Search result: HJ 605-2011
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Soil and Sediment. Determination of Volatile Organic compounds. Purge and Trap Gas Chromatography/Mass Spectrometry Method
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HJ 605-2011
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| Standard ID | HJ 605-2011 (HJ605-2011) | | Description (Translated English) | Soil and Sediment. Determination of Volatile Organic compounds. Purge and Trap Gas Chromatography/Mass Spectrometry Method | | Sector / Industry | Environmental Protection Industry Standard | | Classification of Chinese Standard | Z18 | | Classification of International Standard | 13.080 | | Word Count Estimation | 22,293 | | Date of Issue | 2011-02-10 | | Date of Implementation | 2011-06-01 | | Quoted Standard | GB 17378.3; HJ/T 166 | | Summary | This standard specifies the determination of volatile organic compounds in soils and sediments of the purge and trap/gas chromatography mass spectrometry. This standard applies to soils and sediments 65 kinds of volatile organic compounds measured. If the validation of this standard can be applied to the determination of volatile organic compounds other. |
HJ 605-2011
Soil and Sediment.Determination of Volatile Organic compounds.Purge and Trap Gas Chromatography/Mass Spectrometry Method
National Environmental Protection Standard of the People's Republic
Determination of volatile organic compounds in soils and sediments
Purge and trap/gas chromatography-mass spectrometry
Soil and sediment-Determination of volatile organic compounds
-Purge and trap gas chromatography/mass spectrometry method
Published on.2011-02-10
2011-06-01 Implementation
Ministry of Environmental Protection released
Ministry of Environmental Protection
announcement
No. 9 of.2011
In order to implement the "Environmental Protection Law of the People's Republic of China", protect the environment, protect human health, and standardize environmental monitoring, the water is now approved.
The determination of total mercury is determined by the Cold Atomic Absorption Spectrophotometry and other nine standards for national environmental protection standards.
The standard name and number are as follows.
I. Determination of total mercury in water - Cold atomic absorption spectrophotometric method (HJ 597-2011);
2. Determination of water quality ladders by sodium sulfite spectrophotometry (HJ 598-2011);
3. Determination of water quality ladders N-chlorohexadecylpyridine-sodium sulfite spectrophotometry (HJ 599-2011);
4. Gas chromatographic method (HJ 600-2011) for the determination of water quality ladders, black ropes, and dien ladders;
5. Determination of water quality of formaldehyde - Acetylacetone spectrophotometry (HJ 601-2011);
6. Determination of water quality 石墨 Graphite furnace atomic absorption spectrophotometry (HJ 602-2011);
VII. Determination of water quality 火焰 Flame atomic absorption spectrophotometry (HJ 603-2011);
VIII. Determination of total hydrocarbons in ambient air - Gas chromatography (HJ 604-2011);
The above standards have been implemented since June 1,.2011 and published by the China Environmental Science Press. The standard content can be found on the website of the Ministry of Environmental Protection.
From the date of implementation of the above standards, the following seven national environmental protection standards approved and issued by the former National Environmental Protection Agency shall be abolished.
The name and number are as follows.
1. Determination of total mercury in water quality by cold atomic absorption spectrophotometry (GB 7468-87);
2. Determination of water quality ladders by sodium sulfite spectrophotometry (GB/T 13905-92);
3. Determination of water quality ladders by spectrophotometry (GB/T 13903-92);
4. Determination of water quality TNT, Hessian and Dien, gas chromatography (GB/T 13904-92);
V. Determination of water quality formaldehyde acetylacetone spectrophotometry (GB 13197-91);
6. Determination of water quality 原子 Atomic absorption spectrophotometry (GB/T 15506-1995);
VII. Determination of total hydrocarbons in ambient air Gas chromatography (GB/T 15263-94).
Special announcement.
