Soil and waste characterization - Temperature dependent differentiation of total carbon (TOC400, ROC, TIC900)

This European standard specifies a method for the differentiated determination of the organic carbon content (TOC400) which is released at temperatures up to 400 °C, the residual oxidizable carbon (ROC) (including e.g. lignite (brown coal), hard coal, charcoal, black carbon, soot) and the inorganic carbon (TIC900) which is released at temperatures up to 900 °C.
The basis is the dry combustion to CO2 in a in the presence of oxygen using using temperatures ranging from 150°C to 900 °C in dry solid samples of soil, soil with anthropogenic admixtures and solid waste (see Table 1) with carbon contents of more than 1 g per kg (0,1 % C) (per carbon type in the test portion).

Boden- und Abfallbeschaffenheit - Temperaturabhängige Unterscheidung von Gesamtkohlenstoff (TOC400, ROC, TIC900)

Diese Norm legt ein Verfahren zur differenzierten Bestimmung des Gehalts an organischem Kohlenstoff (TOC400), der bis 400 °C freigesetzt wird, restlichem oxidierbaren Kohlenstoff (ROC) (u. a. Braun-, Stein-, Holzkohle, schwarzer Kohlenstoff, Ruß) und anorganischem Kohlenstoff (TIC900), der bis 900 °C freigesetzt wird, fest.
Grundlage ist die trockene Verbrennung im Sauerstoffstrom zu CO2 mittels Temperaturgradienten von 150 °C bis 900 °C in trockenen Feststoffproben von Boden, Boden mit anthropogenen Beimengungen sowie festen Abfällen (siehe Tabelle 1) mit Gehalten von mehr als 1 g Kohlenstoff je kg (0,1 % C) (je Kohlenstoffart in der Messprobe).
Alternativ darf das Verfahren nach Anhang B verwendet werden.

Caractérisation des sols et des déchets - Différentiation en fonction de la température du carbone total (COT400, COR, CIT900)

Le présent document spécifie une méthode de détermination différenciée de la teneur en carbone organique (COT400) qui est libéré à des températures allant jusqu’à 400 °C, de la teneur en carbone oxydable résiduel (COR) (notamment du lignite (houille brune), de la houille, du charbon, du carbone suie, de la suie, par exemple) et de la teneur en carbone inorganique (CIT900) qui est libéré à des températures allant jusqu’à 900 °C.
La méthode repose sur la formation de CO2 par combustion sèche en présence d’oxygène à des températures allant de 150 °C à 900 °C d’échantillons solides anhydres de sol, de sol avec adjuvants anthropogènes et de déchets solides (voir Tableau 1) présentant des teneurs en carbone de plus de 1 g/kg (0,1 % C) (par type de carbone dans la prise d’essai).
La méthode spécifiée à l’Annexe B peut également être utilisée.

Karakterizacija tal in odpadkov - Diferenciacija celotnega ogljika (TOC400, ROC, TIC900) v odvisnosti od temperature

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SLOVENSKI STANDARD
oSIST prEN 17505:2022
01-september-2022
Karakterizacija tal in odpadkov - Diferenciacija celotnega ogljika (TOC400, ROC,
TIC900) v odvisnosti od temperature

Soil and waste characterization - Temperature dependent differentiation of total carbon

(TOC400, ROC, TIC900)
Boden- und Abfallbeschaffenheit - Temperaturabhängige Unterscheidung von
Gesamtkohlenstoff (TOC400, ROC, TIC900)

Caractérisation des sols et des déchets - Différentiation en fonction de la température du

carbone total (COT400, COR, CIT900)
Ta slovenski standard je istoveten z: prEN 17505
ICS:
13.030.10 Trdni odpadki Solid wastes
13.080.10 Kemijske značilnosti tal Chemical characteristics of
soils
oSIST prEN 17505:2022 en,fr,de

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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oSIST prEN 17505:2022
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oSIST prEN 17505:2022
DRAFT
EUROPEAN STANDARD
prEN 17505
NORME EUROPÉENNE
EUROPÄISCHE NORM
July 2022
ICS 13.030.10; 13.080.10
English Version
Soil and waste characterization - Temperature dependent
differentiation of total carbon (TOC400, ROC, TIC900)

Caractérisation des sols et des déchets - Différentiation Boden- und Abfallbeschaffenheit -

en fonction de la température du carbone total Temperaturabhängige Unterscheidung von

(COT400, COR, CIT900) Gesamtkohlenstoff (TOC400, ROC, TIC900)

This draft European Standard is submitted to CEN members for second enquiry. It has been drawn up by the Technical

Committee CEN/TC 444.

