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Ambient air-Determination of the water soluble cations (Li+, Na+, NH4+, K+, Ca2+, Mg2+) from atmospheric particles-Ion chromatography
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HJ 800-2016
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Basic data Standard ID | HJ 800-2016 (HJ800-2016) | Description (Translated English) | Ambient air-Determination of the water soluble cations (Li+, Na+, NH4+, K+, Ca2+, Mg2+) from atmospheric particles-Ion chromatography | Sector / Industry | Environmental Protection Industry Standard | Classification of Chinese Standard | Z15 | Word Count Estimation | 14,186 | Date of Issue | 2016-05-13 | Date of Implementation | 2016-08-01 | Quoted Standard | GB/T 15265; GB/T 15432; HJ 93; HJ 618; HJ/T 194; HJ/T 374; HJ/T 375 | Regulation (derived from) | Ministry of Environmental Protection Announcement No. 39 of 2016 | Issuing agency(ies) | Ministry of Ecology and Environment |
HJ 800-2016: Ambient air-Determination of the water soluble cations (Li+, Na+, NH4+, K+, Ca2+, Mg2+) from atmospheric particles-Ion 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.
Ambient air-Determination of the water soluble cations (Li, Na, NH4, K, Ca2, Mg2) from atmospheric particles-Ion chromatography
National Environmental Protection Standard of the People 's Republic of China
Water - soluble cations in ambient airborne particulates
(Li, Na, NH4, K, Ca2, Mg2)
Determination of Ion Chromatography
Ambient air-Determination of the water soluble cations
(Li, Na, NH4, K, Ca2, Mg2) from atmospheric particles-
Ion chromatography
2016-05-13 release
2016-08-01 implementation
Ministry of Environmental Protection released
Directory
Preface .ii
1 Scope of application 1
2 normative reference document 1
3 Terms and Definitions
Principle of Method 1
5 interference and elimination
6 reagents and materials
7 Instruments and equipment
8 samples
9 Analysis Step 4
10 results are calculated and expressed
11 Precision and Accuracy
Quality assurance and quality control
13 Waste treatment .7
14 Precautions .7
Appendix A (normative) method of detection limit and lower limit of determination
Appendix B (informative) method of precision and accuracy 9
Appendix C (informative) Cationic standard solution chromatogram
Foreword
In 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 the Prevention and Control of Atmospheric Pollution,
Environment, the protection of human health, regulate the ambient air particles in the determination of water-soluble cations, the development of this standard.
This standard specifies the determination of six kinds of water-soluble cations (Li, PM10, PM2.5, dust, etc.) in ambient air particulate matter (TSP,
Na, NH4, K, Ca2, Mg2).
This standard is the first release.
Appendix A to this standard is a normative appendix, Appendix B to Appendix C are informative.
This standard is organized by the Ministry of Environmental Protection Science and Technology Standards Division.
The main drafting unit of this standard. Gansu Province Environmental Monitoring Center Station.
The standard unit. Xiamen University School of Chemistry and Chemical Engineering, Guangzhou University Analysis and Testing Center, Chinese Academy of Sciences ecological ring
Environmental Research Center, State Key Laboratory of Cryospheric Science, Chinese Academy of Sciences, Environmental Monitoring Station, Hulunbeier City, Inner Mongolia, Guangdong
Environmental Protection Engineering Vocational College and Gansu Jiayuguan City Environmental Protection Monitoring Station.
The environmental protection department of this standard approved on May 13,.2016.
This standard has been implemented since August 1,.2016.
This standard is explained by the Ministry of Environmental Protection.
Water-soluble cations in ambient air particulates (Li, Na, NH4, K, Ca2,
Mg2) was determined by ion chromatography
1 Scope of application
This standard specifies the determination of water-soluble inorganic cations in ambient air particulates (Li, Na, NH4, K, Ca2,
Mg2) by ion chromatography.
This standard applies to environmental air particles (including TSP, PM10, PM2.5, dust, etc.) in the six kinds of water-soluble cation
(Li, Na, NH4, K, Ca2, Mg2).
The ambient air particulate filter sample, when the sample volume is 60 m3 (standard state), the volume of the extract is 100 ml,
When the volume was 25 μl, the detection limit of this method was 0.005 μg/m3 ~ 0.037 μg/m3, and the lower limit of determination was 0.020 μg/m3 ~
0.148 μg/m3; dust samples, when the sampling volume of 0.100 g, the volume of 100 ml extract, injection volume of 25 μl, the
The detection limit was 0.003 mg/g to 0.022 mg/g and the lower limit was 0.012 mg/g to 0.088 mg/g. See Appendix A. for details.
