AS 1038.10.3—1998 Australian Standard™ Coal and coke—Analysis and testing Part 10.3: Determination of trace elements—Coal and coke— Determination of boron content— ICP-AES methodThis Australian Standard was prepared by Committee MN/1, Coal and Coke. It was approved on behalf of the Council of Standards Australia on 27 February 1998 and published on 5 June 1998. ‘The following interests are represented on Committee MN/1: ACIRL ‘Australasian Institute of Mining and Metallurgy Australian Coal Association Australian Coal Preparation Society Australian Institute of Energy Bureau of Steel Manufacturers of Australia Coalfield Geology Council of New South Wales CSIRO, Division of Coal and Energy Technology Department of Mines and Energy, Queensland Electricity Supply Association of Austral Institution of Engineers, Australia Minerals Council of Australia Royal Australian Chemical Institute University of New South Wales University of Newcastle University of Queensland Review of Ausralion Standards. To keep abreast of progress in industry, Australian Standards are subject ‘oped ei and are kept po date by he of amendnent Or ew eon a necenar fis ‘prin efor tht Sana ar care ha th re possesion of te leet eam nd ams eit of lt Ausra Standards and eles pubis wil be fund i he Sanders usralia Cataogue of Pubiicarons this information iv Joe the hast Scmsclet Uatch scbgeting mbes neni wich ges dots of vw pelcaton now edions ‘and amendmen, and of withdrawn Standards. ‘Sgqestions for improvement fo husration Standards, addressed othe head office o Standard Atal re eloomed Notiearion of any inaccuracy orange fou in an Australian Standard shouldbe oa Wlehout delay in onder thatthe mater may be vestigated and propriate action waken This Standard was issued in draft form for comment as DR 96494AS 1038.10.3—1998 Australian Standard” Coal and coke—Analysis and testing Part 10.3: Determination of trace elements—Coal and coke— Determination of boron content— ICP-AES method Originated as AS 1038.10.3— 1988, ‘Second edition 1998 Published by Standards Australia (Standards Association of Australia) 1 The Crescent, Homebush, NSW 2140 ISBN 0 7997 1925 2AS 1038.10.3— 1998 2 PREFACE This Standard was prepared by the Standards Australia Committee MN/1, Coal and Coke to supersede AS 1038.10.3—1988, Coal and coke—Analysis and testing, Part 10.3: Determination of trace elements—Coal, coke and fly-ash—Determination of boron content—Spectrophotometric methods. It was prepared as one of a series of methods for the determination of trace elements in coal and coke. ‘The determination of the trace elements in coal and coke is becoming more important due to the considerable emphasis being placed on the effect of these elements on the environment. International buyers are becoming increasingly aware of the need for more detailed knowledge of the coals that they are purchasing and may request trace element analysis. In order to have accurate and precise results for this analysis it is imperative that standard methods be available. ‘The objective of this Standard is to provide a method for determining the boron content of coal and coke. The objective of the revision is to replace the spectrophotometric method with an inductively coupled plasma atomic emission spectrometric method. (© Copyright ~ STANDARDS AUSTRALIA. 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Ts policy may be varied by Standards Australia at an tne3 AS 1038.10.3—1998 CONTENTS Page 4 4 ® 4 4 4 5 6 6 7 1 o 7 fe SCOPE ata dogo 0 2 REFERENCED DOCUMENTS . 3. DEFINITIONS 4 PRINCIPLE . . 5 SAEBTY...+ . 6 7 8 9 REAGENTS te APPARATUS ..... SAMPLE, PROCEDURE ..... 10 CALCULATION .... 11 REPORTING OF RESULTS 12 PRECISION ... 13. TEST REPORT .AS 1038.10.3—1998 4 STANDARDS AUSTRALIA Australian Standard Coal and coke—Analysis and testing Part 10.3: Determination of trace elements—Coal and coke—Determination of boron content—ICP-AES method 1 SCOPE This Standard sets out a method for the determination of boron in higher rank coal and coke using an inductively-coupled plasma atomic emission spectrometer after ashing of the coal or coke in the presence of Eschka mixture. 2 REFERENCED DOCUMENTS The following documents are referred to in this Standard: AS 1038 Coal and coke—Analysis and testing 1038.3. Part 3: Proximate analysis of higher rank coal 1038.16 Part 16: Assessment and reporting of results 2243 Safety in laboratories (series) 2418 Coal and coke—Glossary of terms 2508 Safe storage and handling information card (series) 2706 Numerical values—Rounding and interpretation of limiting values 3641 Recommended practice for atomic emission spectrometric analysis, 3641.2 Part 2: Inductively coupled plasma excitation 4264 Coal and coke—Sampling 4264.1 Part 1: Higher rank coal—Sampling procedures 4264.2. Part 2: Coke—Sampling procedures 3 DEFINITIONS For the purpose of this Standard, the definitions given in AS 2418 apply. 