If this draft becomes a European Standard, 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.

This draft European Standard was established by CEN 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-CENELEC

Management Centre has the same status as the official versions.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,

Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway,

Poland, Portugal, Republic of North Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and

United Kingdom.

Recipients of this draft are invited to submit, with their comments, notification of any relevant patent rights of which they are

aware and to provide supporting documentation.

Warning : This document is not a European Standard. It is distributed for review and comments. It is subject to change without

notice and shall not be referred to as a European Standard.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels

© 2022 CEN All rights of exploitation in any form and by any means reserved Ref. No. prEN 17505:2022 E

worldwide for CEN national Members.
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oSIST prEN 17505:2022
prEN 17505:2022 (E)
Contents Page

European foreword ....................................................................................................................................................... 3

Introduction .................................................................................................................................................................... 4

1 Scope .................................................................................................................................................................... 5

2 Normative references .................................................................................................................................... 5

3 Terms and definitions ................................................................................................................................... 5

4 Principle ............................................................................................................................................................. 6

5 Interferences .................................................................................................................................................... 6

5.1 Interference due to carbides ....................................................................................................................... 6

5.2 Interference due to sulfur and nitrogen compounds ......................................................................... 6

5.3 Interference due to carbonates .................................................................................................................. 6

5.4 Peak does not reach the baseline .............................................................................................................. 8

5.5 Difficulties in separating ROC peak and TIC peak ................................................................ 10

600 900A

5.6 Interferences due to premature releases and deflagrations ....................................................... 10

5.7 Interferences due to catalytic active metal contents in samples ................................................ 10

6 Reagents .......................................................................................................................................................... 10

6.1 General ............................................................................................................................................................. 10

6.2 Oxygen, O2, purity φ > 99.7 % or synthetic air, purity φ > 99.7 %. ............................................ 11

6.3 Inert gas, e.g. nitrogen, N , (only for the alternative procedure specified in 8.6). ............... 11

6.4 Calcium carbonate, CaCO . ........................................................................................................................ 11

6.5 Activated carbon........................................................................................................................................... 11

6.6 Microcrystalline cellulose ......................................................................................................................... 11

6.7 Aluminium oxide, Al O .............................................................................................................................. 11

2 3

6.8 Graphite ........................................................................................................................................................... 11

6.9 Standards for system control ................................................................................................................... 11

7 Apparatus ........................................................................................................................................................ 12

7.1 Homogenization equipment, e.g. mixer, stirrer, grinders, mills. ................................................ 12

7.2 Analytical balance, (accurate to at least 0,5 % of the test portion weight). ............................ 12

7.3 Equipment for determining different carbon types in solids ...................................................... 12

8 Procedure........................................................................................................................................................ 12

8.1 General ............................................................................................................................................................. 12

8.2 Sample preparation and processing ..................................................................................................... 12

8.3 Calibration ...................................................................................................................................................... 12

8.4 Measurement (Oxidative method A) ..................................................................................................... 12

8.5 Measurement (Mixed oxidative/non-oxidative method B) .......................................................... 14

9 Evaluation ....................................................................................................................................................... 15

9.1 General ............................................................................................................................................................. 15

9.2 Control measurements ............................................................................................................................... 17

10 Expression of results ................................................................................................................................... 17

11 Test report ...................................................................................................................................................... 17

Annex A (informative) Performance characteristics ................................................................................... 18

Annex B (informative) Cooling procedure for methode B .......................................................................... 28

Bibliography ................................................................................................................................................................. 29

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oSIST prEN 17505:2022
prEN 17505:2022 (E)
European foreword

This document (prEN 17505:2022) has been prepared by Technical Committee CEN/TC 444

“Environmental characterization of solid matrices”, the secretariat of which is held by NEN.