Note 1. This method is also applicable to the analysis of samples collected from special particles such as dust aerosols and dust storms in special weather.
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.
Ambient air - Determination of dust emission - Gravimetric method GB/T
Ambient air - Determination of total suspended particulates - Gravimetric method GB/T
Technical Requirements and Test Methods for HJ 93 Environmental Air Particulate (PM10 and PM2.5) Sampler
Determination of ambient air PM10 and PM2.5 by HJ 618
Technical specification for manual monitoring of ambient air quality
Technical Requirements and Test Methods for HJ/T 374 Total Suspended Particulate Sampler
Technical Requirements and Testing Methods for Environmental Air Sampler of HJ/T 375
3 terms and definitions
The following terms and definitions apply to this standard.
3.1 ambient air particles
Through the sampling device, collected in the filter on the ambient air particles (including TSP, PM10, PM2.5, etc.), or through
Dust collectors and other collection devices to collect the ambient air dust.
3.2 water-soluble inorganic cations
A sample of ambient air particles that is dissolved in deionized water without the addition of a chemical reagent. Determination of this method
The cations include Li, Na, NH4, K, Ca2, Mg2.
4 principle of the method
Collected samples of ambient air particulate matter, extracted with deionized water, cationic column exchange separation, with inhibition
Type or non-suppression type conductivity detector detection. According to the retention time qualitative, peak height or peak area quantification.
5 interference and elimination
Two kinds of cations with similar retention times, when their concentration difference is large and affect the determination of low concentration of ions,
Release, adjust the flow rate, change the eluent ratio, etc. to eliminate interference.
6 reagents and materials
Unless otherwise stated, analytical reagents conforming to national standards are used for analysis. The test water is a resistivity ≥18 MΩ · cm
(25 ° C) and filtered through a 0.45 μm microporous membrane.
6.1 concentrated nitric acid (HNO3). excellent grade pure, ρ = 1.42 g/ml.
6.2 lithium nitrate (LiNO3). excellent grade, should be used before the 105 ℃ ± 5 ℃ dry constant weight, placed in a dryer to save.
6.3 sodium nitrate (NaNO3). excellent grade, should be used before the 105 ℃ ± 5 ℃ dry constant weight, placed in a dryer to save.
6.4 ammonium chloride (NH4Cl). excellent grade, should be used before the 105 ℃ ± 5 ℃ dry constant weight, placed in a dryer to save.
6.5 potassium nitrate (KNO3). excellent grade, should be used before the 105 ℃ ± 5 ℃ dry constant weight, placed in a dryer to save.
6.6 calcium nitrate [Ca (NO3) 2 · 4H2O]. excellent grade, should be placed in the dryer before the balance 24 h.
6.7 Magnesium nitrate [Mg (NO3) 2 · 6H2O]. excellent grade, should be placed in the dryer before use for 24 h.
6.8 Methanesulfonic acid. ω (CH3SO3H) ≥99%.
6.9 Nitric acid solution. c (HNO3) = 1 mol/L.
Remove 68.26 ml of concentrated nitric acid (6.1) slowly adding water, dilute to 1000 ml with water and mix well.
6.10 Lithium ion standard stock solution. ρ (Li) = 1000 mg/L.
Weigh 9.9337 g of lithium nitrate (6.2) dissolved in the amount of water, the whole volume into the 1000 ml volumetric flask, diluted with water volume to the standard
Line, mix well. Transferred to the polyethylene bottle, in the 4 ℃ below the cold, dark and sealed can be stored for 6 months. You can also buy commercially available
Standard material.
6.11 sodium ion standard stock solution. ρ (Na) = 1000 mg/L.
Weigh 3.6977 g sodium nitrate (6.3) dissolved in the amount of water, the whole volume into the 1000 ml volumetric flask, diluted with water volume to the standard
Line, mix well. Transferred to the polyethylene bottle, in the 4 ℃ below the cold, dark and sealed can be stored for 6 months. You can also buy commercially available
Standard material.
6.12 ammonium ion standard stock solution. ρ (NH4) = 1000 mg/L.
Weigh 2.9654 g ammonium chloride (6.4) dissolved in the amount of water, the whole volume into the 1000 ml volumetric flask, diluted with water volume to the standard
Line, mix well. Transferred to the polyethylene bottle, in the 4 ℃ below the cold, dark and sealed can be stored for 6 months. You can also buy commercially available
Standard material.
