BRITISH STANDARD BS EN

13137:2001

Characterization of
waste — Determination
of total organic carbon
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(TOC) in waste, sludges

and sediments

The European Standard EN 13137:2001 has the status of a

British Standard

ICS 13.030.01

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 BS EN 13137:2001

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:

— aid enquirers to understand the text;

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— 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.
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
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Compliance with a British Standard does not of itself confer immunity
from legal obligations.

This British Standard, having

been prepared under the
direction of the Sector Policy Summary of pages
and Strategy Committee for This document comprises a front cover, an inside front cover, the EN title page,
Building and Civil pages 2 to 20, an inside back cover and a back cover.
Engineering, was published
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Standards Policy and Strategy document was last issued.
Committee on
28 September 2001

Amendments issued since publication

Amd. No. Date Comments

© BSI 28 September 2001

ISBN 0 580 38053 X

 EUROPEAN STANDARD EN 13137
NORME EUROPÉENNE
EUROPÄISCHE NORM August 2001

ICS 13.030.10, 13.030.20

English version
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Characterization of waste - Determination of total organic carbon

(TOC) in waste, sludges and sediments

Caractérisation des déchets - Dosage du carbone Charakterisierung von Abfall - Bestimmung des Gesamten
organique total (COT) dans les déchets, boues et Organischen Kohlenstoffs (TOC) in Abfall, Schlämmen und
sédiments 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 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 13137:2001 E
worldwide for CEN national Members.
 EN 13137:2001 (E)

Contents

page
Foreword ..................................................................................................................................................................... 3
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Introduction ................................................................................................................................................................ 3
1 Scope...................................................................................................................................................................... 3
2 Normative references ........................................................................................................................................... 4
3 Terms and definitions........................................................................................................................................... 4
4 Principle ................................................................................................................................................................. 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

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 EN 13137:2001 (E)

Foreword
This European Standard has been prepared by Technical Committee CEN/TC 292 "Characterization of
waste", the secretariat of which is held by NEN.
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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

ｗｗｗ．ｂｚｆｘｗ．ｃｏｍ
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.

1 Scope
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.

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 EN 13137:2001 (E)

2 Normative 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.
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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.

3 Terms and definitions

For the purposes of this European Standard, the following terms and definitions apply:

3.1

ｗｗｗ．ｂｚｆｘｗ．ｃｏｍ
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

NOTE Be 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.

4 Principle
The TOC can be measured either by Method A (indirect procedure) or by Method B (direct procedure).

4.1 Method 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.

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 EN 13137:2001 (E)

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.
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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.

NOTE The quality of results of Method B is more dependant on experience and practice, especially regarding
the steps before combustion.

5 Interferences
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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.

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 EN 13137:2001 (E)

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

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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.

NOTE Other 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

ｗｗｗ．ｂｚｆｘｗ．ｃｏｍ
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)

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 EN 13137:2001 (E)

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)

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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 aluminium oxide (7.7) until granular material is
obtained and then comminuted, preferable particle size less than 200 µm. In this case the ratio of
aluminium 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 compounds
except 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 a
clause: "sample dried at 105 °C" respectively "sample dried by freeze drying" (13d)).

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10.2 Water content

The 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 is
calculated 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 in
another way, for instance in accordance with ISO 3733 (distillation method) or ISO 6296 (Karl-Fischer-
method).

10.3 Determination

10.3.1 General

This European Standard gives no recommendation concerning the construction of the apparatus and
method of operation.

The operational characteristics should be selected and checked in accordance with the manufacturer's
instructions.

The weight of the test portion should be as large as possible and shall be chosen so that the liberated
quantity 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 should
be  10 % of the mean. If this is not the case, at least one further determination is necessary; the
coefficient of variation should then be  10 %. If this is not the case, the coefficient of variation shall be
reported together with the result.

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 EN 13137:2001 (E)

10.3.2 Determination of the TC

The 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 the
TC 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 release
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of 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 the
sample with inert material, e.g. silica sand.

The carbon dioxide released during the analysis is measured using one of the detection methods in
accordance with clause 4 and is expressed as carbon.