February 10,.2011
Content
Foreword..iv
1 Scope..1
2 Normative references..1
3 Terms and Definitions.1
4 principle of the method..2
5 reagents and materials. 2
6 instruments and equipment.2
7 samples.3
8 Analysis steps..4
9 Results calculation and representation..7
10 Precision and Accuracy 8
11 Quality Assurance and Quality Control.8
12 Notes 9
Appendix A (Normative Appendix) Detection limit, lower limit of measurement and minimum relative response factor of target 10
Appendix B (informative) Quantitative parameters of target 12
Appendix C (informative) The precision and accuracy of the method.14
Iv
Foreword
In order to implement the Environmental Protection Law of the People's Republic of China, protect the environment, protect human health, and regulate the volatility of soil and sediment.
This standard is established for the measurement method of the machine.
This standard specifies the purge and trap/gas chromatography-mass spectrometry for the determination of volatile organic compounds in soils and sediments.
This standard is the first release.
Appendix A of this standard is a normative appendix, and Appendix B and Appendix C are informative appendices.
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.
This standard is verified by. Liaoning Provincial Environmental Monitoring Experimental Center, Anshan Environmental Monitoring Center Station, Jiangsu Environmental Monitoring Center, Shanghai
Municipal Environmental Monitoring Center and Henan Environmental Monitoring Center Station.
This standard was approved by the Ministry of Environmental Protection on February 10,.2011.
This standard has been implemented since June 1,.2011.
This standard is explained by the Ministry of Environmental Protection.
Determination of volatile organic compounds in soils and sediments
Purge and trap/gas chromatography-mass spectrometry
Warning. The internal standard, substitutes and standard samples used in the experiment are volatile toxic chemicals, and the solution should be prepared in a fume hood.
In the operation, the protective equipment should be worn as required to avoid contact with skin and clothing.
1 Scope of application
This standard specifies the purge and trap/gas chromatography-mass spectrometry for the determination of volatile organic compounds in soils and sediments.
This standard applies to the determination of 65 volatile organic compounds in soils and sediments. If verified by this standard, it can also be applied to other volatilization.
Determination of sex organic matter.
When the sample amount is 5 g and the full-scan analysis is performed by standard quadrupole mass spectrometry, the detection limit of the target is 0.2-3.2 μg/kg.
The lower limit is 0.8 to 12.8 μg/kg. See Appendix A for details.
2 Normative references
The contents of this standard refer to the terms in the following documents. For undated references, the valid version applies to this standard.
GB 17378.3 Marine monitoring specification Part 3. Sample collection, storage and transport
HJ/T 166 Technical Specifications for Soil Environmental Monitoring
3 Terms and definitions
The following terms and definitions apply to this standard.
3.1
Internal standard
Refers to a substance that is not contained in the sample but has similar physicochemical properties to the target to be tested. Usually added before sample analysis, for mesh
Quantitative analysis of the standard.
3.2
Surrogate
Refers to a substance that is not contained in the sample but has similar physicochemical properties to the target to be tested. Usually before sample extraction or other pretreatment
By adding, the recovery rate can be used to evaluate the influence of the sample matrix and the sample processing process on the analysis results.
3.3
Matrix spiked spike
It means that a known amount of the target to be tested is added to the sample for evaluating the recovery rate of the target and the matrix effect of the sample.
3.4
Calibration verification standards
Refers to a standard solution with a concentration near the midpoint of the calibration curve to confirm the validity of the calibration curve.
3.5
Transport blank strip blank
A blank reagent water is placed in the sample vial in the laboratory prior to sampling and brought to the sampling site. Do not open when sampling, then follow
The sample is shipped back to the laboratory and tested in the same operating steps as the sample to check for contamination during transport.
3.6
Full program blank whole program blank
A blank reagent water is placed in the sample vial in the laboratory prior to sampling and brought to the sampling site. Simultaneously with the sample vial
Cover and seal, then transport it back to the laboratory with the sample, and test it in the same way as the sample, for inspection from sample collection to analysis
Whether the process is contaminated.
4 Principle of the method
The volatile organic compounds in the sample are enriched in the trap tube by high-purity helium (or nitrogen) purge, and the trap tube is heated and reversed with high purity helium gas.
