SIST EN 13137:2002
(Main)Characterization of waste - Determination of total organic carbon (TOC) in waste, sludges and sediments
Characterization of waste - Determination of total organic carbon (TOC) in waste, sludges and sediments
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.
NOTE At the time of publication of this European Standard a standardized procedure for determination of elemental carbon in waste is not available.
Charakterisierung von Abfall - Bestimmung des Gesamten Organischen Kohlenstoffs (TOC) in Abfall, Schlämmen und Sedimenten
Anwendungsbereich
Diese Europäische Norm beschreibt zwei Verfahren für die Bestimmung des Gesamten Organischen Kohlen-stoffs
(TOC) in nicht getrockneten Abfallproben mit mehr als 1 g Kohlenstoff je kg Trockenmasse (0,1%).
Diese Norm kann ebenso für Schlämme, Sedimente und vergleichbares Material genutzt werden.
Elementarer Kohlenstoff, Carbide, Cyanide, Cyanate, Isocyanate, Isothiocyanate und Thiocyanate werden, soweit
vorhanden, mit den in dieser Norm beschriebenen Methoden als organischer Kohlenstoff bestimmt. Bei Abfällen
mit hohen Anteilen der oben genannten Komponenten kann daher eine Interpretation des erhaltenen Mess-wertes
problematisch sein. Falls notwendig, sind diese Komponenten getrennt mit geeigneten Verfahren zu
bestimmen und im Prüfbericht mit anzugeben.
ANMERKUNG Zum Zeitpunkt der Veröffentlichung dieser Europäischen Norm ist kein standardisiertes Verfahren zur
Bestimmung des elementaren Kohlenstoffes verfügbar.
Caractérisation des déchets - Dosage du carbone organique total (COT) dans les déchets, boues et sédiments
La présente Norme européenne spécifie deux méthodes de détermination de la teneur en carbone organique total (COT) dans les échantillons de déchets non séchés contenant plus d'1g de carbone par kilogramme de matiere seche (0,1 % m/m). Lorsqu'ils sont présents, le carbone élémentaire, les carbures, cyanures, cyanates, isocyanates et thiocyanates peuvent etre dosés en tant que carbone organique en utilisant les méthodes décrites dans la présente norme européenne.
Karakterizacija odpadkov - Določevanje celotnega organskega ogljika (TOC) v odpadkih, blatu in sedimentih
General Information
Relations
Standards Content (Sample)
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Charakterisierung von Abfall - Bestimmung des Gesamten Organischen Kohlenstoffs (TOC) in Abfall, Schlämmen und SedimentenCaractérisation des déchets - Dosage du carbone organique total (COT) dans les déchets, boues et sédimentsCharacterization of waste - Determination of total organic carbon (TOC) in waste, sludges and sediments13.030.20Liquid wastes. Sludge13.030.10Trdni odpadkiSolid wastesICS:Ta slovenski standard je istoveten z:EN 13137:2001SIST EN 13137:2002en01-januar-2002SIST EN 13137:2002SLOVENSKI
STANDARD
SIST EN 13137:2002
EUROPEAN STANDARDNORME EUROPÉENNEEUROPÄISCHE NORMEN 13137August 2001ICS 13.030.10, 13.030.20English versionCharacterization of waste - Determination of total organic carbon(TOC) in waste, sludges and sedimentsCaractérisation des déchets - Dosage du carboneorganique total (COT) dans les déchets, boues etsédimentsCharakterisierung von Abfall - Bestimmung des GesamtenOrganischen Kohlenstoffs (TOC) in Abfall, Schlämmen undSedimentenThis 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 EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards 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 translationunder the responsibility of a CEN member into its own language and notified to the Management Centre has the same status as the officialversions.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 STANDARDIZATIONCOMITÉ EUROPÉEN DE NORMALISATIONEUROPÄISCHES KOMITEE FÜR NORMUNGManagement Centre: rue de Stassart, 36
B-1050 Brussels© 2001 CENAll rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 13137:2001 ESIST EN 13137:2002
EN 13137:2001 (E)2ContentspageForeword.3Introduction.31Scope.32Normative references.43Terms and definitions.44Principle.45
Interferences.56
Hazards.57
Reagents.68
Equipment.69
Sample storage.710
Procedure Method A (indirect method).711
Procedure Method B (direct method).1112
Performance characteristics.1413
Test report.15Annex A informative)
Additional results of inter-laboratory tests.16SIST EN 13137:2002