10.3.3 Determination of the TIC

The sample prepared according to 10.1 is weighed into the purging vessel (8.4).

The system is closed gas-tight and flushed with carrier gas until no more carbon dioxide from ambient air
is present. Then acid (7.10) is added and the carbon dioxide is stripped by purging or stirring and/or
heating. The released carbon dioxide is transferred to the detector by the carrier gas.

samples. ｗｗｗ．ｂｚｆｘｗ．ｃｏｍ
The addition of anti-foaming agents e.g. silicone oil may be helpful in the case of strongly foaming

The addition of wetting agents e.g. surfactants may improve wetting of the surface of the sample.

The carbon dioxide released during the gas evolution is immediately measured using one of the detection
procedures in accordance with clause 4 and is expressed as carbon.

10.4 Calibration

If a relative method is used for detection, e.g. infrared detection, calibration is necessary.

Examples of calibration substances suitable for TC are calcium carbonate (7.2) or potassium hydrogen
phthalate (7.5). Sodium carbonate (7.3) and Na4-EDTA (7.4) as well as all compounds with EDTA-
structure shall not be used for calibration as they are used as control substances.

Sodium carbonate (7.3) or calcium carbonate (7.2) are suitable for the calibration of TIC.

Other calibration substances may be used provided their suitability is checked.

The following procedure should be adopted during calibration:

Establish the preliminary working range.

Measure a minimum of five (recommended ten) standard samples at least in triplicate. The
concentration of these standard samples shall be distributed evenly over the working range.

Calculate mean values for each concentration.

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 EN 13137:2001 (E)

Carry out a linear regression analysis with the mean values and test the linearity of the calibration
function using ISO 8466-1.

The function should be linear. Otherwise the working range has to be restricted to the linear range.

If an absolute method is used for detection, e.g. coulometry, only control measurements according to 10.5
have to be carried out.

This calibration should be carried out for initial validation purposes or when major changes of the
equipment occur.
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10.5 Control measurements

Control measurements shall be performed to check that the equipment is functioning correctly. They
should be carried out each working day using the control mixture A (7.8) for the procedures according to
10.3.2 (TC) and 10.3.3 (TIC). Analysis of one concentration from the middle of the respective working
range repeated three times is sufficient. For the TC and TIC the mean recovery has to be between 90 %
and 110 % with a coefficient of variation  5 %.

When control charts are used one measurement per batch is sufficient.

A blank value shall be determined for all equipment and reagents used. It shall be taken into account if
necessary.

If the required recoveries are not achieved, the following measures may be helpful:

TC analysis

checking the homogeneity of the control mixture

checking the calibration

increasing the combustion temperature

reducing the flow of the carrier gas

encouraging a turbulent flow in the combustion tube

using modifiers

using post-oxidation of the combustion gases by catalysts

TIC analysis

checking the homogeneity of the control mixture

checking the calibration

increasing the temperature during release of carbon dioxide

optimizing the stirring speed and/or the gas flow in the purging vessel

improving the gas exchange in the purging vessel

avoiding condensation in the system.

10.6 Evaluation

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 EN 13137:2001 (E)

The TC and TIC mass contents of the samples prepared according to 10.1a) or 10.1b) are calculated
from

calibration function and sample mass if relative detection methods are used

specific constants and sample mass if absolute detection methods are used.

The TC and TIC results are reported as means of at least two measurements each. The respective
difference of the two values should be  10 % of the mean. If is this is not the case, at least one further
determination is necessary; then the coefficient of variation should be  10 %. If this is not the case, the
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relevant coefficient of variation shall be reported together with the result.

The calculation of TOC is achieved from the difference of the mean values of TC and TIC according to
equation (1). In case of mixing the sample with aluminium oxide according to 10.1b) a dilution factor
following equation (2) has to be considered:

 TOC  f (
TC 
TIC ) (1)

ms  ma
f  (2)
ms

where:

 TOC is the TOC content as carbon in the original sample in grams per kilogram (g/kg);

TC is the mean value of the TC content as carbon in the sample prepared according to 10.1 in
grams per kilogram (g/kg);

TIC is the mean value of the TIC content as carbon in the sample prepared according to 10.1 in
grams per kilogram (g/kg);

f is the dilution factor resulting from the sample preparation of the original sample according
to 10.1b);

ms is the mass of the original sample (to be mixed with aluminium oxide according to 10.1b);

ma is the mass of aluminium oxide according to 10.1b).