6.13 potassium ion standard stock solution. ρ (K) = 1000 mg/L.
Weigh 2.5857 g of potassium nitrate (6.5) dissolved in the amount of water, the whole volume into the 1000 ml volumetric flask, diluted with water volume to
Marking, mixing. Transferred to the polyethylene bottle, in the 4 ℃ below the cold, dark and sealed can be stored for 6 months. You can also buy commercially available
Certificate of Reference.
6.14 Calcium ion standard stock solution. ρ (Ca2) = 1000 mg/L.
Weigh 5.8919 g calcium nitrate (6.6) dissolved in the amount of water, the full amount into the 1000 ml volumetric flask, add 1.00 ml of nitrate
Acid solution (6.9), diluted with water volume to the mark, mix. Transferred to the polyethylene bottle, in the 4 ℃ below the cold, dark and dense
Sealed for 6 months. You can also purchase commercially available certified materials.
6.15 magnesium ion standard stock solution. ρ (Mg2) = 1000 mg/L.
Weigh 10.5518 g magnesium nitrate (6.7) dissolved in the amount of water, the whole volume into the 1000 ml volumetric flask, add 1.00 ml of nitrate
Acid solution (6.9), diluted with water volume to the mark, mix. Transferred to the polyethylene bottle, in the 4 ℃ below the cold, dark and dense
Sealed for 6 months. You can also purchase commercially available certified materials.
6.16 Mix the standard use of liquid
Respectively, 10.0 ml of lithium ion standard stock solution (6.10), 50.0 ml sodium standard stock solution (6.11), 10.0 ml ammonium
Ion standard stock solution (6.12), 50.0 ml potassium ion standard stock solution (6.13), 250 ml calcium ion standard stock solution (6.14),
50.0 ml magnesium ion standard stock solution (6.15) in 1000 ml volumetric flask, diluted with water volume to the mark, mix. Prepared to contain
10.0 mg/L Li, 50.0 mg/L Na, 10.0 mg/L NH4, 50.0 mg/L K, 250 mg/L Ca2
And 50.0 mg/L Mg2.
6.17 eluent
According to the instrument model and column instructions for the use of conditions for preparation. The eluent conditions given below are for reference.
6.17.1 Methanesulfide leaching stock solution. c (CH3SO3H) = 1 mol/L.
Remove 65.58 ml of methanesulfonic acid (6.8) dissolved in the appropriate amount of water, the whole volume into the 1000 ml volumetric flask, diluted with water volume to
Marking, mixing. The solution is stored in a glass reagent bottle and can be stored at room temperature for 3 months.
6.17.2 Methanesulfonic acid leaching liquid. c (CH3SO3H) = 0.02 mol/L
Remove 40.00 ml of methanesulfonic acid leachate (6.17.1) in a.2000 ml volumetric flask, dilute with volume to the mark, mix
uniform.
6.17.3 Nitrate leaching liquid. c (HNO3) = 7.25 mmol/L
Remove 14.50 ml of nitric acid solution (6.9) in a.2000 ml volumetric flask, dilute the volume with water to the mark, mix well.
7 instruments and equipment
7.1 Ambient air particulate sampler. The sampling device consists of sampling head, sampling pump and flowmeter. Sampling head is equipped with different cut
Cutting machine can collect TSP, PM10 and PM2.5 particles; flow meter for the flow, range 60 L/min ~ 125 L/min; flow indication
Error ≤ 2%; other performance and technical indicators should be consistent with HJ 93, HJ/T 194, HJ/T 374, HJ/T 375 of the relevant provisions.
7.2 ambient air dust sample dust collection tank.
7.3 Sampling filter. the use of high quality blank value of glass fiber, quartz or other material filter, and can meet the particles
Sampling technology requirements of the product.
7.4 Ion Chromatograph. An analytical system consisting of an ion chromatograph, operating software, and required accessories.
7.4.1 Column. cation separation column (polydiorylene benzene/ethyl vinyl benzene, with carboxylic acid or phosphoric acid functional groups, high capacity
Column) and cation protection column. A sample can be used to determine the six cations specified in this method. The separation of the peaks is not less than 1.5.
