
law.
This standard is the first release.
Appendix A of this standard is a normative appendix, and Appendix B is an informative appendix.
This standard was formulated by the Science and Technology Standards Department of the Ministry of Environmental Protection.
This standard is mainly drafted by. Dalian Environmental Monitoring Center and Environmental Standards Research Institute of the Ministry of Environmental Protection.
This standard is verified by. Anshan City Central Monitoring Center Station, Shenyang Environmental Monitoring Center Station, and Fushun City Environmental Monitoring
Xinzhan, Changchun Environmental Monitoring Center Station, Jiangsu Environmental Monitoring Center and Harbin Environmental Monitoring Center Station.
This standard was approved by the Ministry of Environmental Protection on February 17,.2013.
This standard has been implemented since July 1,.2013.
This standard is explained by the Ministry of Environmental Protection.
Determination of Volatile Halohydrocarbons in Ambient Air - Adsorption of Activated Carbon - Carbon Disulfide Solution
Suction/gas chromatography
Warning. Standard samples and carbon disulfide used in the experiment are volatile toxic chemicals, solution preparation process
It should be carried out in a fume hood and the operator should wear protective gear.
1 Scope of application
This standard specifies activated carbon adsorption-carbon disulfide desorption/gas chromatography for the determination of volatile halogenated hydrocarbons in ambient air.
This standard applies to ambient air chlorobenzene, benzyl chloride, 1,1-dichloroethane, 1,2-dichloroethane, trans-1,2-dichloro
Ethylene, cis-1,2-dichloroethylene, 1,2-dichloropropane, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,1,1 -Trichloro
Ethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, tribromomethane, 1-bromo-2-chloroethane, 1,2,3-trichloropropane,
Determination of 21 volatile halogenated hydrocarbons such as 1,1,2,2-tetrachloroethane, tetrachloroethylene, carbon tetrachloride, and hexachloroethane. If passed
This standard is also applicable to the determination of other volatile halogenated hydrocarbons.
When the sampling volume is 10 L, the detection limit of this method is 0.03~10 μg/m3, and the lower limit of determination is 0.12~40.
Gg/m3, see Appendix A for details.
2 Normative references
The contents of this standard refer to the following documents or their terms. Valid versions of undated references
Applicable to this standard.
HJ/T 194 Technical Specifications for Manual Air Quality Monitoring
3 Principle of the method
Volatile halogenated hydrocarbons in ambient air are enriched by activated carbon sampling tubes and desorbed with carbon disulfide (CS2).
Gas chromatograph with an electron capture detector (ECD) was characterized by retention time and quantified by external standard method.
4 interference and elimination
Determination of volatile halogenated hydrocarbons in ambient air by gas chromatography, benzene series, n-hexane, acetic acid in ambient air
Ethyl ester and cyclohexane did not interfere with the assay.
5 reagents and materials
5.1 Carbon disulfide. chromatographically pure, no interference peaks were determined by gas chromatography under the recommended conditions.
5.2 Standard stock solution. Prepare a suitable amount of chromatographically pure volatile halogenated hydrocarbon in a volume of carbon disulfide (5.1).
The body concentration is shown in Table 1. Commercially available certified standard solutions can also be purchased directly.
5.3 Standard use solution. Dilute the standard stock solution (5.2) by 10 times with carbon disulfide (5.1) to prepare a standard use solution.
Available now.
5.4 Carrier gas. nitrogen, purity 99.999%.
5.5 Anhydrous sodium sulfate. After baking at 500 ° C for 4 h, it is placed in a desiccator for use.
6 Instruments and equipment
6.1 Gas Chromatograph. Electronic Capture Detector (ECD).
6.2 Capillary column. 50 m × 0.32 mm, 1.05 μm film thickness, the stationary phase is 100% methyl siloxane. Or use other
Equivalent capillary column.
6.3 sampler
It can accurately maintain the flow rate within 0.1~1.0 L/min, and the flow error should be within ±5%.
6.4 Activated carbon sampling tube
The sampling tube is equipped with two sections of coconut shell activated carbon with a particle size of 0.4-0.8 mm (20-40 mesh) and a section A 100 mg.
Section B 50 mg, as shown in Figure 1. Or use a single-stage sampling tube with 150 mg coconut shell activated carbon.