The TOC value resulting from equation (1) is calculated on dry matter by equation (3). For this purpose
the water content determined separately according to 10.2 is used:

100
   (3)
100  W
TOCdm TOC

where:

 TOC dm is the TOC content as carbon, calculated on dry matter basis in grams per kilogram
(g/kg);

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 EN 13137:2001 (E)

 TOC is the TOC content as carbon in the original sample in grams per kilogram (g/kg);

W is the water content of the original sample according to 10.2 as mass fraction in percent
(%).

The TOC content is usually determined on the undried sample, but it is always reported as carbon on a
dry matter basis. Following equation (3) results are obtained in g/kg. They can be converted into other
units by using appropriate factors.
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11 Procedure Method B (direct method)

11.1 Sample preparation

See 10.1.

11.2 Water content

See 10.2.

11.3 Determination

11.3.1 General

This European Standard gives no recommendation concerning the construction of the apparatus and
method of operation.

The operational characteristics should be selected and checked in accordance with the manufacturer's
instructions.

The weight of the test portion should be as large as possible and shall be chosen so that the liberated
quantity of carbon dioxide lies within the working range of the equipment/calibration.

TOC measurements are made at least twice. The difference of the two values should be  10 % of the
mean. If this is not the case, at least one further determination is necessary; the coefficient of variation
should then be  10 %. If this is not the case, the coefficient of variation shall be reported together with
the result.

11.3.2 Removal of the inorganic carbon and determination of TOC

The sample prepared according to 11.1 is weighed into a suitable vessel (boat or crucible made of e.g.
ceramics, silica glass, platinum or tin). The vessel may be prepared by thermal treatment (in a muffle
oven or the combustion apparatus itself) to minimize carbon blank values.

To remove the inorganic carbon prior to the determination of the TOC the sample is carefully treated with
a small volume of nonoxidizing mineral acid (7.10). Add the acid very slowly, to avoid foaming and
splashing of the sample. Add as little acid as possible but enough to soak the entire sample and to
remove the inorganic carbon completely.

If moistening with the acid is difficult, the sample may be dampened beforehand with as little water as
possible.

The moisture may be partly removed before combustion. The temperature during this sample treatment
shall not exceed 40 °C.

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 EN 13137:2001 (E)

The sample is transferred to the combustion unit and heated carefully to remove the moisture. This may
be realized by programming the temperature of the furnace or by inserting the sample slowly into the
combustion unit. Then the sample is burnt in the carrier gas containing oxygen (7.11).

The combustion temperature has to be high enough to convert the organic carbon completely to carbon
dioxide. The use of modifiers e.g. tin, copper may increase the recovery.

The temperature range of commercially available instruments lies between 900 °C and 1500 °C.

During the combustion of reactive samples detonation or fuming may be prevented by covering the
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sample with inert material e.g. silica sand after removal of the inorganic carbon.

The total carbon dioxide released during the combustion is measured using one of the detection methods
in accordance with clause 4 and is expressed as carbon.

Corrosion of the combustion device may occur as a result of the acid remaining in the sample. Salt
deposits may contaminate the system.

11.4 Calibration

The calibration for TOC has to be done in accordance with the calibration for TC (10.4). The selection of
the calibration substances is analogous.

11.5 Control measurements

Control measurements should be carried out each working day using the control mixture B (7.9) for the
procedure according to 11.3.2. Triple analysis of one point in the middle of the working range is sufficient.
The mean recovery for the complete TOC procedure has to be between 90 % and 110 % with a
coefficient of variation  10 %.

When control charts are used one measurement per batch is sufficient.

A blank value has to be determined for all equipment and reagents used. It shall be taken into account if
necessary.