EN 13137:2001 (E)3ForewordThis European Standard has been prepared by Technical Committee CEN/TC 292 "Characterization ofwaste", the secretariat of which is held by NEN.This European Standard shall be given the status of a national standard, either by publication of anidentical text or by endorsement, at the latest by February 2002, and conflicting national standards shallbe 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 thefollowing 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.IntroductionOrganic carbon in waste as well as in sludges and sediments is found in various forms. Due to thediversity of possible organic carbon compounds, the quantitative determination of all individual organiccomponents of natural and anthropogenic origin is not possible. Therefore, it is necessary to rely on themeasurement of total quantities. One of these is total organic carbon (TOC).This parameter may be used for assessing the suitability of waste for landfilling.1ScopeThis European Standard specifies two methods for the determination of total organic carbon (TOC) inundried 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 andthiocyanates are determined as organic carbon using the methods described in this standard. Aninterpretation of the measured value may therefore be problematical in cases where the waste containsrelevant levels of the above mentioned components. If needed, these components shall be determinedseparately 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 ofelemental carbon in waste is not available.SIST EN 13137:2002
EN 13137:2001 (E)42Normative referencesThis 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 listedhereafter. For dated references, subsequent amendments to or revisions of any of these publicationsapply to this European Standard only when incorporated in it by amendment or revision. For undatedreferences 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 ofperformance 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 - Gravimetricmethod.EN 12880, Characterization of sludges - Determination of dry residue and water content.3Terms and definitionsFor 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 carbon3.2
total inorganic carbon (TIC)the quantity of carbon that is liberated as carbon dioxide by acid treatment3.3
total organic carbon (TOC)the quantity carbon that is converted into carbon dioxide by combustion and which is not liberated ascarbon dioxide by acid treatmentNOTEBe aware that the above definitions are valid for this European Standard only and do not complycompletely with scientific definitions of TC, TOC and TIC.4PrincipleThe 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 TCand TIC.The total carbon (TC) present in the undried sample is converted to carbon dioxide by combustion in anoxygen-containing gas flow free of carbon dioxide. To ensure complete combustion, catalysts and/ormodifiers can be used. The released amount of carbon dioxide is measured by infrared spectrometry,gravimetry, coulometry, conductometry, thermal conductivity detection, flame ionization detection afterreduction to methane, or other suitable techniques.SIST EN 13137:2002
EN 13137:2001 (E)5The TIC is determined separately from another sub-sample by means of acidification and purging of thereleased 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 thesample with acid. The carbon dioxide released by the following combustion step is measured by one ofthe techniques mentioned in 4.1 and indicates the TOC directly.4.3
Applicability of Methods A or BMethods 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. volatilehydrocarbons from sludge of oil separators); side reactions between the sample and the acid take place (e.g. decarboxylation, volatile reactionproducts).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 regardingthe steps before combustion.5
InterferencesVolatile organic substances may be lost during sample preparation. If necessary, the carbon contentresulting 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 coulometricdetection is used; in some cases the classical silver or copper trap can be insufficient to absorb allhalides.6
HazardsSamples may be liable to fermentation and may be infectious. Due to this it is recommended to handlethese samples with special care. The gases which may occur due to the microorganism activities arepotentially flammable. Excessive pressure build-up may cause the sample container to burst, potentiallyresulting in the formation of infectious aerosols and contaminated shrapnel.Harmful compounds may arise during the combustion process and during the acid treatment. The userhas to take appropriate precautions (e.g. activated carbon filters) to avoid these getting into the laboratoryenvironment.Samples with a high organic content may explode at introduction into the furnace. This risk can bereduced by using less sample or covering the sample with inert material.SIST EN 13137:2002
EN 13137:2001 (E)67
Reagents7.1
GeneralAll 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, CaCO37.3