1--glass wool; 2--activated carbon; A--100 mg activated carbon; B--50 mg activated carbon
Figure 1 activated carbon sampling tube
6.5 Microinjectors. 5 μl, 10 μl, 50 μl, 100 μl and 1 ml.
6.6 Brown vial. 2 ml with Teflon liner and solid screw cap.
6.7 Common instruments and equipment used in general laboratories.
7 samples
7.1 Sample collection
7.1.1 The flow rate calibration should be performed on the sampler (6.3) before sampling. At the sampling site, knock an activated carbon sampling tube (6.4)
End, connected to the sampler (6.3), check the air tightness of the sampling system, adjust the flow rate of the sampling device to 0.2 L/min, this sampling
The tube is only used to regulate the flow.
7.1.2 Knock open the ends of the activated carbon sampling tube (6.4) for sampling and connect it to the sampler (6.3) (A section is gas inlet)
mouth). The flow should be checked at any time during sample collection and maintained at a flow rate of 0.2 L/min for 50 min. End of sampling
After that, remove the sampling tube and seal immediately. Record sampling point, time, ambient temperature, atmospheric pressure, sampling start flow,
Information such as sampling end flow rate and sampling tube number.
7.1.3 Collection of blank samples on site
The activated carbon sampling tube is transported to the sampling site, and the two ends are sealed immediately after sealing, and the activated carbon sample of the collected sample is taken.
The tubes are stored together and brought back to the laboratory for analysis. Each batch of samples has at least one blank sample on site.
7.1.4 Sample collection Other requirements and precautions shall be implemented in accordance with the relevant provisions of HJ/T 194.
7.2 Preservation of samples
The collected sampling tube was stored in a dark place and sealed, and measured within 3 days at room temperature. Otherwise it should be placed in a closed container, ice at 4 °C
Store in a box, measure within 7 days, or store in a refrigerator at -20 °C, within 14 days. The sampling tube should be restored to the chamber during analysis
Warm, if there is condensation on the outer wall, dry it with filter paper.
7.3 Preparation of samples
The activated carbon in the collected sampling tube was taken out and placed in a brown sample bottle pre-filled with 0.2 g of anhydrous sodium sulfate (5.5).
(6.6), add 1.00 ml of carbon disulfide (5.1) sealed, gently shake for 1 min, and let stand for 1 h at room temperature.
To be tested.
The desorbent can be stored for 5 days in a 4 °C refrigerator.
7.4 Preparation of blank samples
The activated carbon in the blank sampling tube in the field is taken out, and a blank sample is prepared according to the step (7.3).
8 Analysis steps
8.1 Instrument Reference Conditions
Oven temperature. 35 °C for 8 min, ramp up to 100 °C at 5 °C/min, then rise at 10 °C/min
Temperature to.200 °C for 5 min; column flow. 1.5 ml/min; inlet temperature. 220 °C; detector temperature. 320 °C;
Split ratio. 5.1; makeup flow. 60 ml/min.
8.2 Calibration
8.2.1 Drawing of the calibration curve
Pipette 5.0 μl and 10.0 μl of standard use solution (5.3), 2.0 μl, 5.0 μl and 10.0 μl, respectively, using a microsyringe
The standard stock solution (5.2) was added to the A section of the activated carbon sampling tube (6.4) and blown with 0.2 L/min of nitrogen (5.4).
50 min. Prepare the calibration series of Table 1 according to step (7.3). Remove the meter separately with a micro syringe
1.0 μl of the quasi-series solution was injected into the gas chromatograph (6.1). Target concentration (μg/ml) as the abscissa, corresponding
The response is the ordinate and a calibration curve is drawn.
Table 1 Calibration series concentration of volatile halogenated hydrocarbons
Component
Standard stock solution
Degree (μg/ml)
Standard use
Degree (μg/ml)
Calibration series concentration
(μg/ml)
1,1,1-trichloroethane, carbon tetrachloride, trichloro
Ethylene, tribromomethane, tetrachloroethylene,
1,1,2,2-tetrachloroethane, hexachloroethane
2.00 0.200 0.001, 0.002, 0.004, 0.010, 0.020
1-bromo-2-chloroethane, 1,1,2-trichloroethane,
1,2,3-trichloropropane, 1,2-dichlorobenzene 1,3-
Dichlorobenzene
20.0 2.00 0.010,0.020,0.040,0.100,0.200
3 chloroform, benzyl chloride, 1,4-dichlorobenzene 100 10.0 0.050, 0.100, 0.200, 0.500, 1.00
Trans-1,2-dichloroethylene, 1,1-dichloroethane
Alkane, cis-1,2-dichloroethylene, 1,2-di
Ethyl chloride, 1,2-dichloropropane, chlorobenzene
1000 100 0.500, 1.00, 2.00, 5.00, 10.0
8.2.2 Standard chromatogram
Figure 2 shows the standard chromatogram of 21 volatile halogenated hydrocarbons under the instrument conditions specified in this standard.
