HJ 752-2015Solid Waste. Determination of Beryllium, Nickel, Molybdenum and Copper. Graphite Furnace Atomic Absorption Spectrometry (English PDF)

Foreword

1 Scope of application

2 Normative reference documents

3 Principle of the method

4 Interference and elimination

5 Reagents and materials

6 Instruments and equipment

7 Samples .3

8 Analysis steps

The results are calculated and expressed

10 Precision and Accuracy 7

11 Quality assurance and quality control

12 Waste disposal

13 Notice 8

Appendix A (informative) Method Precision and Accuracy 9

Appendix B (Informative Annex) Standard Addition Act

Appendix C (informative) Microwave digestion method ..12

I preface

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 Environmental Pollution by Solid Wastes, Environment, the protection of human health, regulate solid waste in beryllium, nickel, copper and molybdenum monitoring methods, the development of this standard.

This standard specifies the atomic absorption spectrophotometric method for beryllium, nickel, copper and molybdenum in solid waste and solid waste leachate.

This standard is the first release.

Appendix A, Appendix B and Appendix C of this standard are informative.

This standard is organized by the Ministry of Environmental Protection Science and Technology Standards Division.

The main drafting unit of this standard. Nanjing Environmental Monitoring Center Station.

The standard verification unit. Taizhou City Environmental Monitoring Center Station, Changzhou City Environmental Monitoring Center, Suzhou City Environmental Monitoring Center Station, Zhenjiang City Environmental Monitoring Center Station, Jiangsu Province, physical and chemical testing center, Nanjing Water Corporation Water Quality Monitoring Center.

The Environmental Protection Department of this standard approves on August 21, 2015.

This standard is implemented on October 1, 2015.

This standard is explained by the Ministry of Environmental Protection.

Determination of solid waste beryllium nickel - copper and molybdenum - Graphite furnace atomic absorption spectrophotometric method Warning. The beryllium standard solution used in the experiment is a toxic chemical; perchloric acid, nitric acid, hydrogen peroxide has strong oxidizing properties and corrosive, hydrochloric acid, hydrofluoric acid with strong volatile and strong corrosive, the operation should be required to wear protective equipment, Solution preparation and sample pretreatment should be performed in a fume hood.

1 Scope of application this standard specifies the determination of solid waste leachate and solid waste in the beryllium, nickel, copper and molybdenum content of graphite furnace atomic absorption Spectrophotometric method.

This standard applies to solid waste leachate and solid waste in the determination of beryllium, nickel, copper and molybdenum.

The detection limits of beryllium, nickel, copper and molybdenum in solid waste leachate were 0.1 µg/L, 1 µg/L, 3 µg/L and 2 µg/L, the lower limit of determination was 0.4 µg/L, 4 µg/L, 12 µg/L and 8 µg/L, respectively. When the sampling volume was 0.5 g when the volume of volume is 50.0 ml, the detection limits of the total amount of beryllium, nickel, copper and molybdenum in solid waste are 0.04 Mg/kg, 0.2 mg/kg, 0.3 mg/kg and 0.2 mg/kg, respectively. The lower limit of determination was 0.16 mg/kg, 0.8 mg/kg, 1.2 mg/kg and 0.8 mg/kg.

2 normative reference documents the contents of this standard refer to the following documents or their terms. Any annotated file that does not specify the date, its valid version Applicable to this standard.

Technical specification for SJ sample preparation for industrial solid waste Technical Specification for Hazardous Waste Identification HJ/T 299 Solid waste leaching toxicity leaching method sulfuric acid nitric acid method HJ/T 300 solid waste leaching toxicity leaching method acetic acid buffer solution method HJ 557 Solid waste leaching toxicity leaching method Horizontal oscillation method

3 Principle of the method Solid waste leachate or solid waste by acid digestion, into the graphite furnace atomizer, the sample of beryllium, nickel, Copper and molybdenum by high temperature atomization, the ground state atoms respectively beryllium, nickel, copper, molybdenum characteristic radiation line selective absorption, its absorption intensity in a certain range with the beryllium, nickel, copper and molybdenum concentration is proportional to.

