Unknown BS EN 15169 2007 ICS 13 030 40 NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAW BRITISH STANDARD Characterization of waste — Determination of loss on ignition in waste, s[.]
BRITISH STANDARD Characterization of waste — Determination of loss on ignition in waste, sludge and sediments ICS 13.030.40 NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAW BS EN 15169:2007 BS EN 15169:2007 National foreword This British Standard is the UK implementation of EN 15169:2007 The UK participation in its preparation was entrusted to Technical Committee B/508/3, Characterization of waste A list of organizations represented on this committee can be obtained on request to its secretary This publication does not purport to include all the necessary provisions of a contract Users are responsible for its correct application Compliance with a British Standard cannot confer immunity from legal obligations This British Standard was published under the authority of the Standards Policy and Strategy Committee on 30 June 2009 © BSI 2009 ISBN 978 580 55086 Amendments/corrigenda issued since publication Date Comments BS EN 15169:2007 EN 15169 EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE NORM February 2007 ICS 13.030.40 English Version Characterization of waste - Determination of loss on ignition in waste, sludge and sediments Caractérisation des déchets - Détermination de la perte au feu des déchets, des boues et des sédiments Charakterisierung von Abfall - Bestimmung des Glühverlustes in Abfall, Schlamm und Sedimenten This European Standard was approved by CEN on 13 January 2007 CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN Management Centre or to any CEN member This European Standard exists in three official versions (English, French, German) A version in any other language made by translation under the responsibility of a CEN member into its own language and notified to the CEN Management Centre has the same status as the official versions CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom EUROPEAN COMMITTEE FOR STANDARDIZATION COMITÉ EUROPÉEN DE NORMALISATION EUROPÄISCHES KOMITEE FÜR NORMUNG Management Centre: rue de Stassart, 36 © 2007 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members B-1050 Brussels Ref No EN 15169:2007: E BS EN 15169:2007 EN 15169:2007 (E) Contents Page Foreword Scope Normative references Terms and definitions 4 Principle 5 Interference Hazards Sample preservation and preparation Apparatus .6 Procedure .6 10 Expression of results 11 Performance characteristics 12 Test report Annex A (informative) Summary of general requirements and recommendations 10 Annex B (informative) Additional validation data 11 B.1 General 11 B.2 Type of samples and sample preparation 11 B.3 Homogeneity and stability 11 B.4 Validation data for sludge from EN 12879 .12 Bibliography 13 BS EN 15169:2007 EN 15169:2007 (E) Foreword This document (EN 15169:2007) has been prepared by Technical Committee CEN/TC 292 “Characterization of waste”, the secretariat of which is held by NEN This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by August 2007, and conflicting national standards shall be withdrawn at the latest by August 2007 The method described in this standard has been derived from EN 12879 which was prepared by CEN/TC 308 Anyone dealing with waste and sludge analysis should be aware of the risks of that kind of material, irrespective of the parameters to be determined Waste and sludge samples may contain hazardous (e g toxic, reactive, flammable, infectious) substances, which can be prone to biological and/or chemical reaction Consequently these samples should be handled with special care Gases which may be produced by microbiological or chemical activity are potentially flammable and will pressurise sealed bottles Bursting bottles are likely to result in hazardous shrapnel, dust and/or aerosol National regulations should be followed with respect to all hazards associated with this method According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom BS EN 15169:2007 EN 15169:2007 (E) Scope This European Standard specifies a method for the determination of the loss on ignition This procedure is applicable to all kinds of waste, sludge and sediments The loss on ignition is often used as an estimate for the content of non-volatile organic matter in waste, sludge and sediments It should be noted that any content of elementary carbon and volatilisation of organic materials or chemical reactions by inorganic compounds, is included in the loss on ignition Normative references The following referenced documents are indispensable for the application of this document For dated references, only the edition cited applies For undated references, the latest edition of the referenced document (including any