1-dicarbon disulfide (solvent peak); 2-trans-1,2-dichloroethylene; 3-1,1-dichloroethane; 4-cis-1,2-dichloroethylene; 5-three
Methyl chloride; 6-1,2-dichloroethane; 7-1,1,1-trichloroethane; 8-carbon tetrachloride; 9-1,2-dichloropropane; 10-trichloroethylene; 11-1-
Bromo-2-chloroethane; 12-1,1,2-trichloroethane; 13-tetrachloroethylene; 14-chlorobenzene; 15-tribromomethane; 16-1,1,2,2-tetrachloroethane alkyl;
17-1,2,3-trichloropropane; 18-benzyl chloride; 19-1,4-dichlorobenzene; 20-1,2-dichlorobenzene 1,3-dichlorobenzene; 21-hexachloroethane alkyl
Figure 2 Standard chromatogram of 21 volatile halogenated hydrocarbons
8.3 Determination
Pipette 1.0 μl sample with a micro syringe and inject into the gas chromatograph (6.1) according to the instrument reference conditions (8.1)
The assay was performed and the retention time and response values of the chromatographic peaks were recorded.
8.4 Blank test
Pipette 1.0 μl blank sample with a micro syringe and inject into the gas chromatograph (6.1) according to the instrument reference conditions.
(8.1) Perform the measurement.
9 Calculation and representation of results
9.1 Qualitative analysis
Qualitative according to the retention time of the standard chromatogram components.
9.2 Quantitative analysis
The mass concentration of the target in the sample is calculated using a calibration curve based on the response value of the target.
The mass concentration of the target in the ambient air is calculated according to formula (1).
ndV
V 10001 ××= ρρ ..(1)
In the formula.
ρ - the mass concentration of the target in the ambient air, μg/m3;
1ρ - mass concentration of the target in the sample calculated from the calibration curve, μg/ml;
V--the volume of the sample, ml;
Vnd - the sampling volume in the standard state (101.325 kPa, 273.15 K), L.
9.3 Result representation
When the measurement result is greater than or equal to the method detection limit and less than 100 times the method detection limit, the number of retained digits of the measurement result is
The detection limit is consistent; when the measurement result is greater than or equal to 100 times the method detection limit, the measurement result retains three significant digits.
When using the capillary column specified in this standard, the target of the peak number 20 in Figure 2 is 1,2-dichloro
The sum of both benzene and 1,3-dichlorobenzene.
10 Precision and accuracy
10.1 Precision
6 laboratories respectively unified the three samples of the first point of the curve, the third point of the curve, and the fourth point of the curve.
The relative standard deviations in the laboratory were. 1.4% to 26.1%, 2.4% to 18.3%, and 1.1% to 25.7%;
The relative standard deviations between laboratories were. 4.8% to 22.6%, 4.5% to 20.7%, 4.1% to 24.7%; repeatability limits
They are. 0.02 ~ 13.0 μg/m3, 0.08 ~ 50.0 μg/m3, 0.19 ~ 100 μg/m3; reproducibility limits are. 0.03 ~
23.0 μg/m3, 0.12 to 70.0 μg/m3, 0.40 to 210 μg/m3.
10.2 Accuracy
The calibration of the six laboratories is equivalent to the first point of the corresponding calibration curve of each component, the third point of the curve, and the fourth point of the curve.
The actual samples of the three concentrations were spiked and analyzed. The recoveries of the spiked samples were. 82.3%~114%, 77.7%~
106%, 73.5% to 95.1%.
The results of precision and accuracy are detailed in Appendix B.
11 Quality Assurance and Quality Control
11.1 The relative deviation of the flow at the beginning and end of sampling should be within 10%.
11.2 The correlation coefficient of the calibration curve should be greater than or equal to 0.995.
11.3 The calibration curve should be redrawn using different batches of activated carbon sampling tubes.
11.4 The concentration of the target compound in the blank sample should be less than the method detection limit.
11.5 Each batch of samples (20) should be analyzed with a calibration curve intermediate concentration check point, and the intermediate concentration check point measurement value.