4 interference and elimination 4.1 higher than 20 mg/L of Fe and 75 mg/L of Mg on the determination of beryllium, respectively, negative interference and interference, Body modifier palladium chloride solution, can eliminate interference.

4.2 less than 10 mg/L Cu, Zn, Ni, Pb, Cd, Cr, Mn, Ba, less than 50 mg/L of Ti and 100 mg/L of K, Na, Ca, Al and other coexisting elements on the determination of beryllium without interference.

4.3, less than 10 mg/L Ag, Al, B, Ba, Be, Bi, Cd, Co, Fe, Hg, Cr, Cs, Cu, Mg, Mn, Ni, Pb, Sb, Se, Sn, Sr, Ti, Tl, V, Zn and K, Na, Ca, Mg and the like below 100 mg/L Coexisting elements do not interfere with the determination of molybdenum.

4.4 When the sample matrix interference is serious, the standard addition method can be used for determination, see Appendix B.

25 Reagents and materials

Unless otherwise stated, analytical reagents conforming to national standards are used in the analysis, and the test water is freshly prepared Sub-water.

5.1 hydrochloric acid. rho (HCl) = 1.19 mg/L, excellent grade pure.

5.2 nitric acid. rho (HNO3) = 1.42 g/ml, excellent grade pure.

5.3 hydrofluoric acid. rho (HF) = 1.49 g/ml, excellent grade pure.

5.4 perchloric acid. rho (HClO4) = 1.68 g/ml, excellent grade pure.

5.5 Hydrogen peroxide solution. phi (H2O2) = 30%.

5.6 beryllium sulfate (BeSO4 · 4H2O), excellent grade pure.

5.7 Metal Nickel (Spectrum Pure).

5.8 Metallic copper (pure spectrum).

5.9 Ammonium molybdate {(NH4) 6 [MOO24] · 4H2O}, excellent grade pure.

5.10 palladium chloride (PdCl2).

5.11 magnesium nitrate Mg (NO3) 2, excellent grade pure.

5.12 Nitric acid solution. 1 1 (v/v) Measure 50 ml nitric acid (5.2) with deionized water to 100 ml.

5.13 Nitric acid solution. 1 99 (v/v) Measure 10 ml of nitric acid (5.2) Dilute to 1000 ml with deionized water.

5.14 Substrate modifier I. palladium chloride solution Weigh 0.34 g of palladium chloride (5.10), add a small amount of water and 1 ml of nitric acid (5.2), dissolved in 50 ° C, 100 ml.

5.15 Substrate modifier II. palladium chloride - magnesium nitrate mixed solution Weigh 0.25 g of palladium chloride (5.10), add a small amount of water and 1 ml of nitric acid (5.2), 50 ° C dissolved;

Magnesium nitrate (5.11) is dissolved in a small amount of water. Mix the two solutions and dilute to 100 ml with water.

5.16 beryllium standard stock solution. rho (Be) = 100 mg/L Use a commercially available standard solution (beryllium single element or a multi-element mixed standard solution containing beryllium); or accurately weigh 1.9660 G beryllium sulfate (5.6), with a small amount of water dissolved after the full transfer into the 1 000 ml volumetric flask, add 10 ml of nitric acid (5.2), Water volume to the mark, shake. Stored in a polyethylene bottle, refrigerated, can be used for two years.

5.17 beryllium standard use of liquid. rho (Be) = 50 µg/L with nitric acid solution (5.13) step by step dilution beryllium standard Huaihu solution (5.16) prepared.

5.18 nickel standard stock solution. rho (Ni) = 1 000 mg/L Use a commercially available standard solution (nickel single element or nickel-containing multi-element mixed standard solution); or accurately weigh 1.000 G metal nickel (5.7) dissolved in 10 ml nitric acid (5.2), transferred into a 1 000 mL volumetric flask, Line, shake well. Stored in a polyethylene bottle, refrigerated, can be used for two years.