4 PRINCIPLE A known mass of the sample is ignited in intimate contact with Eschka mixture in an oxidizing atmosphere at 800°C to decompose the organic matter. The residue is then extracted with hydrochloric acid and boron is determined by inductively- coupled plasma atomic emission spectrometry (ICP-AES). 5 SAFETY For information on laboratory safety, reference should be made to the relevant parts of AS 2243 and AS 2508. Reagents used may be hazardous or toxic and reference should be made to the appropriate Material Safety Data Sheets. 6 REAGENTS 6.1 General Unless otherwise specified, all reagents shall be of analytical reagent grade and only distilled water or water of equivalent purity shall be used. 6.2 Eschka mixture A mixture composed of two parts by mass of light magnesium oxide and one part by mass of anhydrous sodium carbonate. COPYRIGHT5 AS 1038.10.3—1998 6.3 Hydrochloric acid, p20 1.16 g/mL to 1.19 g/mL. 6.4 Standard solut 6.4.1. Boron stock solution (100 mg/L) Dissolve 0.2859 +0.0005 g of anhydrous boric acid in approximately 100 mL of water in a plastic beaker, add 10 mL of hydrochloric acid (6.3) and mix. Transfer to a 500 mL volumetric flask and adjust to volume with water. Transfer to and store in a plastic bottle. NOTE: A commercially available certified stock solution of boron may be used as an alternative, 6.4.2 Dilute boron stock solution (5 mg/L) Transfer 5 mL of boron stock solution (6.4.1) to a 100 mL volumetric flask, add 1 mL of hydrochloric acid (6.3) and adjust to volume with water. Transfer to and store in a plastic bottle. 7 APPARATUS 7.1 General All apparatus shall be constructed from materials that are thermally stable and chemically inert under the conditions of the procedure. If glassware is utilized, only Grade A volumetric glassware shall be used. 7.2 Muffle furnace—an electrically heated muffle furnace capable of maintaining a zone within the range 800 #25°C. The ventilation shall be such as to give at least 4 air changes per minute at 800°C. 7.3. Crucible—a shallow silica or platinum crucible of approximately 25 mL capacity. 7.4. Silica plate—6 mm thick, having an easy sliding fit in the muffle furnace. 7.5 Receptacles (a) Plastic bottles—autoclavable with lids, 60 mL. capacity. (b) Glassware—100 mL beakers and 50 mL volumetric flasks. 7.6 Inductively coupled plasma atomic emission spectrometer 7.6.1 General The ICP used shall be satisfactory, if, after optimization according to AS 3641.2, and the manufacturer's instructions, it meets the performance criteria given in Clauses 7.6.2 and 7.6.3. The instrument may be of either a simultaneous or sequential type and capable of measuring the intensity of the emitted radiation of boron at 249.678 nm. NOTE: The iron line at 249,782 nm overlaps the commonly used boron line at 249.773 nm. 7.6.2 Short-term stability Calculate the relative standard deviation (RSD) of at least 10 measurements of the intensity of emission at the boron wavelength while aspirating @ solution containing boron at a concentration in the range 100 to 1000 times the detection limit. The RSD should be 1% or less. 7.6.3 Background equivalent concentration and detection limit Calculate the background equivalent concentration (BEC) and detection limit (DL) as described in AS 3641.2, using a blank and a matrix matched solution containing boron at approximately 10 times the detection limit. The values obtained shall be equal to or less than the following values (a) BEC 0.5 mg/L (b) DL 0.01 mg/L. 7.7 Weighing device—an analytical balance having a minimum capacity of 100 g and readable to the nearest 0.1 8. COPYRIGHTAS 1038, 998 6 8 SAMPLE 8.1 General The sample shall be the analysis sample, prepared to a nominal top size of 212 wm. Sample preparation procedures for coal are described in AS 4264.1 and for coke in AS 4264.2 8.2 Equilibration of the sample The moisture content of the sample shall be equilibrated with the laboratory atmosphere by exposure in a thin layer on a tray. Exposure time shall be kept to a minimum. The sample shall be thoroughly mixed immediately before analysis, Carry out a concurrent moisture determination by the procedure specified in AS 1038.3 to enable calculation of the result to a dry basis. 9 PROCEDURE 9.1 Blank determination A blank determination shall be carried out at the same time and under the same conditions as the actual determination, but omitting the sample. 