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HJ 694-2014 English PDF (HJ694-2014)

HJ 694-2014 English PDF (HJ694-2014)

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HJ 694-2014: Water Quality - Determination of Mercury, Arsenic, Selenium, Bismuth and Antimony - Atomic Fluorescence Spectrometry

This Standard specifies the atomic fluorescence spectrometry for the determination of mercury, arsenic, selenium, bismuth, and antimony in water. This Standard applies to the determination of soluble [Translator: dissolved-state] and total quantity of mercury, arsenic, selenium, bismuth, and antimony in surface water, groundwater, sewage, and industrial waste water.
HJ 694-2014
HJ
NATIONAL ENVIRONMENTAL PROTECTION STANDARD
OF THE PEOPLE REPUBLIC OF CHINA
Water Quality - Determination of Mercury, Arsenic,
Selenium, Bismuth and Antimony ?€?
Atomic Fluorescence Spectrometry
ISSUED ON: MARCH 13, 2014
IMPLEMENTED ON: JULY 01, 2014
Issued by: Ministry of Environmental Protection
Table of Contents
Announcement ... 3
Foreword ... 4
1 Application scope ... 5
2 Normative references ... 5
3 Terms and definitions ... 6
4 Principle of the method ... 6
5 Interference and elimination ... 6
6 Reagents and materials ... 7
7 Instruments and equipment ... 11
8 Samples ... 11
9 Analysis steps ... 12
10 Result calculation and representation ... 15
11 Precision and accuracy ... 15
12 Quality assurance and quality control ... 17
13 Waste disposal ... 18
14 Notes ... 18
Annex A ... 19
Announcement
2014 No. 17
Ministry of Environmental Protection of the People's Republic of China
To implement the ?€?Environmental Protection Law of the People's Republic of China?€?, protect the environment, protect human health, and regulate environmental monitoring, two standards, including ?€?Water Quality - Determination of Mercury, Arsenic, Selenium, Bismuth and Antimony - Atomic Fluorescence Spectrometry?€?, are approved as national environmental protection standards, and are published. The standard names and numbers are as follows:
1. ?€?Water Quality - Determination of Mercury, Arsenic, Selenium, Bismuth and Antimony - Atomic Fluorescence Spectrometry?€? (HJ 694-2014);
2. ?€?Soil - Determination of organic carbon - Combustion oxidation nondispersive infrared absorption method?€? (HJ 695-2014).
Above standards are implemented since July 1, 2014, and are published by China Environmental Press. The standard content can be inquired at the website of the Ministry of Environmental Protection (bz.mep.gov.cn).
Notice is hereby given.
Ministry of Environmental Protection
March 13, 2014
Foreword
To implement the ?€?Environmental Protection Law of the People's Republic of China?€? and "Water Pollution Prevention Law of the People's Republic of China?€?, protect the environment, protect human health, and regulate the monitoring methods of mercury, arsenic, selenium, antimony, and bismuth in water, this Standard is formulated. This Standard specifies the atomic fluorescence spectrometry for determination of mercury, arsenic, selenium, bismuth, and antimony in water.
This Standard is released for the first time.
Annex A of this Standard is informative.
This Standard was formulated by the Department of Science, Technology and Standards of Ministry of Environment Protection.
Main drafting organization of this Standard: Nanjing Environmental Monitoring Center. Verification organizations of this Standard: Jiangsu Environment Monitoring Center, Jiangsu Physical and Chemical Testing Center, Wuxi Environmental Monitoring Center Station, Changzhou Environmental Monitoring Center, Zhenjiang
Environmental Monitoring Center Station, and Taizhou Environmental Monitoring Center.
This Standard was approved by the Ministry of Environmental Protection on March 13, 2014.
This Standard shall be implemented from July 1, 2014.
This Standard shall be interpreted by the Ministry of Environmental Protection. Water Quality - Determination of Mercury, Arsenic,
Selenium, Bismuth and Antimony ?€?
Atomic Fluorescence Spectrometry
Warning: nitric acid, hydrochloric acid, and perchloric acid have a strong corrosivity and a strong oxidability, so it shall wear protective equipment when operating, so as to avoid contact with skin and clothing. The pretreatment process of all samples shall be carried out in a fume hood.
