【BS英国标准】BS EN 13137-2001 Characterisation of waste. Determination of total organic carbon (TOC) in waste, sludges and sediments.pdf

BRITISH STANDARD BS EN 13137:2001 Characterization of waste Determination of total organic carbon (TOC) in waste, sludges and sediments The European Standard EN 13137:2001 has the status of a British Standard ICS 13.030.01 NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAW Licensed Copy: :FULLNAME, : DATE, Uncontrolled Copy, (c) BSI BS EN 13137:2001 This British Standard, having been prepared under the direction of the Sector Policy and Strategy Committee for Building and Civil Engineering, was published under the authority of the Standards Policy and Strategy Committee on 28 September 2001 © BSI 28 September 2001 ISBN 0 580 38053 X National foreword This British Standard is the official English language version of EN 13137:2001. The UK participation in its preparation was entrusted by Technical Committee B/508, Waste management, to Subcommittee B/508/3, Waste characterization, which has the responsibility to: A list of organizations represented on this subcommittee can be obtained on request to its secretary. Cross-references The British Standards which implement international or European publications referred to in this document may be found in the BSI Standards Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Find” facility of the BSI Standards Electronic Catalogue. A British Standard does not purport to include all the necessary provisions of a contract. Users of British Standards are responsible for their correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. aid enquirers to understand the text; present to the responsible European committee any enquiries on the interpretation, or proposals for change, and keep the UK interests informed; monitor related international and European developments and promulgate them in the UK. Summary of pages This document comprises a front cover, an inside front cover, the EN title page, pages 2 to 20, an inside back cover and a back cover. The BSI copyright date displayed in this document indicates when the document was last issued. Amendments issued since publication Amd. No. DateComments Licensed Copy: :FULLNAME, : DATE, Uncontrolled Copy, (c) BSI EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE NORM EN 13137 August 2001 ICS 13.030.10, 13.030.20 English version Characterization of waste - Determination of total organic carbon (TOC) in waste, sludges and sediments Caractérisation des déchets - Dosage du carbone organique total (COT) dans les déchets, boues et sédiments Charakterisierung von Abfall - Bestimmung des Gesamten Organischen Kohlenstoffs (TOC) in Abfall, Schlämmen und Sedimenten This European Standard was approved by CEN on 18 June 2001. 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 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 Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMITÉ EUROPÉEN DE NORMALISATION EUROPÄISCHES KOMITEE FÜR NORMUNG Management Centre: rue de Stassart, 36 B-1050 Brussels © 2001 CENAll rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 13137:2001 E Licensed Copy: :FULLNAME, : DATE, Uncontrolled Copy, (c) BSI EN 13137:2001 (E) 2 Contents page Foreword. 3 Introduction 3 1Scope 3 2Normative references . 4 3Terms and definitions. 4 4Principle. 4 5 Interferences. 5 6 Hazards 5 7 Reagents . 6 8 Equipment. 6 9 Sample storage. 7 10 Procedure Method A (indirect method) 7 11 Procedure Method B (direct method). 11 12 Performance characteristics. 14 13 Test report. 15 Annex A informative) Additional results of inter-laboratory tests. 16 Licensed Copy: :FULLNAME, : DATE, Uncontrolled Copy, (c) BSI w w w . b z f x w . c o m EN 13137:2001 (E) 3 Foreword This European Standard 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 February 2002, and conflicting national standards shall be withdrawn at the latest by February 2002. Annex A of this European Standard is informative. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and the United Kingdom. Introduction Organic carbon in waste as well as in sludges and sediments is found in various forms. Due to the diversity of possible organic carbon compounds, the quantitative determination of all individual organic components of natural and anthropogenic origin is not possible. Therefore, it is necessary to rely on the measurement of total quantities. One of these is total organic carbon (TOC). This parameter may be used for assessing the suitability of waste for landfilling. 