If the required recovery is not achieved, the following measures may be helpful:

TOC analysis

checking the homogeneity of the control mixture;

checking the calibration;

increasing the combustion temperature:

reducing the flow of the carrier gas;

encouraging a turbulent flow in the combustion tube;

using modifiers:

using post-oxidation of the combustion gases by catalysts.

Removal of carbonates

decreasing the drying temperature of the acidified sample;

decreasing the drying time of the acidified sample;

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 EN 13137:2001 (E)

omitting the drying step.

11.6 Evaluation

The TOC mass contents of the samples prepared according to 10.1 a) or b) are calculated from

calibration function and sample mass if relative detection methods are used,

specific constants and sample mass if absolute detection methods are used.
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The TOC results are reported as a mean of at least two measurements. The difference of the two values
should be  10 % of the mean. If this is not the case, at least one further determination is necessary;
then the coefficient of variation should be  10 %. If this is not the case, the coefficient of variation shall
be reported together with the result.

The TOC is calculated on dry matter basis by equation (4). For this purpose the water content determined
separately according to 10.2 and, if necessary, the dilution factor resulting from sample preparation is
used.

100
 TOCdm  f 
TOC  (4)
100  W
where:



TOCdm is the TOC content as carbon, calculated on dry matter basis in grams per kilogram (g/kg);

f is the dilution factor resulting from the sample preparation of the original sample according
to 10.1 b) and in accordance with equation (2);

TOC is the mean value of TOC content as carbon in the sample prepared according to 10.1 in
grams per kilogram (g/kg);

W is the water content of the original sample according to 10.2 as mass fraction in percent (%).

The TOC content is usually determined on the undried sample, but it is always reported as carbon on a
dry matter basis. Following equation (4) results are obtained in g/kg. They can be converted into other
units by using appropriate factors.

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 EN 13137:2001 (E)

12 Performance characteristics
The performance data of method A and B given in Table 1 have been established in an European
intercomparison study on five samples of waste and sludge and one synthetic mixture carried out in 1999.

Table 1 – Performance data (method A and B)

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Sample p N O m sR SR sr Sr
(%) (% wdr) (%wdr) (%) (%wdr) (%)

METHOD A

S1 synthetic mixture1) 20 76 0 8,662 0,7614 8,79 0,1854 2,14

S2 filter cake 20 76 1 7,798 1,4925 19,14 0,1716 2,20

S3 bottom ash 19 73 5 3,631 0,5548 15,28 0,1205 3,32
S4 electro-plating sludge 18 71 8 3,333 0,4029 12,09 0,1303 3,91
S5 dredged sludge 19 71 0 7,559 1,8239 24,13 0,3409 4,51
S6 rubble 19 71 5 6,759 0,8408 12,44 0,2156 3,19
METHOD B

S1 synthetic mixture1) 10 40 20 8,332 0,4874 5,85 0,2316 2,78

S2 filter cake 12 46 8 8,498 0,8354 9,83 0,2507 2,95

S3 bottom ash 11 42 16 3,779 0,9905 26,21 0,1629 4,31
S4 electro-plating sludge 10 40 20 3,413 0,4792 14,04 0,1782 5,22
S5 dredged sludge 13 50 0 7,903 1,6588 20,99 0,4939 6,25
S6 rubble 11 43 12 6,327 1,6482 26,05 0,2461 3,89

1) = 9,1 % (theoretical value)

p Number of laboratories
N Number of observed values
O Percentage of outliers
m General mean
wdr Dry matter

sR Estimate of the reproducibility standard deviation

sr Estimate of the repeatability standard deviation

SR Estimate of the relative reproducibility standard deviation

Sr Estimate of the relative repeatability standard deviation

14
 EN 13137:2001 (E)

13 Test report
The test report shall contain at least the following details:

a) reference to this European Standard and the Method used (A or B);

b) all necessary information on the full identification of the sample;

c) the result according to 10.6 or 11.6 respectively;

Licensed Copy: :FULLNAME, : DATE, Uncontrolled Copy, (c) BSI

d) details of all procedural steps which deviate from this standard together with all circumstances that
may have influenced the result.