1 Application scope
This Standard specifies the atomic fluorescence spectrometry for the determination of mercury, arsenic, selenium, bismuth, and antimony in water.
This Standard applies to the determination of soluble [Translator: dissolved-state] and total quantity of mercury, arsenic, selenium, bismuth, and antimony in surface water, groundwater, sewage, and industrial waste water.
According to the method of this Standard, the detection limit of mercury is 0.04??g/L, the determination lower limit of mercury is 0.16??g/L; the detection limit of arsenic is 0.3??g/L, the determination lower limit of arsenic is 1.2??g/L; the detection limit of selenium is 0.4??g/L, the determination lower limit of selenium is 1.6??g/L; the detection limit of bismuth and antimony is 0.2??g/L, the determination lower limit of bismuth is 0.8??g/L.
2 Normative references
This Standard references the following documents or its terms. For undated references, the latest version applies to this Standard.
GB/T 21191 Atomic fluorescence spectrometer
HJ/T 91 Technical specifications requirements for monitoring of surface water and waste water
HJ/T 164 Technical specifications for environmental monitoring of groundwater HJ 493 Water quality - Technical regulation of the preservation and handling of samples
HJ 494 Water quality - Guidance on sampling techniques
3 Terms and definitions
The following terms and definitions apply to this Standard.
3.1
Soluble mercury, arsenic, selenium, bismuth and antimony
It refers to the content of mercury, arsenic, selenium, bismuth, and antimony determined in the filtrate of the not-acidified sample, after being filtered through the filter membrane with a pore size of 0.45??g.
3.2
Total quantity of mercury, arsenic, selenium, bismuth and antimony
It refers to the content of mercury, arsenic, selenium, bismuth, and antimony determined in the unfiltered sample, after being dissolved.
3.3
Determined elements
It refers to mercury, arsenic, selenium, bismuth, and antimony elements. 4 Principle of the method
The test solution after pretreatment is put into the atomic fluorescence spectrometer; under potassium borohydride (or sodium borohydride)?€?s reducing effects at acidic conditions, it generates arsine, bismuthine, antimony hydrogen, hydrogen selenide, and mercury atoms; the hydride forms ground-state atoms in argon and hydrogen flames; its ground-state atoms and mercury atoms generate atomic fluorescence by the excitation of the light emitted by element (mercury, arsenic, selenium, bismuth, and antimony) lights; the atomic fluorescence intensity is in direct proportion to the content of determined elements in the sample solution within a certain range. 5 Interference and elimination
5.1 The elements in acidic medium, that can react with potassium borohydride and generate hydride, would affect each other and produce interference; adding thiourea + ascorbic acid solution (6.20) can substantially eliminate the interference. 5.2 Copper and other transition metals that are above a certain concentration may interfere to the determination; adding thiourea + ascorbic acid solution (6.20) can eliminate most of the interference. Under the experimental conditions of this Standard, samples containing less than 100mg/L of Cu2+, less than 50mg/L of Fe2+, less than 1mg/L of Co2+, less than 10mg/L of Pb2+ (5mg/L for selenium), and less than 150mg/L of Mn2+ (2mg/L for selenium) do not affect the determination.
5.3 Common anions do not interfere to the determination.
5.4 Physical interference elimination. Select two-layer-structure quartz tube atomizer; with the outer and inner layers filled with argon gas, form a protective outer layer to isolate air, so that the ground-state atom of determined elements do not collide with oxygen and nitrogen in the air, so as to reduce the fluorescence quenching effect on the determination.
6 Reagents and materials
Unless otherwise indicated, use analytically chemical reagents that comply with national standards when analyzing, water for test is freshly prepared deionized or distilled water.