1Scope This European Standard specifies two methods for the determination of total organic carbon (TOC) in undried waste samples containing more than 1 g carbon per kg of dry matter (0,1 %). This standard can be applied as well to sludges, sediments and comparable materials. When present, elemental carbon, carbides, cyanides, cyanates, isocyanates, isothiocyanates and thiocyanates are determined as organic carbon using the methods described in this standard. An interpretation of the measured value may therefore be problematical in cases where the waste contains relevant levels of the above mentioned components. If needed, these components shall be determined separately by means of a suitable validated procedure and be recorded in the test report. NOTEAt the time of publication of this European Standard a standardized procedure for determination of elemental carbon in waste is not available. Licensed Copy: :FULLNAME, : DATE, Uncontrolled Copy, (c) BSI w w w . b z f x w . c o m EN 13137:2001 (E) 4 2Normative references This European Standard incorporates by dated or undated reference, provisions from other publications. These normative references are cited at the appropriate places in the text, and the publications are listed hereafter. For dated references, subsequent amendments to or revisions of any of these publications apply to this European Standard only when incorporated in it by amendment or revision. For undated references the latest edition of the publication referred to applies (including amendments). ISO 3733, Petroleum products and bituminous materials - Determination of water - Distillation method. ISO 8466-1, Water quality - Calibration and evaluation of analytical methods and estimation of performance characteristics - Part 1: Statistical evaluation of the linear calibration function. ISO 6296, Petroleum products - Determination of water Potentiometric Karl Fischer titration method. ISO 11465, Soil quality - Determination of dry matter and water content on a mass basis - Gravimetric method. EN 12880, Characterization of sludges - Determination of dry residue and water content. 3Terms and definitions For the purposes of this European Standard, the following terms and definitions apply: 3.1 total carbon (TC) the quantity of carbon present in waste in the form of organic, inorganic and elemental carbon 3.2 total inorganic carbon (TIC) the quantity of carbon that is liberated as carbon dioxide by acid treatment 3.3 total organic carbon (TOC) the quantity carbon that is converted into carbon dioxide by combustion and which is not liberated as carbon dioxide by acid treatment NOTEBe aware that the above definitions are valid for this European Standard only and do not comply completely with scientific definitions of TC, TOC and TIC. 4Principle The TOC can be measured either by Method A (indirect procedure) or by Method B (direct procedure). 4.1Method A (indirect procedure) In this procedure the TOC is obtained by the difference between the results of the measurements of TC and TIC. The total carbon (TC) present in the undried sample is converted to carbon dioxide by combustion in an oxygen-containing gas flow free of carbon dioxide. To ensure complete combustion, catalysts and/or modifiers can be used. The released amount of carbon dioxide is measured by infrared spectrometry, gravimetry, coulometry, conductometry, thermal conductivity detection, flame ionization detection after reduction to methane, or other suitable techniques. Licensed Copy: :FULLNAME, : DATE, Uncontrolled Copy, (c) BSI w w w . b z f x w . c o m EN 13137:2001 (E) 5 The TIC is determined separately from another sub-sample by means of acidification and purging of the released carbon dioxide. The carbon dioxide is measured by one of the techniques mentioned above. 4.2 Method B (direct procedure) In this procedure the carbonates present in the undried sample are previously removed by treating the sample with acid. The carbon dioxide released by the following combustion step is measured by one of the techniques mentioned in 4.1 and indicates the TOC directly. 4.3 Applicability of Methods A or B Methods A and B have the same applicability in the terms of TOC content and/or TIC to TOC ratio. Method B may lead to incorrect results in following cases: ? the sample contains volatile substances that evaporate during the acidification (e.g. volatile hydrocarbons from sludge of oil separators); ? side reactions between the sample and the acid take place (e.g. decarboxylation, volatile reaction products). If these restrictions can be excluded, Methods A and B lead to comparable results. In case of doubt, Method A should be preferred. NOTEThe quality of results of Method B is more dependant on experience and practice, especially regarding the steps before combustion. 