The components which are blown and thermally desorbed enter the gas chromatograph and are separated, and then detected by a mass spectrometer. By comparing with the standard mass spectrum of the target to be tested
The comparison and retention time were qualitative and the internal standard method was used for quantification.
5 reagents and materials
5.1 Blank reagent water. double distilled water or water prepared by pure water equipment.
A blank test is required before use to confirm that there is no interference peak in the retention time interval of the target or that the target substance is rich.
The degree is below the method detection limit.
5.2 Methanol (CH3OH). Analytical grade of pesticide residues.
5.3 Standard stock solution. ρ = 1 000 ~ 5 000 mg/L.
Commercially available certified standard solutions can be purchased directly or formulated with standard materials.
5.4 Standard use solution. ρ=10.0～100.0 mg/L.
Standard use of volatile targets such as dichlorodifluoromethane, methyl chloride, trichlorofluoromethane, ethyl chloride, methyl bromide and vinyl chloride
Prepared separately, the shelf life is usually one week, the standard use of other target materials is one month, or according to the manufacturer's instructions.
5.5 Internal standard solution. ρ=25 μg/ml.
Fluorobenzene, chlorobenzene-D5 and 1,4-dichlorobenzene-D4 should be used as internal standards. Can be purchased directly from commercially available certified standard solutions, or with high quality
Formulated in a standard solution.
5.6 Alternative standard solution. ρ = 25 μg/ml.
Dibromofluoromethane, toluene-D8 and 4-bromofluorobenzene should be used as alternatives. Can be purchased directly from commercially available certified standard solutions, or with high quality
Formulated in a concentration standard solution.
5.7 4-bromofluorobenzene (BFB) solution. ρ = 25 μg/ml.
It can be purchased directly from a commercially available certified standard solution or prepared with a high quality standard solution.
5.8 Helium. Purity (volume fraction) is 99.999% or more.
5.9 Nitrogen. Purity (volume fraction) is 99.999% or more.
Note. All the above standard solutions are treated with methanol as solvent, stored at 4 ° C or less in the dark or with reference to the manufacturer's product description. Should be restored to before use
Mix at room temperature.
6 Instruments and equipment
6.1 Vials. 60 ml brown wide-mouth glass bottles with Teflon-silica-lined screw caps (or larger than 60 ml glass of other sizes)
Bottle), 40 ml brown glass bottle and colorless glass bottle.
6.2 Sampler. Disposable plastic syringe or stainless steel dedicated sampler.
6.3 Gas Chromatograph. With split/splitless inlet, it can control the electronic pressure of the carrier gas and can be programmed.
6.4 Mass spectrometer. Electron bombardment (EI) ionization source, scanning from 35 u to 270 u in 1 s; with NIST mass spectrometer, manual/auto tuning
Harmonics, data acquisition, quantitative analysis and library search.
6.5 Purge and trap device. The purging device can heat the sample to 40 ° C, and the trap tube is mixed with 1/3 Tenax, 1/3 silica gel and 1/3 activated carbon.
Adsorbent or other equivalent adsorbent. If a purge and trap without an autosampler is used, the purge tube should be equipped with at least 5 g
Sample and 10 ml of water.
6.6 Capillary column. 30 m × 0.25 mm, 1.4 μm film thickness (6% nitrile propyl phenyl 94% dimethyl polysiloxane fixative); or use other
Capillary column for equivalent performance.
6.7 Balance. Accuracy is 0.01 g.
6.8 Hermetic syringe. 5 ml.
6.9 Microinjectors. 10, 25, 100, 250 and 500 μl.
6.10 Brown glass bottle. 2 ml with Teflon-silica liner and solid screw cap.
6.11 Disposable Pasteur glass pipettes.
6.12 Shovel.
6.13 Medicine spoon. PTFE or stainless steel.
6.14 Common instruments and equipment used in general laboratories.
7 samples
7.1 Sample collection
The collection of soil and sediment samples is based on the relevant provisions of HJ/T 166 and GB 17378.3, respectively. Can be used at the sampling site for the swing
The portable instrument for the determination of the organic matter measures the sample at a high level of the target. At least 3 parallel samples should be collected for all samples
And use a 60 ml vial (or larger than 60 ml vials of other sizes) to collect another sample for high-volume samples.