amendments) applies EN 14346, Characterisation of waste — Calculation of dry matter by determination of dry residue or water content Terms and definitions For the purposes of this document, the following terms and definitions apply 3.1 loss on ignition change in mass as a result of heating a sample under specified conditions The loss on ignition is expressed in weight percent of the dry matter 3.2 residue on ignition mass remaining after heating a sample under specified conditions The residue on ignition is expressed in weight percent of the dry matter 3.3 dry residue wdr remaining mass fraction of a sample after a drying process at 105 °C, as specified in EN 14346 3.4 water content ww mass fraction of water in a sample determined by Karl-Fischer titration, as specified in EN 14346 3.5 dry matter wdm mass fraction of a sample excluding water expressed as a percentage by mass, calculated by determination of dry residue or water content according to EN 14346 3.6 constant mass constant mass is obtained when the change in mass during a further period of heating of h is within 0,5 % (m/m) or mg, whatever is greater BS EN 15169:2007 EN 15169:2007 (E) Principle A test portion is heated in a furnace up to (550 ± 25) °C The difference in mass before and after the heating process is used to calculate the loss on ignition The determination is performed on a beforehand dried sample following EN 14346 or directly on the undried sample including a drying step or by referring to the dry matter Interference In principle there are no interferences connected to the determination, as the loss on ignition is an empirical parameter However, for many purposes the determination is used for assessing the content of organic matter in waste, sludge or sediment samples It should be noted that any elementary carbon in the sample will be included in the loss on ignition value Furthermore, any volatilisation or chemical reactions of inorganic compounds will also be included in the loss of ignition value NOTE Chemically bound water or volatile metals (e g in hydroxides from flue gas cleaning processes) could be released during heating, contributing to the loss on ignition with a positive amount NOTE Iron or other metals present in the sample in the metallic state could be oxidised during heating, contributing to the loss on ignition with a negative amount NOTE Sulphides present in the sample could be oxidised to sulphate during heating, contributing to the loss on ignition with a negative amount Hazards It is advised not to store samples in the open laboratory If samples are to be stored, this has to be done in a well ventilated place 7.1 Sample preservation and preparation Preservation When not analysed immediately samples should be stored in tight containers For biologically inactive samples special preservation may not be necessary Biologically active samples may need to have the lids loosened to prevent build-up of gas pressure If samples are known to be biologically active they should be made inactive e g by freezing or air drying BS EN 15169:2007 EN 15169:2007 (E) 7.2 Preparation The samples supplied for analysis should be as homogeneous as possible Depending on the nature and appearance of the sample, different procedures can be used according EN 15002, e g a) Solid samples may be directly comminuted (avoiding heat) and reduced to a granular powder, preferably a particle size less than 200 µm If no volatiles are present samples may be air-dried prior to comminuting The drying temperature shall not exceed 40 °C b) Moist or pasty-like samples may be mixed with aluminium oxide until a granular material is obtained and then comminuted, preferably a particle size less than 200 µm In this case the ratio of aluminium oxide to sample shall be considered in the calculation of the loss on ignition c) Liquid samples shall be homogenized immediately prior to weighing Foreign bodies or non comminutable material (e g metallic parts such as nuts, bolts, scrap) should be separated from the sample and the weight and nature of the material be recorded Apparatus 8.1 Flat bottom crucible, typically 50 mm to 70 mm in diameter, suitable for heating to 550 °C e g made of porcelain, silica, nickel or platinum 8.2 Muffle furnace or equivalent equipment, capable of maintaining a temperature of (550 ± 25) °C 8.3 Desiccator, containing a desiccant 8.4 Analytical balance with an accuracy of mg or better 8.5 Metal plate 9.1 Procedure Samples not containing volatiles The determination of loss on ignition and the determination of dry matter are performed as separate operations on different portions of the same sample For some materials, however, it is convenient to carry out the determination of both dry residue and loss on ignition in successive operations in the same crucible Procedure for