5 Interferences Volatile organic substances may be lost during sample preparation. If necessary, the carbon content resulting from volatile organic substances shall be determined separately. The procedures may lead to unreliable TOC results if the TIC to TOC ratio is very high (e.g. ? 10). Depending on the detection method used, different interferences may occur, for instance: ? the presence of cyanide can interfere with the coulometric detection of TIC by modifying the pH value (dissolution of HCN); ? high content of halogenated compounds may lead to an overestimation of TOC when coulometric detection is used; in some cases the classical silver or copper trap can be insufficient to absorb all halides. 6 Hazards Samples may be liable to fermentation and may be infectious. Due to this it is recommended to handle these samples with special care. The gases which may occur due to the microorganism activities are potentially flammable. Excessive pressure build-up may cause the sample container to burst, potentially resulting in the formation of infectious aerosols and contaminated shrapnel. Harmful compounds may arise during the combustion process and during the acid treatment. The user has to take appropriate precautions (e.g. activated carbon filters) to avoid these getting into the laboratory environment. Samples with a high organic content may explode at introduction into the furnace. This risk can be reduced by using less sample or covering the sample with inert material. Licensed Copy: :FULLNAME, : DATE, Uncontrolled Copy, (c) BSI w w w . b z f x w . c o m EN 13137:2001 (E) 6 7 Reagents 7.1 General All reagents used shall be at least of analytical grade and suitable for their specific purposes. Hygroscopic substances shall be stored in a desiccator. 7.2 Calcium carbonate, CaCO3 7.3 Sodium carbonate, Na2CO3, anhydrous 7.4 Tetrasodium ethylenediamine tetraacetate-tetra-hydrate, Na4-EDTA·4H2O, C10H12N2O8Na4·4H2O, heated at 80 °C for two hours. NOTEOther forms of Na4-EDTA hydrates may be used if the water content is exactly known. Then the composition of the control mixtures has to be recalculated accordingly (see also 7.8 and 7.9). 7.5 Potassium hydrogen phthalate, C8H5O4K 7.6 Sodium salicylate, C7H5O3Na 7.7 Aluminium oxide, Al2O3, neutral, granular size 200 µm, annealed at 600 °C 7.8 Control mixture A: sodium carbonate (7.3), Na4-EDTA·4H2O (7.4) and aluminium oxide (7.7) in a mass ratio of 2,34 : 1,00 : 1,97. The mixture shall be homogenized. It should contain 50,00 g/kg TIC and 50,00 g/kg TOC (e.g. 44,13 g of sodium carbonate, 18,83 g of Na4-EDTA·4H2O, 37,04 g of aluminium oxide). 7.9 Control mixture B: sodium salicylate (7.6), calcium carbonate (7.2), Na4-EDTA·4H2O (7.4) and aluminium oxide (7.7) in a mass ratio of 1,00 : 4,36 : 1,97 : 8,40. The mixture shall be homogenized. It should contain 33,3 g/kg TIC and 66,6 g/kg TOC (e.g. 6,36 g of sodium salicylate, 27,78 g of calcium carbonate, 12,50 g of Na4-EDTA·4H2O, 53,36 g of aluminium oxide). 7.10 Non-oxidizing mineral acid used for carbon dioxide expulsion, e.g. phosphoric acid H3PO4 (w = 85 %) 7.11 Synthetic air, nitrogen, oxygen, argon, free of carbon dioxide and organic impurities in accordance with the manufacturer's instructions 8 Equipment 8.1 Homogenization device, for example mixers, stirrers, grinders, mills 8.2 Analytical balance, accurate to at least 0,5 % of test portion weight 8.3 Equipment for determination of carbon in solids; with accessories 8.4 Purging unit for TIC determination (to Method A only) Licensed Copy: :FULLNAME, : DATE, Uncontrolled Copy, (c) BSI w w w . b z f x w . c o m EN 13137:2001 (E) 7 9 Sample storage The samples are collected in glass or other suitable containers. Biologically active samples should be analysed immediately or stored at, at least - 18 °C. For biologically inactive samples special preservation may not be necessary. 10 Procedure Method A (indirect method) 10.1 Sample preparation The samples supplied for analysis should be as homogeneous as possible and undried. Depending on the nature and appearance of the sample different procedures can be used, for example: a)Solid samples may be directly comminuted (avoiding heat) and reduced to a granular powder, preferable particle size less than 200 µm. b)Moist or paste-like samples may be mixed with al