Volatile organic matter and sample moisture content.
7.1.1 Sampling method for manual injection method
This sampling method is suitable for a purging and trapping device without an autosampler.
Use a shovel or a spatula to collect the sample as quickly as possible into a 60 ml vial (or larger than 60 ml vials of other sizes) and fill as much as possible.
Quickly remove the sample from the vial thread and the attached surface and seal the vial.
7.1.2 Sampling method for automatic injection mode
This sampling method is suitable for purging and trapping devices with an autosampler.
Place a clean magnetic stir bar in each 40 ml brown vial before sampling, seal, label and weigh (accurate to
0.01 g), record its weight and indicate on the label. When sampling, use the sampler to collect the appropriate amount of sample into the sample vial and quickly remove the vial.
The sample is adhered to the thread and the sample adhered to the outer surface.
Note 1. If a sample is taken using a disposable plastic syringe, the diameter of the syringe section should extend into the neck of the 40 ml vial. Syringe section at the end of the syringe
The points should be cut off before sampling. A syringe can only be used to collect one sample. If a stainless steel special sampler is used, the sampler must be equipped with a booster.
The soil can be pushed into the vial.
Note 2. If the target content in the sample is initially determined to be less than.200 μg/kg, about 5 g sample is collected; if the target content in the sample is initially determined to be greater than or equal to
At.200 μg/kg, approximately 1 g and 5 g samples should be taken separately.
7.2 Preservation of samples
Samples should be refrigerated after collection. It should be analyzed as soon as possible after being shipped back to the laboratory. The sample storage area in the laboratory should be free of organic interference at 4 °C.
The following save time is 7 days.
7.3 Determination of moisture content of the sample
Take 5 g (accurate to 0.01 g) sample at (105 ± 5) °C for at least 6 h, divide the difference in sample quality before and after drying by drying
The mass of the pre-sample is multiplied by 100 to calculate the sample moisture content w (%) to the nearest 0.1%.
8 Analysis steps
8.1 Instrument Reference Conditions
8.1.1 Purge and trap reference conditions
Purge flow rate. 40 ml/min; purge temperature. 40 ° C; preheating time. 2 min; purge time. 11 min; dry blowing time. 2 min;
Pre-desorption temperature. 180 ° C; desorption temperature. 190 ° C; desorption time. 2 min; baking temperature..200 ° C; baking time. 8 min;
Transmission line temperature..200 ° C. The rest of the parameters are set according to the instruction manual of the instrument.
8.1.2 Gas Chromatography Reference Conditions
Inlet temperature..200 ° C; carrier gas. helium; split ratio. 30.1; column flow (constant current mode). 1.5 ml/min; temperature program.
38 ° C (1.8 min) → 10/min ° C → 120 ° C → 15/min ° C → 240 ° C (2 min).
8.1.3 Mass Spectrometry Reference Conditions
Scanning mode. full scan; scanning range. 35 ~ 270 u; ionization energy. 70 eV; electron multiplier voltage. with tuning voltage
To; interface temperature. 280 ° C; the rest of the parameters are set according to the instrument manual.
Note 1. In order to improve the sensitivity, the selective ion scanning method can also be used for analysis. The characteristic ion selection is referred to Appendix B.
8.2 Calibration
8.2.1 Instrument performance check
Pipette 1~2 μl BFB solution (5.7) with a micro syringe, directly into the gas chromatograph for analysis or add 5 ml blank reagent
The water (5.1) was injected into the gas chromatograph by a purging and trapping device for analysis. Key ion abundance of BFB obtained by quadrupole mass spectrometry
Meet the standards specified in Table 1, otherwise you need to adjust the parameters of the mass spectrometer or consider cleaning the ion source. If the instrument software cannot be automatically determined
When the critical ion abundance of BFB meets the criteria in Table 1, the average value of the ion abundance of the peak scanning point and the two scanning points before and after it can be taken.