dry residue see EN 14346 In all cases necessary precautions should be taken to avoid absorption of atmospheric humidity by the sample until it is weighed Prepare a crucible (8.1) by placing it in the furnace (8.2) and heat at (550 ± 25) °C for at least 20 Transfer the crucible from the furnace (8.2) after initial cooling on a metal plate (8.5) to a desiccator (8.3) and finish cooling to ambient temperature Weigh the empty crucible to constant mass to the nearest mg (m(a)) on an analytical balance (8.4) Transfer 0,5 g to g of the sample to the crucible and weigh to the nearest mg (m(b)) Larger masses may be taken if appropriate NOTE Masses larger than g should not be used, unless it has been proven that a complete combustion of the actual sample material can be obtained at a higher loading BS EN 15169:2007 EN 15169:2007 (E) If the determination of loss on ignition and determination of dry matter are performed in successive operations, weigh the crucible with the dried sample to the nearest mg (m(d)) Insert the crucible into the furnace (8.2) and heat at (550 ± 25) °C for at least h NOTE If the dry matter is of high organic content, losses may occur as a result of rapid ignition or deflagration of the sample In this case heat the sample slowly Remove the hot crucible from the furnace (8.2) and allow cooling on a clean metal plate (8.5) for a few While still warm, transfer the crucible to a desiccator (8.3) and finish cooling to ambient temperature Weigh the crucible containing the ignition residue to the nearest mg (m(c)) as soon as ambient temperature is reached Ignition can be regarded as complete when a constant mass is obtained If even after a third heating at (550 ± 25) °C constant mass is not obtained, record the value determined as the last measurement This shall be recorded along with the result NOTE If black carbon particles are still present (some organic substances burn slowly at 550 °C), wet the residue using a few drops of ammonium nitrate solution After repeated drying insert the crucible into the furnace and slowly heat to avoid losses by deflagration and continue heating the residue to (550 ± 25) °C Ammonium nitrate solution is prepared by dissolving 10 g of reagent grade ammonium nitrate, NH4NO3, in 100 ml of demineralised water 9.2 Samples containing volatiles For samples containing significant amounts of volatile components dry matter can not be determined as dry residue In this case the dry matter is calculated from the water content For procedure see EN 14346 In this case the loss on ignition is always performed directly on the undried sample Prepare a crucible (8.1) by placing it in the furnace (8.2) and heat to (550 ± 25) °C for at least 20 Transfer the crucible from the furnace (8.2) after initial cooling on a metal plate (8.5) to a desiccator (8.3) and finish cooling to ambient temperature Weigh the empty crucible to constant mass to the nearest mg (m(a)) on an analytical balance (8.4) Transfer 0,5 g to g of the sample to the crucible and weigh to the nearest mg (m(b)) Larger masses may be taken if appropriate All necessary precautions should be taken to avoid loss of volatiles from the sample until it is weighed NOTE Masses larger than g should not be used unless it has been proven that a complete combustion of the actual sample material can be obtained at a higher loading NOTE To avoid splashing from escaping vapours or sudden fire it is recommended to carefully remove most of the volatile components from the sample into a drying oven or at ambient temperature into a fume hood prior to ignition NOTE Samples of highly flammable waste e g solvents or waste oil should be ignited in the crucible and allowed to burn in a fume hood before being inserted into the furnace When ready the crucible is inserted into a cold furnace (8.2) and heated to temperature for h Remove the hot crucible from the furnace (8.2) and allow it to cool on a clean metal plate (8.5) for a few minutes While still warm, transfer the crucible to a desiccator (8.3) and finish cooling to ambient temperature Weigh the crucible containing the ignition residue to the nearest mg (m(c)) as soon as ambient temperature is reached Ignition is complete when constant mass is obtained In cases when even after a third heating at (550 ± 25) °C constant mass is still not obtained, record the value determined as the last of the measurements This shall be reported along with the result NOTE If black carbon particles are still present (some organic substances burn slowly at 550 °C), wet the residue using a few drops of ammonium nitrate solution After repeated drying insert the crucible into the furnace and slowly heat to avoid losses by deflagration and continue heating the residue to (550 ± 25) °C Ammonium nitrate solution is prepared by dissolving 10 g of reagent