The relative error of the concentration corresponding to the calibration curve should not exceed 20%. If the allowable range is exceeded, the standard stock should be reconstituted
Liquid, draw a calibration curve.
11.6 Make at least 10% parallel sample determination for each batch of samples. When the sample size is less than 10, make at least one flat.
For the sample, the relative deviation of the parallel samples should be within 30%.
11.7 After the chromatographic instrument is repaired, the calibration curve should be redrawn.
Appendix A
(normative appendix)
Target detection limit and lower limit of measurement
When the sampling volume is 10 L, the method detection limits and lower limit of measurement for 21 targets are shown in Table A.1.
Schedule A.1 Detection limit and lower limit of determination of target
Serial number component name English name CAS No.
The detection limit
(μg/m3)
Lower limit of measurement
(μg/m3)
1 trans-1,2-dichloroethylene trans-1,2-Dichloroethylene 156-60-5 10 40
2 1,1-Dichloroethane 1,1-Dichloroethane 75-34-3 9 36
3 cis-1,2-dichloroethylene cis-1,2-Dichloroethylene 156-59-2 7 28
4 Chloroform Chloroform 67-66-3 1 4
5 1,2-dichloroethane 1,2-Dichloroethane 107-06-2 3 12
6 1,1,1-trichloroethane 1,1,1-Trichloroethane 71-55-6 0.05 0.20
7 Carbon tetrachloride Carbon tetrachloride 56-23-5 0.7 2.8
8 1,2-dichloropropane 1,2-Dichloropropane 78-87-5 4 16
9 Trichloroethylene 79-01-6 0.04 0.16
10 1-Bromo-2-chloroethane 1-Bromo-2-chloroethane 107-04-0 0.2 0.8
11 1,1,2-trichloroethane 1,1,2-Trichloroethane 79-00-5 0.4 1.6
12 Tetrachloroethylene 127-18-4 0.2 0.8
13 Chlorobenzene Chlorobenzene 108-90-7 7 28
14 Tribromomethane Bromoform 75-25-2 0.07 0.28
15 1,1,2,2-tetrachloroethane 1,1,2,2-Tetrachloroethane 79-34-5 0.07 0.28
16 1,2,3-trichloropropane 1,2,3-Trichloropropane 96-18-4 0.3 1.2
17 Benzyl chloride Benzyl chloride 100-44-7 1 4
18 1,4-dichlorobenzene 1,4-Dichlorobenzene 106-46-7 2 8
19 1,2-dichlorobenzene 1,3-dichlorobenzene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
95-50-1
541-73-1
0.4 1.6
20 Hexachloroethane Hexachloroethane 67-72-1 0.03 0.12
Appendix B
(informative appendix)
Method precision and accuracy
The precision and accuracy data of the method's repeatability limit, reproducibility limit and spiked recovery rate are shown in Appendix B.1.
Schedule B.1 Precision and Accuracy
Serial number
Compound
name
Blank plus
concentration
(μg/m3)
Mean value
(μg/m3)
Laboratory interior
Standard deviation
(%)
Interlaboratory
standard deviation(%)
Repeatability limit r
(μg/m3)
Reproducibility limit R
(μg/m3)
_2 pSP ±
(%)
Trans-1,2-
Dichloroethylene
50.0 50.5 4.0~13.0 8.0 10 20 101±16.2
200 188 3.7~12.8 11.5 50 70 93.8±21.4
500 430 2.1~12.9 9.4 100 150 85.9±16.2
2 1,1-dichloroethane