Key ion abundance is obtained after deducting the background value and should meet the criteria in Table 1. The background value can be selected from the 20 scan points before the BFB peak.
At any point, the background value should be due to column bleed or instrument background ions.
Note 2. BFB key ion abundance standards can be performed with reference to the instrument manufacturer's instructions when using ion traps or other types of mass spectrometers.
Table 1 BFB key ion abundance standards
Mass ion abundance standard mass ion abundance standard
50% 95% of 5% to 40% 174 is greater than 50% of mass 95
75 quality 95% to 80% 175 quality 174 5% to 9%
95 base peak, 100% relative abundance 176 quality 174 93% ~ 101%
96% 95% 5% to 9% 177 Quality 5% 5% to 9%
173 is less than 2% of mass 174 - -
8.2.2 Drawing of the calibration curve
Transfer a certain amount of standard use solution (5.4) and substitute standard solution (5.6) to blank reagent water (5.1) with a micro syringe.
The standard series of target and substitute mass concentrations of 5.00, 20.0, 50.0, 100 and.200 μg/L were prepared.
5.00 ml of the above standard series to 40 ml vials with a gas tight syringe (if no autosampler is added, join directly
To the purge tube, add 10.0 μl of the internal standard solution (5.5), so that the internal standard concentration of each point is 50.0 μg/L. By instrument
Refer to condition (8.1), measure from low concentration to high concentration, record the retention time and quantitative deviation of the standard series target and corresponding internal standard.
The response value of the sub (first or second characteristic ion).
Figure 1 shows the total ion chromatogram of the target under the instrument conditions specified in this standard.
Abundance
2.00 time --> 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00
1-dichlorodifluoromethane; 2-chloromethane; 3-chloroethylene; 4-bromomethane; 5-chloroethane; 6-trichlorofluoromethane; 7-1,1-dichloroethylene; 8-acetone; - iodomethane; 10-disulfide
Carbon; 11-dichloromethane; 12-trans-1,2-dichloroethylene; 13-1,1-dichloroethane; 14-2,2-dichloropropane; 15-cis-1. 2-dichloroethylene; 16-2-butanone; 17-bromochloride
Methane; 18-chloroform; 19-dibromofluoromethane; 20-1,1,1-trichloroethane; 21-carbon tetrachloride; 22-1,1-dichloropropene; 23-benzene; 24-1 ,2-dichloroethane; 25-fluorobenzene;
26-trichloroethylene; 27-1,2-dichloropropane; 28-dibromomethane; 29-monobromodichloromethane; 30-4-methyl-2-pentanone; 31-toluene-D8; 32-toluene ;33-1,1,2-trichloro
Ethane; 34-tetrachloroethylene; 35-1,3-dichloropropane; 36-2-hexanone; 37-dibromochloromethane; 38-1,2-dibromoethane; 39-chlorobenzene-D5 40-chlorobenzene; 41-1,1,1,2-
Tetrachloroethane; 42-ethylbenzene; 43-1,1,2-trichloropropane; 44-m-, p-xylene; 45-o-xylene; 46-styrene; 47-bromoform; Cumene; 49-4-bromofluorobenzene;
50-bromobenzene; 51-1,1,2,2-tetrachloroethane; 52-1,2,3-trichloropropane; 53-n-propylbenzene; 54-2-chlorotoluene; 55-1,3 , 5-trimethylbenzene; 56-4-chlorotoluene; 57-tert-butyl
Benzene; 58-1,2,4-trimethylbenzene; 59-sec-butylbenzene; 60-1,3-dichlorobenzene; 61-4-isopropyltoluene; 62-1,4-dichlorobenzene -D4; 63-1,4-dichlorobenzene; 64-n-butylbenzene;
65-1,2-dichlorobenzene; 66-1,2-dibromo-3-chloropropane; 67-1,2,4-trichlorobenzene; 68-hexachlorobutadiene; 69-naphthalene; 70- 1,2,3-trichlorobenzene
Figure 1 Total ion chromatogram of the target
8.2.2.1 Drawing a calibration curve with an average relative response factor
The relative response factor (RRFi) of the target (or surrogate) in point i of the standard series is calculated according to equation (1).