grade ammonium nitrate, NH4NO3, in 100 ml of demineralised water BS EN 15169:2007 EN 15169:2007 (E) 10 Expression of results 10.1 Loss on ignition, samples not containing volatiles The loss on ignition WLOI is expressed in weight percent of the dry matter If the loss on ignition is performed on an undried sample the result shall be calculated from equation (1) If the loss on ignition is performed in successive operation with the determination of dry residue (in the same crucible) the result shall be calculated from equation (2) m(b) − m(c) 100 ×100 − (100 − wdm ) × WLOI = m(b) − m(a) wdm (1) m(d ) − m(c) × 100 WLOI = m(d ) − m(a) (2) where WLOI is the loss on ignition of the sample in percents of the dry residue or water-free sample; wdm is the dry matter content of the sample in percent; m(a) is the mass of the empty crucible in grams; m(b) is the mass of the crucible containing the undried sample in grams; m(c) is the mass of the crucible containing the ignition residue in grams; m(d) is the mass of the crucible containing the dried sample in grams The result shall be rounded to the nearest 0,1 percent 10.2 Loss of ignition, samples containing volatiles The loss on ignition is expressed in weight percent of the dry matter The result shall be calculated from equation (3) m(b) − m(c) 100 ×100 − ww × WLOI = m(b) − m(a) 100 − ww where WLOI is the loss on ignition of the sample in per cents of the dry residue or water-free sample; ww is the water content of the sample in percent; m(a) is the mass of the empty crucible in grams; m(b) is the mass of the crucible containing the undried sample in grams; m(c) is the mass of the crucible containing the ignition residue in grams The results shall be rounded to the nearest 0,1 percent (3) BS EN 15169:2007 EN 15169:2007 (E) 10.3 Residue on ignition The residue on ignition WROI of a sample expressed in weight percent of the dry matter shall be calculated from equation (4): W ROI = 100 − WLOI (4) where WLOI is the loss on ignition of the sample in percents of the dry residue or water-free sample; WROI is the residue on ignition of the sample in percents of the dry residue or water-free sample 11 Performance characteristics The method performance characteristics given in Table have been established in a European intercomparison study, carried out in 2005, on two typical wastes and one contaminated soil sample Additional information of the intercomparison study is given in Annex B (B.1 – B.3) Also in Annex B (B.4) validation data concerning determination of loss on ignition in sludge according to EN 12879 can be found Table — Performance characteristics for the determination of the loss on ignition in waste Material p N O x sr Sr sR SR % LOI % m/m, dry matter % % % % Contaminated soil 26 77 5,58 0,13 2,39 0,34 6,13 Dredged sludge 25 74 11,38 0,23 1,99 0,97 8,50 Nickel sludge 24 72 11,74 0,31 2,65 1,32 11,26 p N O x sR sr SR Sr Number of participating laboratories Number of outlier-free individual analytical results Percentage of outliers mean value Estimate of the reproducibility standard deviation Estimate of the repeatability standard deviation Estimate of the relative reproducibility standard deviation expressed in percent Estimate of the relative repeatability standard deviation expressed in percent 12 Test report The test report shall contain the following information: a) reference to this European Standard; b) all information necessary to completely identify the waste, sludge or sediment sample; c) results of the determination according to clause 10; d) any details not specified in this European Standard and any other factors that may have affected the result; e) removal of any foreign bodies from the sample BS EN 15169:2007 EN 15169:2007 (E) Annex A (informative) Summary of general requirements and recommendations Purpose of this summary is to support the organization for sampling and sample pre-treatment processes The information given should be helpful for preparing a sampling plan Requirements not mentioned in this document are considered as recommendations Table A.1 Matrix restrictions No restrictions Typical working range > % (m/m) of loss on ignition Sampling instruments No restrictions Container pre-treatment Clean and dry Container material Any air-tight container of amber glass or plastic with no migration of constituents e g PP or PE Transport conditions Dark and cool Preservation Biological active samples may need to have the lids loosened to prevent build-up of gas pressure Biological active samples should be made inactive e g by freezing or air drying Storage conditions Store in tight containers Required amount About 500 g Larger masses may be taken if needed for related determinations Test portion 500 mg to gram Larger masses may be taken if appropriate Drying procedure