7.4.2 Cationic Suppressor (optional).
7.4.3 Conductivity detector.
7.5 Filtration box. Teflon (PTFE) or polystyrene (PS) material.
7.6 Vials. hard glass or polyethylene material, volume ≥100 ml, with screw cap.
7.7 Ultrasonic Cleaner. Frequency 40 KHz ~ 60 KHz.
7.8 Suction filter device. with a pore size ≤ 0.45 μm of acetate fiber or polyethylene filter.
7.9 Sample tube. Polypropylene (PP) or polytetrafluoroethylene (PTFE) material with screw cap.
7.10 Disposable water microporous membrane syringe filter. aperture 0.45 μm.
7.11 disposable syringes. 1 ml to 10 ml.
7.12 General laboratory equipment and equipment commonly used.
8 samples
8.1 Collection of environmental air particulate filter samples
In accordance with the relevant provisions of HJ 618, GB/T 15432 and HJ/T 194. Sampling flow 100 L/min, sampling time
24 h ± 1 h.
8.2 Collection of environmental airborne dust samples
Before sampling can not be added in the collection of copper sulfate, antifreeze and other chemical reagents, sampling time 30 d ± 2 d; other sampling to
In accordance with the relevant provisions of GB/T 15265 implementation.
8.3 Transport and storage of samples
Ambient air particulate filter sample. Store and store in filter box (7.5) during transport and storage to avoid folding or squeezing;
In the non-irritating gas, to avoid sunlight at room temperature under the conditions of environmental protection, placed in the dryer sealed, 7 d to complete the determination.
Ambient air dust sample. placed in the vial, stored in the dryer, 30 d to complete the determination.
8.4 Preparation of sample
8.4.1 Preparation of particulate filter samples
Carefully cut 1/1 ~ 1 particle filter sample, into the vial (7.6), add 100.0 ml experimental water immersion
The membrane was immersed for 30 min and then placed in an ultrasonic cleaner (7.7) for 20 min. The extract was filtered by suction
The device (7.8) is filtered and poured into the sample tube (7.9) by direct injection of the ion chromatograph. Also available
Single syringe (7.11) with water microporous filter syringe filter (7.10) Manual injection determination.
8.4.2 Preparation of dust samples
Accurately weighed 0.1000 g dust samples, the whole volume into the vial (7.6), the total amount of water is 100.0 ml. Set it up
Ultrasonic extraction in an ultrasonic cleaner (7.7) for 20 min. The extract is filtered through an evacuation filter (7.8) to prepare a ring
Airborne dust samples, to be tested. When the dust sample is less than 0.1000 g, it can be weighed.
8.5 Preparation of laboratory blank samples
Particulate filter laboratory blank sample. the use of samples with the same batch of blank filter collection, in accordance with the particulate filter test
Preparation of the same procedure (8.4.1). Dust Labs White Sample. Do not weigh dust samples, follow the sample with dust
Preparation of the same procedure as in Preparation (8.4.2).
8.6 Preparation of full program blank samples
Will be collected with the sample batch of blank filter to the sampling site, do not collect particulate samples, according to the sample transport and
Save (8.3) with the sample back to the laboratory, follow the same procedure as the preparation of the particulate filter sample (8.4.1)
preparation.
9 Analysis steps
9.1 Ion chromatographic analysis of the reference conditions
According to the instrument manual to optimize the measurement conditions or parameters, according to the actual sample of the matrix and composition optimization of eluent concentration
degree. The following conditions are given for the analysis of ion chromatographic conditions.
9.1.1 Reference condition 1
Cation separation column (7.4.1). (6.17.2), flow rate. 1.0 ml/min, inhibitory conductivity detector,
Continuous self - circulation regenerator. Injection volume. 25 μl. The standard solution chromatogram for this reference is shown in Figure C.1 in Appendix C.
9.1.2 Reference condition 2
Cation separation column (7.4.1). Nitrate leaching using liquid (6.17.3), flow rate. 0.9 ml/min, non-suppression type conductivity detector.
Injection volume. 25 μl. The standard solution chromatogram for this reference is shown in Figure C.2 in Appendix C.
9.2 Standard curve drawing
Respectively, accurate removal of 0.00 ml, 1.00 ml, 2.00 ml, 5.00 ml, 10.0 ml, 20.0 ml mixed standard use of liquid (6.16)
Placed in a group of 100 ml volumetric flask, water volume to the mark, mix. Prepared into six different concentrations of mixed standard series,
The mass concentration of each ion in the standard series is shown in Table 1. According to the concentration of the measured sample to determine the appropriate standard series concentration range.
According to their concentration from low to high order in turn into the ion chromatograph, record the peak area (or peak height). With the mass concentration of each ion
For the abscissa, the peak area (or peak height) for the vertical axis, draw the standard curve.