15
 EN 13137:2001 (E)

Annex A
(informative)

Additional results of inter-laboratory tests

Licensed Copy: :FULLNAME, : DATE, Uncontrolled Copy, (c) BSI

A.1 Influence of temperature and modifiers on the decomposition of barium

carbonate as an example for a refractory compound

Table A.1 – Influence of temperature and modifiers on the decomposition of barium carbonate

- - 900 °C 1100 °C 1300 °C

modifier ratio TC %
BaCO3:modifier

no modifier - < 0,1 < 0,1 5,8

vanadium pentoxide 1:2 6,3 6,3 6,3
tungsten oxide 1:2 < 0,1 6,0 6,3
copper/tungsten [Link] - 5,5 6,2
tin 1:10 6,0 - 6,0

Result:

The use of modifiers may increase the recovery of TC for carbonates that originally decompose at higher
temperatures, see Table A.1.

16
 EN 13137:2001 (E)

A.2 Influence of aluminium oxide or sodium sulphate used for sample

preparation on the recovery of TOC

A real, moist sample (filter cake) was examined by several laboratories. The laboratories used aluminium
oxide as well as sodium sulphate for sample preparation (see 10.1 and 11.1). To get a granular powder, it
was necessary to mix the moist or pasty sample with aluminium oxide in a ratio 1:3 or with sodium
sulphate in a ratio 1:4 to 1:14, see Table A.2.
Licensed Copy: :FULLNAME, : DATE, Uncontrolled Copy, (c) BSI

Table A.2 – Influence of aluminium oxide or sodium sulphate used for sample preparation on the
recovery of TOC

Laboratory TC TOC
identification
%
method A method B
% %
- original sample+ sample+ original sample+ sample+ original sample+ sample+
sample Al2O3 Na2SO4 sample Al2O3 Na2SO4 sample Al2O3 Na2SO4

1 11,7 12,8 11,3 - - - 11,4 12,3 11,0

2 11,8 11,9 11,0 11,5 11,6 10,9 - - -
3 11,6 11,9 - 11,4 11,6 - 11,7 11,7 -
4 12,0 12,1 11,6 11,8 11,8 11,5 12,0 11,3 -
5 11,1 11,6 11,4 10,8 11,5 11,4 - - -
6 11,9 12,0 10,6 11,6 11,8 10,5 - - -
7 12,9 13,8 10,7 - - - 9,7 12,7 5,8
8 11,8 11,7 10,7 11,7 11,4 10,6 - - -
9 11,6 11,1 10,6 11,5 11,0 10,6 - - -
mean 11,8 12,1 11,0 11,5 11,5 10,9 11,2 12,0 8,4
standard 0,48 0,78 0,40 0,33 0,28 0,44 1,03 0,62 -
deviation
coefficient of 4% 6% 4% 3% 2% 4% 9% 5% -
variation

Results:

The use of sodium sulphate for sample preparation leads to

high consumption of sodium sulphate necessary to get a granular powder

a higher limit of determination

problems in the use of quartz combustion tubes

generally reduced results compared with those from the original untreated sample.

The use of aluminium oxide for sample preparation leads to similar results compared with those from the
original untreated samples and does not show the disadvantages cited above.

17
 Licensed Copy: :FULLNAME, : DATE, Uncontrolled Copy, (c) BSI
EN 13137:2001 (E)

A.3 Influence of TIC/TOC ratio on the recovery and the coefficient of variation
Synthetic mixtures containing different ratios of calcium carbonate, glucose and aluminium oxide (TIC to TOC ratios 1:1 to 50:1) were examined by several laboratories,
see Table A.3.1 and A.3.2.