6.1 Hydrochloric acid: ??(HCl) = 1.19g/ml, guarantee reagent.
6.2 Nitric acid: ??(HNO3) = 1.42g/ml, guarantee reagent.
6.3 Perchloric acid: ??(HClO4) = 1.68g/ml, guarantee reagent.
6.4 Hydrogen sodium hydride (NaOH).
6.5 Potassium borohydride (KBH4).
6.6 Thiourea (CH4N2S).
6.7 Ascorbic acid (C6H8O6).
6.8 Potassium dichromate (K2Cr2O7): guarantee reagent.
6.9 Mercuric chloride (HgCl2): guarantee reagent.
6.10 Arsenic trioxide (As2O3): guarantee reagent.
6.11 Selenium powder: high-purity (the mass fraction is more than 99.99%). 6.12 Bismuth: high-purity (the mass fraction is more than 99.99%).
6.13 Antimony trioxide (Sb2O3), guarantee reagent.
6.14 Hydrochloric acid solution: 1 + 1.
6.15 Hydrochloric acid solution: 5 + 95.
6.16 Nitric acid solution: 1 + 1.
6.17 Hydrochloric acid - nitric acid solution
Weigh 300ml of hydrochloric acid (6.1) and 100ml of nitrate (6.2) respectively; add to 400ml of water; mix well.
6.18 Mixture acid of nitric acid - perchloric acid
Prepare by mixing an equal volumes of nitric acid (6.2) and perchloric acid (6.3). Prepare it when it is to be used.
6.19 Reducing agents
6.19.1 Potassium borohydride Solution A
Weigh 0.5g of sodium hydroxide (6.4); dissolve in 100ml of water; add 1.0g of potassium borohydride (6.5); mix well. This solution is used for the determination of mercury; prepare it when it is to be used; stored in a plastic bottle.
6.19.2 Potassium borohydride solution B
Weigh 0.5g of sodium hydroxide (6.4); dissolve in 100ml of water; add 2.0g of potassium borohydride (6.5); mix well. This solution is used for the determination of arsenic, selenium, bismuth, and antimony; prepare it when it is to be used; stored in a plastic bottle.
Note: It can also use potassium hydroxide, potassium borohydride to prepare reducing agents. 6.20 Thiourea - ascorbic acid solution
Weigh 5.0g of sulfur urea (6.6) and ascorbic acid (6.7) respectively; dissolve with 100ml of water; mix well. Prepare it at the day of determination.
6.21 Mercury standard solution
6.21.1 Mercury standard fixative
Weigh 0.5g of potassium dichromate (6.8) and dissolve in 950ml of water; add 50ml of nitric acid (6.2); mix well.
6.21.2 Mercury standard stock solution: ??(Hg) = 100mg/L.
Purchase the commercially available certified reference materials; or weigh 0.1354g of mercuric chloride (6.9) that has been placed on a silica dryer overnight; transfer into a 1000ml flask after dissolved with a small amount of mercury standard fixative (6.21.1); dilute with mercury standard fixative (6.21.1) to the mark; mix well. Store in a glass bottle. It can be stored at 4??C for 2 years.
6.21.3 Mercury standard intermediate solution: ??(Hg) = 1.00mg/L.
Pipette 5.00ml of mercury standard solution (6.21.2) into a 500ml volumetric flask; add 50ml of hydrochloric acid (6.14); use mercury standard fixative (6.21.1) to dilute to the mark; mix well. Store in a glass bottle. It can be stored at 4??C for 100 d [Translator: days].
6.21.4 Mercury standard using solution: ??(Hg) = 10.0g/L.
Pipette 5.00ml of mercury standard intermediate solution (6.21.3) into a 500ml volumetric flask; add 50ml of hydrochloric acid (6.14); dilute with water to the mark; mix well. Store in a glass bottle. Prepare it when it is to be used.
6.22 Arsenic standard solution
6.22.1 Arsenic standard stock solution: ??(As) = 100mg/L.
Purchase the commercially available certified reference materials; or weigh 0.1320g of guarantee-reagent arsenic trioxide (6.10) that has been dried at 105??C for 2h; dissolve in 5ml of 1mol/L sodium hydroxide solution; use 1mol/L hydrochloric acid to neutralize until phenolphthalein red fades off; transfer into a 1000ml volumetric flask; dilute with water to the mark; mix well. Store in a glass bottle. It can be stored at 4??C for 2 years.