9.2 Preparation of test solution The procedure, carried out in duplicate, shall be as follows: (a) Weigh approximately 0.5 g of the sample to the nearest 0.1 mg and mix intimately with 0.8 g of Eschka mixture (6.2) in the crucible (7.3). Level the contents of the crucible and cover with 0.2 g of the Eschka mixture (6.2) (’) Place the charged crucible on the silica plate (7.4), insert both into the muffle furnace (7.2) at ambient temperature, heat at a uniform rate to 800°C over 2h. ‘Maintain at this temperature for a further 2 bh. (c) Remove the silica plate and crucible from the furnace and allow to cool (4) Transfer the contents of crucible to a tared plastic bottle (7.5(a)) or alternatively to a 100 mL glass beaker (7.5(b)). Wash the residue into the bottle or beaker with 5 mL to 10 mL of water. (©) Add 10 mL of hydrochloric acid (6.3) to the crucible and transfer to the bottle or beaker. Wash the crucible with a further 5 mL of water and transfer the washings to the bottle or beaker. () Cap the bottle and heat on a water bath at 60°C to 70°C for 1 h (alternatively place the beaker on the hotplate, cover with a watch glass and simmer at just below boiling for 30 min). (g) Remove the bottle from the water bath and allow to cool and adjust the mass of the solution to 50.0 g with water (alternatively remove the beaker, allow to cool and transfer the solution to a 50 mL. volumetric flask and make up to volume). Allow any insoluble residue to settle, This is the test solution. 9.3. Preparation of calibration solutions Calibration solutions shall be prepared as follows: (a) Add 1 g of Eschka mixture (6,2) to seven tared plastic bottles (7.5(a)) (alternatively to glass beakers (7.5(b)). Add approximately 10 mL of water and 10 mL of hydrochloric acid (6.3) to dissolve the Eschka mixture (6.2) (b) Allow the solutions to cool. Adjust one solution to $0.0 g (alternatively transfer solution to 50 mL volumetric flasks and adjust one to volume with water). This is the calibration blank. To the other bottles (or flasks) add respectively, 1, 3, 5, 10, 15 and 20 +0.02 mL of the dilute stock solution (6.4.2). Adjust the mass of solution to 50.0 g (alternatively 50.0 mL). These calibration standards are 0.1, 0.3, 0.5, 1.0, 1.5, 2.0 ug B/g of solution (or mg/L if the solutions are prepared in a volumetric flask). ‘COPYRIGHT7 AS 1038.10.3—1998 9.4 Calibration of the inductively coupled plasma atomic emission spectrometer The ICP-AES is calibrated as follows: (a) Set up the instrument to measure the emission at 249.678 nm according to the instrument manufacturer's instructions. (b) Calibrate the spectrometer by reading the blank and standard calibration solutions. A calibration graph is prepared by plotting emission intensity versus concentration. 9.8 Determination of boron Boron is determined as follows: (a) _Recalibrate the instrument or normalize the calibration prior to the measurement of the sample test solutions. The normalization is generally done by reading a blank and one calibration standard and adjusting the slope and intercept of the calibration graph. (b) Aspirate the blank and test solutions into the inductively coupled plasma atomic emission spectrometer and measure the emission of the boron line using the same conditions as used for the calibration and normalization. Convert the emission intensities to concentration of boron in g/mL by reference to the calibration graph. This is usually carried out by the computing system of the instrument. 10 CALCULATION The result for boron in the coal or coke sample shall be calculated using the following equation: Boron in coal or coke expressed as mg/kg = (B, ~ By) x 5O/M. where B, = concentration of boron in test solution, in micrograms per millilitre B, = Concentration of boron in blank test solution, in micrograms per millilitre ‘M = mass of sample, in grams 11 REPORTING OF RESULTS The result, the mean of duplicate determinations, shall be reported to the nearest 1 mg/kg, rounded in accordance with AS 2706. 12 PRECISION The values for repeatability and reproducibility should not exceed those listed in Table 1. Otherwise, reference shall be made to AS 1038.16. 13. TEST REPORT The test report shall include the following information: (2) Complete identification of the sample tested, — (b) Reference to this Australian Standard, i.e. AS 1038.10.3. (©) The boron content of the sample, expressed in mg/kg. (d) The basis for reporting, e.g. air-dry. (©) The moisture content of the sample. TABLE 1 PRECISION DATA Boron content | Repeatability | Reproducibility R my/kg r <50 5 10 250 10% of mean | 20% of mean ‘COPYRIGHT