This document is currently submitted to the CEN Enquiry.
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oSIST prEN 17505:2022
prEN 17505:2022 (E)
Introduction

Carbon occurs in soils and materials similar to soil in a variety of compounds and forms. When

determining carbon in soils or soil-like materials, an overall determination of the different mass fractions

is most feasible. The summarized declaration of carbon is yet done by differentiating organic and

inorganic carbon (EN 15936, ISO 10694). In the proportion classified as “organic carbon”, a fraction of

very stable highly aromatic and highly condensed carbon compounds can be present, sometimes in

significant mass fractions. Since this black (pyrogenic) carbon is only very slowly decomposed and

released, its environmental relevance has to be differently evaluated than the proportions of organic

carbon which are faster chemical-biologically decomposed. The environmental relevance is estimated if

e.g. the suitability of soils and soil-like materials for disposal in landfill is assessed. For a differentiated

assessment, a separate declaration of the different mass fractions of organic, black (pyrogenic) and

inorganic carbon is necessary. Using the specified temperature-gradient method and utilizing the

combustion characteristic(s), the various bond types of carbon in soil and soil-like materials can be

differentiated.

In respect of the hazard potential, the content of solely organically bonded carbon in solids determined

with the described method can be important for disposal and/or recycling.

The method has been validated with the materials listed in Table 1, see also Annex A.

Table 1 — Materials used for validation
Material type Materials used for validation
soils from natural material mineral soils
soil with anthropogenic admixtures (urban
soils)
tailing material (tailings) tailing material from coal mining
sediment sediment
waste waste incineration ash
foundry sand
construction waste
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oSIST prEN 17505:2022
prEN 17505:2022 (E)
1 Scope

This document specifies a method for the differentiated determination of the organic carbon content

(TOC ) which is released at temperatures up to 400 °C, the residual oxidizable carbon (ROC) (including

400

e.g. lignite (brown coal), hard coal, charcoal, black carbon, soot) and the inorganic carbon (TIC ) which

900
is released at temperatures up to 900 °C.

The basis is the dry combustion or decomposition of carbon to CO in the presence of oxygen or non-

oxygen conditions using temperatures ranging from 150 °C to 900 °C in dry solid samples of sediment,

soil, soil with anthropogenic admixtures and solid waste (see Table 1) with carbon contents of more than

1 g per kg (0,1 % C) (per carbon type in the test portion).

NOTE TIC’ includes the TIC measured after acid addition e.g. by ISO 10694 or EN 15936. TOC400 is the carbon

black free portion of TOC measurement e.g. by ISO 10694 or EN 15936.
2 Normative references
There are no normative references in this document.
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.

ISO and IEC maintain terminological databases for use in standardization at the following addresses:

IEC Electropedia: available at https://www.electropedia.org/
ISO Online browsing platform: available at https://www.iso.org/obp
3.1
total organic carbon which is released up to 400 °C - TOC
400

quantity of carbon which is determined in the range between 150 °C to the 1st signal minimum at (400 ±

20) °C, in the case of dry combustion in the presence of oxygen

Note 1 to entry: TOC is the carbon black free portion of TOC measured e.g. by ISO 10694 or EN 15936. This

400

carbon fraction is important regarding the hazard potential for disposal and/or recycling.

3.2
residual oxidizable carbon measured at 600°C - ROC
600

quantity of carbon which is determined between the signal minima at (400 ± 20) °C and at (600 ± 20) °C,

in the case of dry combustion in the presence of oxygen following method A (procedure see 8.4)

3.3
residual oxidizable carbon measured at 900°C - ROC
900

quantity of carbon which is determined during dry combustion in the presence of oxygen after the

completed carbon release for the TOC and TIC measurement at (900 ± 20) °C following method B

400 900B
(procedure see 8.5)
3.4

total inorganic carbon which is released up to 900 °C C in the presence of oxygen TIC

900A

quantity of carbon which is determined between the signal minima at (600 ± 20) °C and at (900 ± 20) °C,

in the case of dry combustion in the presence of oxygen following method A (procedure see 8.4)

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prEN 17505:2022 (E)
3.5

total inorganic carbon which is released up to 900 °C during non-oxidizing conditions - TIC

900B

quantity of carbon which is determined during non-oxidizing conditions between the signal minima at

(400 ± 20) °C and at (900 ± 20) °C before the ROC measurement following method B (procedure see

900B
8.5)
3.6
total carbon

quantity of carbon present in the sample representing the sum of organic (TOC ), inorganic (TIC and

400 900A
TIC ) and residual oxidizable carbon (ROC or ROC )
900B 600 900
4 Principle

The determination of organic carbon (TOC ), residual oxidizable carbon (ROC and ROC ) and

400 600 900

inorganic carbon (TIC and TIC ) in solids is affected by means of thermal oxidation or

900A 900B

decomposition of the different bond types of carbon at different temperatures to CO , if necessary,

supported by changing between oxidizing and non-oxidizing carrier gases.