6.22.2 Arsenic intermediate standard solution: ??(As) = 1.00mg/L.
Pipette 5.00ml of arsenic standard stock solution (6.22.1) into a 500ml volumetric flask; add 100ml of hydrochloric acid (6.14); dilute with water to the mark ; mix well. It can be stored at 4??C for 1 year.
6.22.3 Arsenic standard using solution: ??(As) = 100??g/L.
Pipette 10.00ml of arsenic standard intermediate solution (6.22.2) into a 100ml volumetric flask; add 20ml of hydrochloric acid (6.14); dilute with water to the mark; mix well. It can be stored at 4??C for 30 d.
6.23 Selenium standard solution
6.23.1 Selenium standard stock solution: ??(Se) = 100mg/L.
Purchase the commercially available certified reference materials; or weigh 0.1000g of high-purity selenium powder (6.11) in a 100ml beaker; add 20ml of nitric acid (6.2); heat at a low temperature to dissolve; cool to room temperature; transfer into a 1000ml volumetric flask; dilute with water to the mark; mix well. Stored in a glass bottle. It can be stored at 4??C for 2 years.
6.23.2 Selenium standard intermediate solution: ??(Se) = 1.00mg/L.
Pipette 5.00ml of selenium standard stock solution (6.23.1) into a 500ml volumetric flask; add 150ml of hydrochloric acid (6.14); dilute with water to the mark; mix well. It can be stored at 4??C for 100 d.
6.23.3 Selenium standard using solution: ??(Se) = 10.0??g/L.
Pipette 5.00ml of selenium standard intermediate solution (6.23.2) into a 500ml volumetric flask; add 150ml of hydrochloric acid (6.14); dilute with water to the mark; mix well. Prepare it when it is to be used.
6.24 Bismuth standard solution
6.24.1 Bismuth standard stock solution: ??(Bi) = 100mg/L.
Purchase the commercially available certified reference materials; or weigh 0.1000g of high-purity mental bismuth (6.12) in a 100ml beaker; add 20ml of nitric acid (6.2); heat at a low temperature to dissolve completely; cool down; transfer into a 1000ml volumetric flask; dilute with water to the mark; mix well. Store in a glass bottle. It can be stored at 4??C for 2 years.
6.24.2 Bismuth standard intermediate solution: ??(Bi) = 1.00mg/L.
Pipette 5.00ml of bismuth stock standard solution (6.24.1) into a 500ml volumetric flask; add 100ml of hydrochloric acid (6.14); dilute with water to the mark; mix well. It can be stored at 4??C for 1 year.
6.24.3 Bismuth standard using solution: ??(Bi) = 100??g/L.
Pipette 10.00ml of bismuth standard intermediate solution (6.24.2) into a 100ml volumetric flask; add 20ml of hydrochloric acid (6.14); dilute with water to the mark; mix well. Prepare it when it is to be used.
6.25 Antimony standard solution
6.25.1 Antimony standard stock solution: ??(Sb) = 100mg/L.
Purchase the commercially available certified reference materials; or weigh 0.1197g of antimony trioxide (6.13) that has been dried at 105??C for 2h; dissolve in 80ml of hydrochloric acid (6.1); transfer into a 1000ml volumetric flask; add 120ml of hydrochloric acid (6.1); dilute with water to the mark; mix well. Stored in a glass bottle. It can be stored at 4??C for 2 years.
6.25.2 Antimony standard intermediate solution: ??(Sb) = 1.00mg/L.
Pipette 5.00ml of antimony standard stock solution (6.25.1) into a 500ml volumetric flask; add 100ml of hydrochloric acid (6.14); dilute with water to the mark; mix well. It can be stored at 4??C for 1 year.
6.25.3 Antimony standard using solution: ??(Sb) = 100??g/L.
Pipette 10.00ml of antimony standard intermediate solution (6.25.2) into a 100ml volumetric flask; add 20ml of hydrochloric acid (6.14); dilute with water to the mark; mix well. Prepare it when it is to be used.