Table A.3.1 – Method A: influence of TIC/TOC ratio on the recovery and the coefficient of variation

Laboratory 1 2 3 4 5 6
identification
ratio mean recovery coefficient of
variation
TIC:TOC expected found
TC 5:5 10 9,9 10,0 9,7 9,9 9,7 9,94 9,85 98 % 1%
measurements
%
5:1 6 6,1 6,0 5,9 5,9 5,9 5,92 5,94 99 % 1%
5:0,5 5,5 5,4 5,5 5,5 5,5 5,5 5,43 5,45 99 % 0%
5:0,1 5,1 5,1 5,1 5,0 5,0 5,0 4,99 5,02 98 % 1%
TIC 5:5 5 4,4 5,0 4,8 4,9 4,8 4,89 4,78 96 % 4%
measurements
%
5:1 5 4,8 5,0 4,9 4,9 4,9 4,88 4,90 98 % 1%
5:0,5 5 4,9 5,0 4,8 5,1 5,0 4,86 4,93 99 % 2%
5:0,1 5 4,9 5,0 4,8 4,9 4,9 4,90 4,89 98 % 1%
TOC results 5:5 5 5,5 5,0 4,9 5,0 4,9 5,05 5,06 101 % 5%
%
5:1 1 1,2 1,0 1,0 1,0 1,0 1,04 1,05 105 % 9%
5:0,5 0,5 0,6 0,5 0,7 0,4 0,4 0,57 0,52 104 % 20 %
5:0,1 0,1 0,1 0,1 0,2 0,0 0,2 0,08 0,11 112 % 51 %

18
 Licensed Copy: :FULLNAME, : DATE, Uncontrolled Copy, (c) BSI
EN 13137:2001 (E)

Table A.3.2 - Method B: influence of TIC/TOC ratio on the recovery and the coefficient of variation

laboratory A B C D E
identification
ratio mean recovery coefficient of
variation
TIC:TOC expected found
TOC 5:5 5 5,3 5,1 5,0 4,5 4,5 4,91 98 % 7%
measurements
%
5:1 1 1,4 1,1 1,0 0,9 0,9 1,05 105 % 20 %
5:0,5 0,5 0,6 0,5 0,5 0,9 0,4 0,57 114 % 32 %
5:0,1 0,1 0,0 0,1 0,1 0,3 0,1 0,14 137 % 65 %

Result:

Up to a TIC to TOC ratio of 10:1 good recoveries and coefficients of variation were obtained for both methods (A and B). Within this limit there is no significant
difference between the two methods.

19
 EN 13137:2001 (E)

A.4 Method A: recovery of TOC for the control mixture A (7.8)

A synthetic mixture of sodium carbonate, Na4EDTA·4H2O and aluminium oxide (TOC=TIC=5%) was analysed by
seven laboratories using method A. Results, see Table A.4.

Table A.4 – Method A: recovery of TOC for the control mixture

Laboratory TC Recovery TIC Recovery TOC Recovery

Licensed Copy: :FULLNAME, : DATE, Uncontrolled Copy, (c) BSI

identification % % % % % %
1 9,4 94 4,7 94 4,8 95
2 9,9 99 4,8 95 5,2 104
3 9,4 94 5,0 99 4,4 88
4 9,8 98 4,9 98 4,9 98
5 10,1 101 4,9 97 5,3 106
6 9,8 98 4,9 97 5,0 100
7 9,6 96 4,9 99 4,6 92
expected 10 - 5 - 5 -
mean 9,71 97 4,84 97 4,87 97
standard deviation 0,28 0,10 0,31
coefficient of variation 3% - 2% - 6% -

Result: For method A the required recovery was generally achieved.

A.5 Method B: influence of the temperature during the removal of inorganic carbon on the
recovery of TOC

The control mixture B (7.9) with an expected value of 6,66% was analysed by one laboratory using the procedure of
method B (11.3.2).

Table A.5 – Method B: influence of temperature during the removal of inorganic carbon on the recovery
of TOC

Temperature TOC Recovery

°C % %
20 6,6 99
30 6,5 98
40 6,3 94
50 5,3 80
70 4,1 62

Result:

Temperatures higher than 40 °C during the removal of inorganic carbon lead to poor recoveries of TOC, see Table
A.5.

20
 Licensed Copy: :FULLNAME, : DATE, Uncontrolled Copy, (c) BSI

blank
 BS EN
13137:2001
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