50.0 48.8 4.5~13.7 13.8 13 22 97.5±27.0
200 191 3.1~13.2 5.4 45 50 95.4±10.2
500 431 3.3~10.3 12.3 88 168 86.2±21.2
Cis-1,2-
Dichloroethylene
50.0 52.7 1.4~12.2 7.2 12 16 105±15.2
200 202 2.6~12.2 6.1 46 55 101±12.2
500 441 1.8~9.6 15.9 82 210 88.1±28.0
4 chloroform
5.00 4.12 8.8~20.6 8.8 2 2 82.3±14.4
20.0 17.3 7.8~17.3 15.3 6 9 86.8±26.6
50.0 38.6 7.7~25.7 12.6 17 21 77.3±19.6
5 1,2-dichloroethane
10.0 9.86 5.3~15.7 14.4 3 5 98.6±28.4
40.0 40.0 3.3~12.0 9.0 9 13 100±18.0
100 88.0 1.5~9.9 14.5 19 40 88.0±25.4
1,1,1-trichloro
Ethane
0.100 0.0946 5.8~12.7 10.2 0.03 0.04 94.7±19.4
0.400 0.375 3.2~13.1 13.8 0.09 0.17 93.7±25.8
1.00 0.83 1.1~10.5 20.0 0.20 0.50 83.0±33.2
7 carbon tetrachloride
1.00 0.868 7.1~22.6 12.5 0.4 0.5 86.7±21.6
4.00 3.11 7.4~15.1 6.2 1 1 77.7±9.6
10.0 8.36 4.8~10.9 12.4 2 3 83.6±20.6
8 1,2-dichloropropane
10.0 9.34 11.1~14.1 14.2 3 5 93.4±26.6
40.0 38.5 2.4~11.9 8.4 8 12 96.2±16.2
100 85.7 1.5~10.3 13.4 19 37 85.7±23.0
9 trichloroethylene
0.100 0.0941 8.0~15.8 11.0 0.03 0.04 94.1±20.6
0.400 0.349 5.8~15.0 20.7 0.09 0.22 87.3±36.0
1.00 0.865 3.3~16.4 24.7 0.25 0.64 86.5±42.6
1-bromo-2-chloro
Ethane
0.500 0.507 5.3~11.9 13.4 0.1 0.2 101±27.2
2.00 1.86 2.6~11.3 9.9 0.4 0.6 93.0±18.4
5.00 4.36 1.5~9.3 15.6 0.8 2 87.2±27.2
1,1,2-trichloro
Ethane
1.00 1.03 3.9~14.2 16.5 0.2 0.5 103±24.2
4.00 3.70 4.4~11.4 9.5 0.8 1.2 92.5±17.6
10.0 8.48 2.1~9.8 15.9 1.9 4.2 84.8±27.0
12 tetrachloroethylene
0.500 0.426 8.3~22.4 7.9 0.2 0.2 85.3±13.4
2.00 1.69 6.7~17.9 8.3 0.6 0.6 84.5±14.0
5.00 4.13 3.4~17.1 18.4 1.3 2.4 82.7±30.4
13 chlorobenzene
50.0 50.1 2.6~8.5 15.0 9 23 100±30.0
200 175 5.6~8.5 12.0 37 68 87.6±21.0
500 400 2.9~6.8 15.2 52 176 80.0±24.2
14 tribromomethane
0.100 0.0994 3.6~23.4 22.6 0.03 0.07 99.4±44.8
0.400 0.337 6.3~16.9 8.1 0.12 0.13 84.2±13.8
1.00 0.951 2.8~13.5 18.0 0.3 0.55 95.1±34.2
1,1,2,2-tetrachloro
Ethane
0.100 0.114 5.7~10.2 4.8 0.02 0.03 114±11.0
0.400 0.425 5.0~16.5 5.3 0.13 0.13 106±11.4
1.00 0.942 5.8~14.5 11.5 0.28 0.4 94.2±21.6
1,2,3-trichloro
Propane
1.00 0.956 4.5~11.0 14.4 0.2 0.4 95.6±27.6
4.00 3.34 4.1~13.7 7.1 1 1.1 83.5±11.8
10.0 7.78 1.8~11.8 14.9 2 3.7 77.8±23.2
17 benzyl chloride
5.00 5.56 7.2~15.6 7.6 2 2 111±16.8
20.0 18.1 3.7~10.1 5.4 4 4 90.3±9.8
50.0 41.3 4.0~15.8 8.3 10 13 82.6±13.8
18 1,4-dichlorobenzene
5.00 4.37 5.0~8.1 17.1 1 2 87.4±29.8
20.0 19.2 6.2~10.4 11.3 4 7 96.1±21.6
50.0 43.8 6.1~18.5 8.8 14 16 87.5±15.4
1,2-dichlorobenzene
(1,3-dichloro
benzene)
1.00 1.06 6.5~19.3 10.2 0.4 0.5 106±21.8
4.00 3.37 6.7~10.9 11.7 0.8 1.3 84.3±19.6
10.0 7.82 6.2~16.6 7.7 2.1 2.5 78.2±12.0
20 hexachloroethane
0.100 0.101 6.0~14.3 15.3 0.03 0.05 101±30.8
0.400 0.354 3.9~12.2 9.3 0.08 0.12 88.5±16.4
1.00 0.856 3.9~11.9 15.8 0.19 0.41 85.6±27.0
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