5.19 nickel standard use of liquid. rho (Ni) = 250 µg/L with nitric acid solution (5.13) step by step dilution of nickel standard Huaihu solution (5.18) from the preparation.

5.20 copper standard stock solution. rho (Cu) = 1 000 mg/L Use commercially available standard solution (copper single element or copper-containing multi-element mixed standard solution); or accurately weigh 1.000 3g of copper (5.8) dissolved in 10 ml of nitric acid (5.2), transferred into a 1 000 mL volumetric flask, Line, shake well. Stored in a polyethylene bottle, refrigerated, can be used for two years.

5.21 copper standard use of liquid. rho (Cu) = 250 µg/L with nitric acid solution (5.13) by dilution of copper standard stock solution (5.20) from the preparation.

5.22 molybdenum standard stock solution. rho (Mo) = 1 000 mg/L Use commercially available standard solution (molybdenum single element or molybdenum containing multi-element mixed standard solution); or accurately weigh 1.840 G ammonium molybdate (5.9), with a small amount of water dissolved after the full transfer into the 1 000 ml volumetric flask, the volume of water to the mark, shake.

Stored in a polyethylene bottle, refrigerated, can be used for two years.

5.23 molybdenum standard use of liquid. rho (Mo) = 250 µg/L with nitric acid solution (5.13) by dilution of molybdenum standard stock solution (5.22) prepared.

5.24 argon. purity 99.999%.

6 instruments and equipment

6.1 Graphite Furnace Atomic Absorption Spectrophotometer.

6.2 graphite tube. pyrolytic coated graphite tube.

6.3 microwave digestion device (power 600W ~ 1 500W).

6.4 Electric plate. with temperature control function (temperature stability ± 5 °C).

6.5 Common laboratory equipment and equipment.

7 samples

7.1 Acquisition and storage the collection and storage of solid waste samples are carried out in accordance with HJ/T 20 and HJ/T 298.

7.2 Sample preparation

7.2.1 Solid waste leachate the solid waste leachate was prepared by HJ/T 299, HJ/T 300 or HJ 557. Leaching solution if not timely into the Line analysis, should be added nitric acid (5.2) acidification to pH 8 Analysis steps

8.1 Instrument measurement reference conditions refer to the conditions listed in Table 1 to set the instrument so that the instrument is in the best working condition.

Table 1 Instrument reference measurement conditions

Element Be Ni Cu Mo

Light source beryllium hollow cathode lamp nickel hollow cathode lamp copper hollow cathode lamp molybdenum hollow cathode lamp Lamp current (mA) 5.0 4.0 4.0 7.0 Determination of wavelength (nm) 234.9 232.0 324.7 313.3 Sub - sensitive line (nm) - 352.5 217.9 320.9 Passband width (nm) 1.0 0.2 0.5 0.5 Drying temperature (° C)/time (s) 85 to 120/55 85 to 120/55 85 to 120/55 85 to 120/55 Ashing temperature (° C)/time (s) 1.200 ~ 1 400 / 10 ~ 15 900 ~ 1 100 / 10 ~ 15 1 000 ~ 1 100 / 15 ~ 20 1.200 ~ 1 400 / 15 ~ 20 Atomic temperature (° C)/time (s) 2 600/2.9 2 500/2.9 2 500/3 2 800/3 Clear temperature (° C)/time (s) 2 650/2 2 550/2 2 550/2 2 850/2 Does the atomization phase stop Argon flow (ml - min-1) 300 300 300 300 5 matrix modifier matrix modifier I matrix modifier II matrix modifier II matrix modifier II the volume of the matrix modifier (L) is from 2 to 5 2 to 5 2 to 5 2 to 5 Injection volume (L) 20 20 20 20 Background correction method Zeeman background correction Zeeman background correction Zeeman background correction Zeeman background correction

8.2 Calibration curve Respectively, remove 0.00 ml, 0.50 ml, 1.00 ml, 2.00 ml, 3.00 ml, 5.00 ml beryllium standard use of liquid (5.17) in 50 ml volumetric flask, with nitric acid solution (5.13) constant volume to the scale, shake. The standard concentration of beryllium is shown in Table 2.