Table 1 Cationic Standard Series Concentration
Cationic Name Standard Series Concentration (mg/L)
Li 0.00 0.10 0.20 0.50 1.00 2.00
Na 0.00 0.50 1.00 2.50 5.00 10.0
NH4 0.00 0.10 0.20 0.50 1.00 2.00
K 0.00 0.50 1.00 2.50 5.00 10.0
Ca2 0.00 2.50 5.00 12.5 25.0 50.0
Mg2 0.00 0.50 1.00 2.50 5.00 10.0
9.3 Determination of samples
The sample (8.4) was injected into an ion chromatogram according to the same chromatographic conditions (9.1) and (9.2) as the standard curve
The cation concentration was measured to preserve the time qualitative and the instrument response was quantified.
Note 2. If the concentration of the cation to be measured exceeds the standard curve, the test specimen and the laboratory blank should be diluted to the same multiple and then the dilution factor
(D).
9.4 Determination of laboratory blank samples
The laboratory blank sample (8.5) was injected according to the same chromatographic conditions (9.1) and (9.2) as the standard curve
The ion concentration was determined by ion chromatography, and the time was qualitative and the instrument response was quantified.
9.5 Determination of the whole program blank sample
The whole program blank sample (8.6) was injected according to the same chromatographic conditions (9.1) and (9.2) as the standard curve for drawing
The ion concentration was determined by ion chromatography, and the time was qualitative and the instrument response was quantified.
10 results are calculated and expressed
10.1 Calculation of water-soluble cation content in ambient air particulate matter (filter sample)
The mass concentration (ρ, μg/m3) of the cation (Li, Na, NH4, K, Ca2, Mg2) in the filter particles was
Calculated according to formula (1).
() 1 0
Nd
- VND
Ρ ρρ × × × =
(1)
Where. mass concentration of cation in ρ - filter sample, μg/m3;
1ρ - mass concentration of cation in sample, mg/L;
0p - average value of cationic mass concentration in blank laboratory samples, mg/L;
V - the volume of the extract, 100.0 ml;
N - filter cut the number of copies, take the whole membrane filter extraction is N = 1, take 1/4 filter is N = 4;
D - dilution of sample;
NdV - the total volume of the sample (101.325 kPa, 273 K) in the standard state, m3.
10.2 Calculation of water-soluble cation content in ambient air particulate matter (dust-reducing sample)
The mass fraction (ω, mg/g) of the water-soluble cation (Li, Na, NH4, K, Ca2, Mg2) in the dust-
According to formula (2) calculation.
() 31 0-V 10 D
Ω ωω
- × × × = (2)
Where. ω - dust samples in the cationic mass fraction, mg/g;
1ω - mass concentration of cation in sample, mg/L;
0ω - average concentration of cationic mass concentration in dusty laboratory blank sample, mg/L;
V - the volume of the extract, 100.0 ml;
D - sample dilution factor;
M - the quality of the dust sample, g.
10.3 Results indicated
When the sample content is less than 1 μg/m3 (or mg/g), the result is retained to three decimal places; when the sample content is greater than or equal to
1 μg/m3 (or mg/g), the result retains three significant digits.
11 precision and accuracy
11.1 precision
7 laboratories on the Li, Na, NH4, K, Ca2, Mg2 different concentrations of ambient air particles unified
The relative standard deviations in the laboratory range from 0.1% to 7.0%; the relative standard deviation between the laboratory
Around 0.9% to 10.0%. Method The precision test results are given in Table B.1 in Appendix B.
11.2 Accuracy
7 laboratories for different types of environmental air particles unified matrix spiked samples were spiked recovery determination, plus standard
The yield ranged from 83.5% to 114.2%. The accuracy of the method is shown in Table B.2 in Appendix B.
12 quality assurance and quality control
12.1 Environmental Air Particulate Sampling Equipment (7.1) Flow calibration and air tightness inspection shall be carried out before each sampling.
The quantity assurance and quality control measures are carried out in accordance with the relevant requirements of HJ/T 194.
12.2 per batch (≤20) Particulate filter samples or dust samples should be analyzed at least 2 laboratory blanks, laboratory
Blank measurement results should be lower than the lower limit of the method, blank parallel sample measured value of the relative deviation of ≤ 20%.
12.3 per batch (≤ 20) particulate filter samples should be at least one full program blank, the whole program blank determination results should be
Below the method to determine the lower limit. Otherwise, the cause should be identified and the sample can be measured by re-sampling the analysis until it is passed.
12.4 The...
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