IS
IS
RRF ii
Iρ
ρ= × (1)
Where. RRFi - the relative response factor of the i-th target (or substitute) in the standard series;
Ai--the response value of the quantified ion of the i-th target (or substitute) in the standard series;
AISi--the ith point of the standard series corresponds to the target (or substitute) corresponding to the internal standard quantitation ion response value;
ρIS--the mass concentration of the internal standard in the standard series, 50 μg/L;
Ρi--the mass concentration of the i-th target (or substitute) in the standard series, μg/L.
The average relative response factor RRF of the target (or surrogate) is calculated according to equation (2).
RRF
RRF
==
(2)
Where. RRF - the average relative response factor of the target (or substitute);
RRFi--the relative response factor of the i-th target (or substitute) in the standard series;
n--Standard series points, 5.
The standard deviation (SD) of the RRF is calculated according to equation (3).
(RRF RRF)
SD
= −
(3)
The relative standard deviation (RSD) of the RRF is calculated according to equation (4).
SDRSD 100%
RRF
= × (4)
The relative standard deviation (RSD) of the standard series of targets (or substitutes) relative response factor (RRF) should be less than or equal to 20%.
8.2.2.2 Drawing a calibration curve using least squares
If the relative standard deviation (RSD) of a target relative to the response factor (RRF) in the standard series is greater than 20%, then the target needs
Calibration is performed using a least squares calibration curve. That is, the ratio of the response value of the target object and the corresponding internal standard is the ordinate, and the concentration ratio is the abscissa,
Calibration curve.
Note 3. If the relative standard deviation (RSD) of a target relative to the response factor (RRF) in the standard series is greater than 20%, then the target can also be used.
The nonlinear fitting curve is calibrated and its correlation coefficient should be greater than or equal to 0.99.
8.3 Determination
Before the measurement, remove the vial from the refrigerator and return it to room temperature.
8.3.1 Determination of low content samples
If it is preliminarily determined that the volatile organic content in the sample is less than.200 μg/kg, it is directly determined by using 5 g sample; the preliminary determination is.200~1.
At 1000 μg/kg, it was directly measured with 1 g of sample.
8.3.1.1 If the purging and trapping device does not have an autosampler, first weigh the purging tube, add the appropriate amount of the standard solution, and weigh again (accurate
To 0.01 g), the purge tube is placed in the purge trap. Add 10.0 μl of internal standard (5.5) and 10.0 μl of replacement with a micro-syringe
The standard solution (5.6) is taken as a sample in 5.0 ml of blank reagent water (5.1) taken with a hermetic syringe, placed in a purge tube, and
The instrument is measured according to the conditions (8.1).
8.3.1.2 If the purging and trapping device is equipped with an autosampler, gently shake the vial in 7.1.2 to confirm that the sample in the vial can
Move freely, weigh and record the vial weight (accurate to 0.01 g). Use a gas tight syringe to measure 5.0 ml of blank reagent water (5.1).
The micro-syringe is separately added to the sample vial by adding 10.0 μl of the internal standard solution (5.5) and 10.0 μl of the replacement standard solution (5.6).
The measurement was carried out according to the instrument reference conditions (8.1).
Note 4. When using 1 g sample analysis, if the target is not detected, re-analyze 5 g sample; if the target mass concentration exceeds the highest point of the standard series,
The sample should be reanalyzed according to the high sample determination method (8.3.2).
8.3.2 Determination of high content samples
For samples with a preliminary determination of target content greater than 1 000 μg/kg, from 60 ml vials (or larger than 60 ml samples of other sizes)
Take about 5 g of the sample in a pre-weighed 40 ml colorless vial and weigh it (accurate to 0.01 g). Quickly add 10.0 ml A
Alcohol (5.2), cover the cap a......
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