The application of the gradient method with a suitable temperature program allows the determination of

organic carbon (TOC ), residual oxidizable carbon (ROC) and inorganic carbon (TIC ) and the

400 900
calculation of total carbon (TC) by totalling these contents.

The final analysis of CO can be performed with different methods, e.g. by means of infrared detection or

CO sensitive sensors.
5 Interferences
5.1 Interference due to carbides
Several carbides can interfere with this method.
5.2 Interference due to sulfur and nitrogen compounds

Depending on the measuring technique used, high contents of sulfur or nitrogen compounds can result

in overestimations or underestimations. This can be controlled by means of selected standard samples

(e.g. potassium sulfate, potassium nitrate). Furthermore, the information provided by the equipment

manufacturer shall be considered.
5.3 Interference due to carbonates

The thermal stability of carbonates exhibits a great bandwidth (for examples see Figures 1, 2 and 3).

Therefore, carbonates might be detected in both the TOC peak range and the ROC range. In the

400 600

presence of certain carbonates or carbonate mixtures which decompose at low temperature ranges, the

identification of the TIC peak is sometimes difficult or impossible. Alternatively, the impact of

900A

carbonates on the TOC analysis can be determined by stripping with acid (e.g. Scheibler method

400
EN ISO 10693).

For samples containing the more thermally stable carbonates, e.g. barium carbonate, the liberation of

carbon dioxide can be improved by increasing temperature or using additives such as tungsten oxide.

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oSIST prEN 17505:2022
prEN 17505:2022 (E)
Key
X time
Y1 signal intensities
Y2 temperature in °C
Figure 1 — Example diagram FeCO
Key
X time
Y1 signal intensities
Y2 temperature in °C
Figure 2 — Example diagram MnCO ·fH O
3 2
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oSIST prEN 17505:2022
prEN 17505:2022 (E)
Key
X time
Y1 signal intensities
Y2 temperature in °C
Figure 3 — Example diagram PbCO
5.4 Peak does not reach the baseline

For some materials, the temperature plateau according to the temperature ramp does not last long

enough and the peak does not reach the baseline (see Figure 4). A reasonable prolongation of the plateau

at the temperature level can improve the result in terms of a significantly better return of the signal to

the baseline (see Figure 5).

NOTE A homogeneous distribution of the sample in the combustion vessel optimizes the reaction with oxygen.

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oSIST prEN 17505:2022
prEN 17505:2022 (E)
Key
X time in s
Y1 signal intensities
Y2 temperature in °C
Figure 4 — Example diagram for cases where peaks do not reach the baseline
Key
X time in s
Y1 signal intensities
Y2 temperature in °C

Figure 5 — Example diagram for the prolongation of the temperature plateau so peaks can reach

the baseline
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oSIST prEN 17505:2022
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5.5 Difficulties in separating ROC600 peak and TIC900A peak

If the temperature ramp does not allow the separation (resolution) of the ROC peak from the TIC

600 900A

peak (see Figure 6), the influence of carbonates on the ROC analysis or of ROC on the TIC

600 600 900A

measurement can be determined by stripping with acid (e.g. Scheibler EN ISO 10693). Alternatively, the

method specified in 8.6 can be used. The method has to be documented with the measuring result.

In the case of deviating determination of TIC by means of acid, the information provided by the

900A
equipment manufacturer should be consulted.
Key
X time
Y1 signal intensities
Y2 temperature in °C
Figure 6 — Difficulties in separating ROC and TIC peaks
600 900A
5.6 Interferences due to premature releases and deflagrations

During the combustion of reactive samples, deflagration or carbon black (soot) formation can occur, and

it is also known that the remaining carbon might undergo premature ignition resulting in superposition

(overlapping) and misidentification. This can be prevented by covering the sample with a layer of inert

material, e.g. quartz sand or aluminium oxide.
5.7 Interferences due to catalytic active metal contents in samples

In waste samples from high temperature treatment with catalytic active metal contents can lead to

overestimated TOC values.
400
6 Reagents
6.1 General

All reagents used shall be at least of analytical grade and shall be suitable for their specific purposes.