Generally determination of LOI is performed on undried sample For some samples not containing volatiles, it is convenient to carry out the determination of dry residue (105 °C) and loss on ignition in successive operations in the same crucible Sieving (particle size) Particle sizes < 200 µm are favourable Foreign bodies or non comminutable material should be separated from the sample and the weight and nature of the material should be recorded Grinding Solid samples may be directly comminuted (avoid heating) and reduced to a granular powder, preferable less than 200 µm If no volatiles are present samples may be air dried prior to comminuting at temperatures up to 40 °C Moist or pasty-like samples may be mixed with aluminium oxide until a granular material is obtained and then comminuted, preferable particle size less than 200 µm Compatibility with Loss on ignition (LOI) may be used as a characteristic of the sample material as well as a reference for other parameters and as the result of other parameters may be expressed relative to LOI residue on ignition Storage and handling of the sample may introduce changes in the result of LOI Thus the test portion for loss on ignition should be identical to the test portion used for the related determinations 10 BS EN 15169:2007 EN 15169:2007 (E) Annex B (informative) Additional validation data B.1 General Except for direct validation data, a validation study contains a number of additional data which may be relevant for users of this European Standard B.2 Type of samples and sample preparation a) Contaminated soil The sample was taken from an old industrial site It was sieved (2 mm) and spiked with activated charcoal (4 %, w/w) to ensure practical data for loss on ignition Afterwards, it was homogenized by shaking in a plastic drum b) Dredged sludge The sample was taken from a stagnant riparian water zone on the river Rhine It was dried at room temperature for 30 h, sieved (2 mm) and homogenized in a plastic drum c) Nickel sludge This mixture of inorganic waste material consisted mainly of carbonates resulting from a metallurgical process The material was sieved (3 mm) and after drying at room temperature overnight, it was homogenized in a plastic drum B.3 Homogeneity and stability For investigation of homogeneity, repeated analyses from different sample vessels were performed Data from homogeneity testing are given in Table B.1 Stability and in-bottle-homogeneity of samples were tested by to repeated analyses from one sample container Analyses were performed during the experimental phase of the study Vials a, b, c and d were analyzed at different dates during the validation study Results showed that all samples were stable 11 BS EN 15169:2007 EN 15169:2007 (E) Table B.1 — Results from homogeneity testing Material different bottles x s LOI % Dredged sludge Contaminated soil Nickel sludge x s S Three repeated measurements in one bottle S x % LOI % s S % 12,68 0,24 1,87 12,33 0,15 1,24 6,04 0,07 1,23 6,07 0,15 2,52 14,03 0,35 2,46 13,3 0,78 5,87 Mean value Standard deviation Relative standard deviation expressed in percent B.4 Validation data for sludge from EN 12879 Table B.2 cites the validation data from EN 12879 Table B.2 — Validation data from EN 12879 Material p N O x SR Sr p N O x Sr SR % LOI % m/m, dry matter % % Sludge 15 63,1 0,41 1,02 Sludge 15 90,1 0,12 0,12 Sludge 23 25 68,1 0,45 1,89 Sludge 23 25 79,8 0,41 0,89 Sludge 13 73,9 0,83 2,31 Sludge 13 61,5 0,55 3,24 Number of participating laboratories Number of outlier-free individual analytical results Percentage of outliers Mean value Estimate of the relative reproducibility standard deviation Estimate of the relative repeatability standard deviation Sludges and are not listed due to a lack of data in EN 12879 (missing number of results) 12 BS EN 15169:2007 EN 15169:2007 (E) Bibliography [1] EN 12879, Characterization of sludges — Determination of the loss on ignition of dry mass [2] EN 15002, Characterization of waste — Preparation of test portions from the laboratory sample 13 BS EN 15169:2007 BSI - British Standards Institution BSI is the independent national body responsible for preparing British Standards It presents the UK view on standards in Europe and at the international level It is incorporated by Royal Charter Revisions British Standards are updated by amendment or revision Users of British Standards should make sure that they possess the latest amendments or editions It is the constant aim of BSI to improve the quality of our products and services We would be grateful if anyone finding an inaccuracy or ambiguity while using this British Standard would inform the Secretary of the technical committee responsible, the identity of which can be found on the inside front cover 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