Remove the 0.00 ml, 1.00 ml, 2.00 ml, 4.00 ml, 6.00 ml, 10.00 ml nickel standard solution (5.19) in 50 ml volumetric flask, with nitric acid solution (5.13) constant volume to the scale, shake. The nickel standard series is shown in Table 2.

Respectively, remove 0.00 ml, 1.00 ml, 2.00 ml, 4.00 ml, 6.00 ml, 10.00 ml copper standard use of liquid (5.21) in 50 ml volumetric flask, with nitric acid solution (5.13) constant volume to the scale, shake. The copper standard series is shown in Table 2.

Remove the 0.00 ml, 1.00 ml, 2.00 ml, 4.00 ml, 6.00 ml, 10.00 mol molybdenum standard solution (5.23) in 50 ml volumetric flask, with nitric acid solution (5.13) constant volume to the scale, shake. The molybdenum standard series is shown in Table 2.

In accordance with the instrument measurement conditions (8.1), from the low concentration to high concentration in turn to the graphite tube by adding 20 µl standard solution and 2 µl to 5 µl matrix modifier to measure absorbance. With the corresponding absorbance as the ordinate, the standard series of various elements of the quality of thick Degrees for the abscissa, draw the elements of the calibration curve.

Table 2 Elements of the standard series Unit. µg/L

Element Standard Series Beryllium 0.00 0.50 1.00 2.00 3.00 5.00 Nickel 0.00 5.00 10.0 20.0 30.0 50.0 Copper 0.00 5.00 10.0 20.0 30.0 50.0 Molybdenum 0.00 5.00 10.0 20.0 30.0 50.0 8.3 blank test the reagent blank sample was prepared according to the procedure of 7.3 and measured at 8.4.

8.4 Determination

The prepared samples were measured with the same instrumental analysis conditions as the calibration curve.

9 Results calculation and representation

9.1 Calculation of solid waste leachate test results the mass concentration rho (µg/L) of elements (beryllium, nickel, copper and molybdenum) in the solid waste leaching solution is calculated according to the formula (1)

01) (V

Vx - = (1)

Where. - mass concentration of element in solid waste leachate, µg/L;

1 - Determine the mass concentration of the elements in the test sample from the calibration curve, µg/L;

0_1 - Mass concentration in the laboratory blank sample, µg/L;

1V - volume of the sample after digestion of the leachate, ml;

2V - Sampling volume of solid waste leachate, ml.

9.2 Calculation of solid waste test results

9.2.1 Solid and dry semi-solid solid waste the content of elements (beryllium, nickel, copper and molybdenum) in solid waste is calculated as follows. (2) 001 10) (-xxx-= V (2) where. - Element content in solid waste, mg/kg;

1 - Check the calibration curve to determine the mass concentration of the elements in the sample, µg/L;

0_1 - Mass concentration in the laboratory blank sample, µg/L;

0V - volume of the sample after digestion, ml;

M1 - the amount of solid waste sample weighed, g;

M2 - the mass of the solid waste sample after drying, g;

M3 - the amount of sample to be sieved, g;

9.2.2 Liquid and non-dry semi-solid solid waste the content of elements (beryllium, nickel, copper and molybdenum) in solid waste (mg/kg) is calculated according to formula (3) 001 10) (-xx-= V (3) where. - Element content in solid waste, mg/kg;

1 - Check the mass concentration of the elements in the sample by the calibration curve, µg/L;

0_1 - Mass concentration in the laboratory blank sample, µg/L;

0V - volume of the sample after digestion, ml;

M3 - the amount of solid waste sample weighed, g;

9.3 The result is shown for solid waste leachate determination, when the determination of less than 100 µg/L, the beryllium determination results retained after the decimal point One, nickel, copper and molybdenum determination results remain to the integer position; when the determination is greater than or equal to 100 µg/L, the retention of three effective number.