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oSIST prEN 17505:2022
prEN 17505:2022 (E)
6.2 Oxygen, O2, purity φ > 99.7 % or synthetic air, purity φ > 99.7 %.

6.3 Inert gas, e.g. nitrogen, N , (only for the alternative procedure specified in 8.6).

6.4 Calcium carbonate, CaCO3.
6.5 Activated carbon
NOTE Activated carbon does not contain 100 % elemental carbon.
6.6 Microcrystalline cellulose
6.7 Aluminium oxide, Al2O3.
6.8 Graphite
NOTE Graphite does not contain 100 % elemental carbon.
6.9 Standards for system control

For a control standard for method A (8.5) containing 2 % TOC 2 % ROC and 2 % TIC , carefully

400 600 900A

homogenize appropriate amounts of microcrystalline cellulose (6.6), CaCO3 (6.4), activated carbon (6.5)

O (6.7). First comminute the activated carbon (6.5) and Al O (6.7) in a suitable device. Then add

and Al2 3 2 3

the microcrystalline cellulose (6.6) and CaCO (6.4) and mix it. In preparing this standard, appropriate

homogenization equipment (7.1) should be used. The standard should be stored in a glass vessel at a dry

place. The stability of the standard should be checked in regular intervals by means of a TC analysis.

EXAMPLE For 10 g of the control standard, carefully homogenize 0,45 g microcrystalline cellulose (6.6), 1,67 g

CaCO3 (6.4), 0,22 g activated carbon (6.5; carbon content 90 % C) and 7,66 g Al2O3 (6.7). First comminute the

activated carbon (6.5) and Al2O3 (6.7) in a suitable device. Then add the microcrystalline cellulose (6.6) and

CaCO (6.4) and mix it. The activated carbon does not contain 100 % elemental carbon. The standard prepared as

above contains 2 % TOC400, 2 % ROC600 and 2 % TIC900A.

Depending on matrices of the measured samples in the lab or guidance of the manufacturer of the

analyser other certified system control standards also with different carbon contents can be used. For

system check every carbon fraction (TOC , ROC , TIC ) shall be part of this mixture. These mixtures

400 600 900A
shall fulfil the quality requirements in Chapter 9.2.

For a control standard for method B (8.6) containing 2 % TOC , 2 % ROC and 2 % TIC , carefully

400 900 900B

homogenize appropriate amounts of microcrystalline cellulose (6.6), CaCO (6.4), graphite (6.8) and Al O

3 2 3

(6.7). First comminute the graphite (6.8) and Al O (6.7) in a suitable device. Then add the

2 3

microcrystalline cellulose (6.6) and CaCO (6.4) and mix it. In preparing this standard, appropriate

homogenization equipment (7.1) should be used. The standard should be stored in a glass vessel at a dry

place. The stability of the standard should be checked in regular intervals by means of a TC analysis.

EXAMPLE For 10 g of the control standard, carefully homogenize 0,45 g microcrystalline cellulose (6.6), 1,67 g

CaCO (6.4), 0,206 g graphite (6.8; carbon content 97 % C) and 7,674 g Al O (6.7). First comminute the graphite

3 2 3

(6.8) and Al O (6.7) in a suitable device. Then add the microcrystalline cellulose (6.6) and CaCO (6.4) and mix it.

2 3 3

The graphite does not contain 100 % elemental carbon. The standard prepared as above contains 2 % TOC400, 2 %

and 2 % TIC .
ROC900 900B

Depending on matrices of the measured samples in the lab or guidance of the manufacturer of the

analyser other certified system control standards also with different carbon contents can be used. For

system check every carbon fraction (TOC , ROC , TIC ) shall be part of this mixture. These mixtures

400 900 900B
shall fulfil the quality requirements in Chapter 9.2.
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oSIST prEN 17505:2022
prEN 17505:2022 (E)
7 Apparatus
7.1 Homogenization equipment, e.g. mixer, stirrer, grinders, mills.
7.2 Analytical balance, (accurate to at least 0,5 % of the test portion weight).
7.3 Equipment for determining different carbon types in solids
Equipment which consists of:

a) a sample zone which fulfils the requirements for the temperature program as specified in 8.5;

b) a post-combustion zone which, depending on the catalyst or filler material used, can be heated to a

temperature of at least 850 °C;

c) a section to process the measuring gas (e.g. drying, absorption of corrosive components);

d) a suitable detector unit for the time-resolved measurement of the CO contained in the measuring gas

(e.g. an IR detector).
8 Procedure
8.1 General

This standard does not give any recommendations regarding the type and operation of the apparatus to

be used. Operational data should be chosen and checked in accordance with the information provided by

the equipment manufacturers.