Sodium carbonate, Na2CO3, anhydrous7.4
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 thecomposition of the control mixtures has to be recalculated accordingly (see also 7.8 and 7.9).7.5
Potassium hydrogen phthalate, C8H5O4K7.6
Sodium salicylate, C7H5O3Na7.7
Aluminium oxide, Al2O3, neutral, granular size < 200 µm, annealed at 600 °C7.8
Control mixture A: sodium carbonate (7.3), Na4-EDTA·4H2O (7.4) and aluminium oxide (7.7) in amass 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 ofsodium 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) andaluminium 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 ofsodium salicylate, 27,78 g of calcium carbonate, 12,50 g of Na4-EDTA·4H2O, 53,36 g of aluminiumoxide).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 inaccordance with the manufacturer's instructions8
Equipment8.1
Homogenization device, for example mixers, stirrers, grinders, mills8.2
Analytical balance, accurate to at least 0,5 % of test portion weight8.3
Equipment for determination of carbon in solids; with accessories8.4
Purging unit for TIC determination (to Method A only)SIST EN 13137:2002
EN 13137:2001 (E)79
Sample storageThe samples are collected in glass or other suitable containers. Biologically active samples should beanalysed immediately or stored at, at least - 18 °C. For biologically inactive samples special preservationmay not be necessary.10
Procedure Method A (indirect method)10.1
Sample preparationThe 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 aluminium oxide (7.7) until granular material isobtained and then comminuted, preferable particle size less than 200 µm. In this case the ratio ofaluminium oxide to sample shall be considered in the calculation of TOC (10.6 or 11.6).If samples contain - according to the accuracy of the method - negligible amounts of volatile compoundsexcept water, the samples may be dried at 105 °C before homogenization. For analysing liquid sludges,especially sewage sludge, freeze drying may also be used. In these cases the test report has to contain aclause: "sample dried at 105 °C" respectively "sample dried by freeze drying" (13d)).10.2
Water contentThe determination of the water content shall be performed on a separate subsample.For samples containing no or negligible amounts of volatile organic compounds the water content iscalculated from the determination of the dry matter according to ISO 11465, respectively EN 12880.In case of samples containing volatile organic compounds the water content should be determined inanother way, for instance in accordance with ISO 3733 (distillation method) or ISO 6296 (Karl-Fischer-method).10.3
Determination10.3.1
GeneralThis European Standard gives no recommendation concerning the construction of the apparatus andmethod of operation.The operational characteristics should be selected and checked in accordance with the manufacturer'sinstructions.The weight of the test portion should be as large as possible and shall be chosen so that the liberatedquantity of carbon dioxide lies within the working range of the equipment/calibration.Measurements are made at least twice for TC as well as for TIC. The difference of the two values shouldbe
10 % of the mean. If this is not the case, at least one further determination is necessary; thecoefficient of variation should then be
10 %. If this is not the case, the coefficient of variation shall bereported together with the result.SIST EN 13137:2002
EN 13137:2001 (E)810.3.2
Determination of the TCThe sample prepared according to 10.1 is weighed into a suitable vessel (boat or crucible made of e.g.ceramics, silica glass, platinum or tin). The vessel may be pretreated by heating (in a muffle-oven or theTC apparatus itself) to minimize carbon blank values.The sample is burned or decomposed in a flow of carrier gas containing oxygen (7.11).The combustion temperature has to be high enough to convert all carbon completely to carbon dioxide.For samples containing carbonates which are difficult to decompose, e.g. barium carbonate, the releaseof the carbon dioxide may be improved by increasing the temperature or by the use of modifiers, e.g. tin,copper.The temperature range of commercially available instruments is between 900 °C and 1500 °C.During the combustion of reactive samples, detonation or fuming may be prevented by covering thesample with inert material, e.g. silica sand.The carbon dioxide released during the analysis is measured using one of the detection methods inaccordance with clause 4 and is expressed as carbon.10.3.3
Determination of the TICThe sample prepared accord
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