For the total amount of solid waste determination, when the determination of less than 10.0 mg/kg, the beryllium determination results retained after the decimal point after two Bit, nickel, copper and molybdenum determination results retained after the decimal point; when the determination is greater than or equal to 10.0 mg/kg, retained Three valid digits.

710 precision and accuracy

10.1 Precision

Six laboratories used electric plate method to digest the actual solid waste leachate samples containing beryllium, nickel, copper and molybdenum the relative standard deviations in the laboratory were 3.2% ~ 9.7%, 4.5% ~ 10.6%, 5.7% ~ 11.3% 4.1% ~ 11.4%. The relative standard deviation ranges were 8.4% ~ 10.4%, 8.4% ~ 11.0%, 7.0% ~ 10.5%, 3.4% ~ 7.1%, and the repeatability limits were 0.5 µg/L ~ 0.8 µg/L, 2 µg/L ~ 5 µg/L, 5 µg/L ~ 22 Mg/L, 3 µg/L ~ 10 µg/L, the reproducibility limits were. 0.9 µg/L ~ 1.7 µg/L, 4 µg/L ~ 6 µg/L, 7 µg/L ~ 28 µg/L, 3 µg/L to 12 µg/L.

Six laboratories tested the actual solid waste samples containing beryllium, nickel, copper and molybdenum using a hot plate method.

The relative standard deviations (RSDs) were 4.4% ~ 10.6%, 4.5% ~ 11.0%, 4.5% ~ 8.4% and 4.9% ~ 13.0%, respectively.

The relative standard deviations of the laboratory were 5.9% ~ 6.6%, 5.5% ~ 8.2%, 5.9% ~ 12.5%, 9.2% ~ 13.6%; repeatability limit. 0.03 mg/kg ~ 0.05 mg/kg, 1.4 mg/kg ~ 4.9 mg/kg, 6.25 mg/kg ~ 13.5 mg/kg, 0.4 mg/kg ~ 1.0 mg/k, the reproducibility limits were. 0.03 mg/kg ~ 0.06 mg/kg, 1.7 mg/kg ~ 6.0 mg/kg, 13.1 mg/kg to 18.9 mg/kg, 0.5 mg/kg to 2.6 mg/kg.

Details of precision data are shown in Schedule A.1 and Schedule A.2.

10.2 Accuracy

Six laboratories used hot plate method for the actual solid waste leaching solution containing beryllium, nickel, copper and molybdenum the recoveries were as follows. 81.0% ~ 117%, 82.3% ~ 114%, 81.4% ~ 117%, 81.5% ~ 115% respectively.

Six laboratories used hot plate method to test the actual solid waste of beryllium, nickel, copper and molybdenum, the recoveries were as follows. 81.3% ~ 115%, 85.8% ~ 119%, 80.8% ~ 114%, 82.0% ~ 119%.

The accuracy data are detailed in Schedule A.3 and Schedule A.4.

11 quality assurance and quality control 11.1 each batch of samples to do at least two laboratory reagents blank, blank target elements of the determination of the results should not be greater than the square Legal limit.

11.2 The calibration curve should be plotted for each analysis and linearly fitted with the least squares method. The correlation coefficient should be >=0.995, Otherwise you need to redraw the calibration curve.

Each batch of samples (up to 20 samples) after the analysis of the need to determine the calibration series of zero concentration and the concentration of the middle point of the school Quasi-verification. Zero concentration point determination should be lower than the method detection limit, the intermediate concentration of the measured value and the relative deviation of the concentration should be <= 10%, otherwise the ...