6.26 Argon: purity ??? 99.999%.
7 Instruments and equipment
7.1 Atomic fluorescence spectrometer: Instrument performance indicators shall comply with specifications of GB/T 21191.
7.2 Element light (mercury, arsenic, selenium, bismuth, antimony).
7.3 Thermostat heating plate.
7.4 Thermostatic water bath device: temperature control accuracy is ??1??C. 7.5 Filtration device: water-system microporous filter membrane with a pore size of 0.45??m.
7.6 Analytical balance: accuracy is 0.0001g.
7.7 Sample container: hard glass bottles or polyethylene bottles (barrels). 7.8 Commonly used laboratory ware: grade-A glass gauges and glassware that comply with the national standard.
8 Samples
8.1 Sample collection
Sample collection is conducted by referring to the relevant specifications of HJ/T 91 and HJ/T 164. Soluble samples and total quantity samples are collected separately. 8.2 Sample preservation
Sample preservation is conducted by referring to the relevant specifications of HJ 493.
8.2.1 Filterable mercury, arsenic, selenium, bismuth, antimony samples
Filter the sample with 0.45??m filter membrane (7.5) as soon as possible after sample collection; discard the initial 50ml of filtrate; clean sample bottle with a small amount of the filtrate; collect the filtrate in the sample bottle. Determine mercury samples; if the water sample is neutral, add hydrochloric acid in a ratio of adding 5ml of hydrochloric acid (6.1) per liter of water sample; determine arsenic, selenium, antimony, bismuth samples; add hydrochloric acid in a ratio of adding 2ml of hydrochloric acid (6.1) per liter of water sample. Sample preservation period is 14 d.
8.2.2 Total quantity samples of mercury, arsenic, selenium, bismuth, antimony Except that samples are not filtered after collection, other treatment methods and preservation period are same as 8.2.1.
8.3 Sample preparation
8.3.1 Mercury
Weigh 5.0ml of mixed sample (8.2.1) or (8.2.2) in a 10ml colorimetric tube; add 1ml of hydrochloric acid - nitric acid solution (6.17); put on a stopper and mix well; place in boiling water bath to heat to dissolve for 1h; shake for 1 to 2 times during heating, and open the stopper to deflate. Cool down; dilute with water to the mark; mix well for test. 8.3.2 Arsenic, selenium, bismuth, antimony
Weigh 50.0ml of mixed sample (8.2.1) or (8.2.2) in a 150ml conical flask; add 5ml of mixture acid of nitric acid - perchloric acid (6.18); heat on a heating plate until white smoke emits; cool down. Then add 5ml of hydrochloric acid solution (6.14); heat until brown smoke disappears; transfer into a 50ml volumetric flask after cooling down; diluted with water to constant volume; mix well for test.
8.3.3 Blank samples
Use water to replace the sample, prepare blank samples according to the steps of 8.3. 9 Analysis steps
9.1 Instrument adjustment
Adjust the instrument to the optimal working condition according to instrument?€?s instructions for use. Reference measurement conditions are shown in Table 1. Table 1 Reference measurement conditions
Elements
Negative
high
voltage/
Light
current/
mA
Atomizer
preheat
temperature/
??C
Carrier
gas flow/
(ml/min)
Shielding
gas flow/
(ml/min)
Integration
method
Hg 240~280 15~30 200 400 900~1000 Peak area
As 260~300 40~60 200 400 900~1000 Peak area
Se 260~300 80~100 200 400 900~1000 Peak area
Sb 260~300 60~80 200 400 900~1000 Peak area
Bi 260~300 60~80 200 400 900~1000 Peak area
9.2 Calibration
9.2.1 Preparation of calibration standard series
9.2.1.1 Mercury
Pipette respectively 0ml, 1.00ml, 2.00ml, 5.00ml, 7.00ml, 10.00ml of mercury standard using solution (6.21.4) in 100ml volumetric flasks; add 10.0ml of hydrochloric acid - nitric acid solution respectively; dilute with water to the mark; mix well. 9.2.1.2 Arsenic
Pipette respectively 0ml, 0.50ml, 1.00ml, 2.00ml, 3.00ml, 5.00ml of arsenic standard using solution (6.22.3) in 50ml volumetric flasks; add respectively 10ml of hydrochloric acid solution (6.14) and 10ml of thiourea - ascorbic acid solution (6.20); plac...

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