The weighed portion of the test sample should be as large as possible and shall be chosen so that the

liberated quantity of carbon dioxide lies within the calibration range.
8.2 Sample preparation and processing

Pre-treat the sample according to EN 16179 or EN 15002, if not otherwise specified.

If samples contain – depending on the accuracy of the method – negligible amounts of volatile compounds

except water, the samples may be dried.
NOTE The soil drying method can affect the result weighed portion

The processed sample (particle size < 250 µm) is weighed into a suitable sample carrier (boat or crucible,

e.g. made of stainless steel, nickel, ceramics, silica glass or platinum). For many measuring instruments,

the weighed portion depends on the carbon content; a weighed portion of at least 20 mg is recommended.

It shall be ensured that the carbon content is within the calibration range.
8.3 Calibration

The measuring instrument shall be calibrated according to the manufacturer’s instructions.

8.4 Measurement (Oxidative method A)

During the measurement, the carbon contained in the sample is released in an oxidizing atmosphere in

the temperature range from 150 °C to 900 °C and subsequently converted to CO in the post-combustion

process. Detection is accomplished by e.g. infrared detection or CO sensitive sensors.

The temperature program for the sample zone starts at a temperature of 150 °C and follows a linear

increase with holding times according to Table 2. Figure 7 shows an example of the separation of the

bond types of carbon under oxidative conditions.
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oSIST prEN 17505:2022
prEN 17505:2022 (E)
Table 2 — Temperature program for sample zone
Parameter Initial Rate of Final Minimum
Carrier gas
temperature temperature temperature holding time
(examples)
increase
°C °C/min °C s
TOC 150 70 400 120 O
400
ROC 400 70 600 100 O
600
TIC 600 70 900 100 O
900A

If only TOC is of interest it is possible to stop the run after the first heating rate at the 1 signal

400
minimum at (400 ± 20) °C and a minimum holding time of 120 s.

NOTE If the method is stopped at (400 ± 20) °C it might be useful to start a post heating process for cleaning

the system and to minimize the contamination risk.
Key
X time in s 1 TOC
400
Y1 signal intensities (according Table 2) 2 ROC
600
Y2 temperature in °C 3 TOC900A

Figure 7 — Example diagram for the separation of carbon types under oxidative conditions

For heterogenous materials as waste e.g. foundry sand, mining waste or urban soils samples it is

necessary to measure the TOC at least twice. The respective difference of the two values shall be ≤ 10 %

400

of the mean. If this is not the case, at least one further determination is necessary; then the coefficient of

variation shall be ≤ 10 %. If this is not the case, the relevant coefficient of variation shall be reported

together with the result or all results of the different determination shall be reported.

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8.5 Measurement (Mixed oxidative/non-oxidative method B)

As an alternative to the described oxidative method, the combination of oxidizing and non-oxidizing

carrier gases in one course of analysis can be applied to separate the bond types of carbon. Here, the

. Subsequently, the

sample is first converted in the presence of oxygen at 400 °C to determine TOC400

carrier gas is switched to an inert gas (Clause 6.3) while simultaneously increasing the temperature to

900 °C. Under these conditions, the TIC contained in the sample is converted to CO . In a 3rd step, the

carrier gas is switched back to O while maintaining the temperature of 900 °C. This leads to the oxidation

of the residual oxidizable carbon (ROC ) still contained in the sample to CO . The temperature program

900 2

is run according to Table 3. Figure 8 shows an example of the separation of the bond types of carbon with

alternative carrier gas.
Table 3 — Temperature program for sample zone
Rate of
Initial Final Minimum Carrier gas
Parameter temperature
temperature temperature Holding time (examples)
increase
°C °C/min °C s
TOC 150 70 400 120
400 2
TIC 400 > 70 900 250
900B
ROC 900 — 900 100
900

If only TOC is of interest it is possible to stop the run after the first heating rate at the 1 signal

400
minimum at (400 ± 20) °C and a minimum holding time of 120 s.

NOTE If the method is stopped at (400 ± 20) °C it might be useful to start a post heating process for cleaning

the system and to minimize the contamination risk.
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prEN 17505:2022
...

SLOVENSKI STANDARD
oSIST prEN 17505:2020
01-april-2020
Karakterizacija tal in odpadkov - Diferenciacija celotnega ogljika (TOC400, ROC,
TIC900) v odvisnosti od temperature

Soil and waste characterization - Temperature dependent differentiation of total carbon

(TOC400, ROC, TIC900)
Boden- und Abfallbeschaffenheit - Temperaturabhängige Unterscheidung von
Gesamtkohlenstoff (TOC400, ROC, TIC900)
Ta slovenski standard je istoveten z: prEN 17505
ICS:
13.030.10 Trdni odpadki Solid wastes
13.080.10 Kemijske značilnosti tal Chemical characteristics of
soils
oSIST prEN 17505:2020 en,fr,de

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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DRAFT
EUROPEAN STANDARD
prEN 17505
NORME EUROPÉENNE
EUROPÄISCHE NORM
April 2020
ICS 13.030.10; 13.080.10
English Version
Soil and waste characterization - Temperature dependent
differentiation of total carbon (TOC400, ROC, TIC900)
Boden- und Abfallbeschaffenheit -
Temperaturabhängige Unterscheidung von
Gesamtkohlenstoff (TOC400, ROC, TIC900)

This draft European Standard is submitted to CEN members for enquiry. It has been drawn up by the Technical Committee

CEN/TC 444.

If this draft becomes a European Standard, 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.

This draft European Standard was established by CEN 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-CENELEC

Management Centre has the same status as the official versions.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,

Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway,

Poland, Portugal, Republic of North Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and

United Kingdom.

Recipients of this draft are invited to submit, with their comments, notification of any relevant patent rights of which they are

aware and to provide supporting documentation.

Warning : This document is not a European Standard. It is distributed for review and comments. It is subject to change without

notice and shall not be referred to as a European Standard.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels

© 2020 CEN All rights of exploitation in any form and by any means reserved Ref. No. prEN 17505:2020 E

worldwide for CEN national Members.
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Contents Page

European foreword ....................................................................................................................................................... 3

Introduction .................................................................................................................................................................... 4

1 Scope .................................................................................................................................................................... 5

2 Normative references .................................................................................................................................... 5

3 Terms and definitions ................................................................................................................................... 5

4 Principle ............................................................................................................................................................. 6

5 Interferences .................................................................................................................................................... 6

5.1 Interference due to carbides ....................................................................................................................... 6

5.2 Interference due to sulfur and nitrogen compounds ......................................................................... 6

5.3 Interference due to carbonates .................................................................................................................. 6

5.4 Peak does not reach the baseline .............................................................................................................. 8

5.5 Difficulties in separating ROC peak and TIC peak .................................................................... 10

900

5.6 Interferences due to premature releases and deflagrations ....................................................... 10

6 Reagents .......................................................................................................................................................... 11

6.1 General ............................................................................................................................................................. 11

6.2 Oxygen, O , purity > 99,7 % (V/V) or synthetic air, purity > 99,7 %. ........................................ 11

6.3 Inert gas, e.g. nitrogen, N , (only for the alternative procedure specified in Annex B). .... 11

6.4 Calcium carbonate, CaCO . ....................................................................................................................... 11

6.5 Activated carbon........................................................................................................................................... 11

6.6 Microcrystalline cellulose ......................................................................................................................... 11

6.7 Aluminium oxide, Al O . ........................................................................................................................... 11

2 3

6.8 Standard for system control ..................................................................................................................... 11

7 Apparatus ........................................................................................................................................................ 11

7.1 Homogenization equipment, e.g. mixer, stirrer, grinders, mills. ................................................ 11

7.2 Analytical balance, (accurate to at least 0,5 % of the test portion weight). ............................ 11

7.3 Equipment for determining different carbon types in solids, which consists of: ................. 11

8 Procedure........................................................................................................................................................ 12

8.1 General ............................................................................................................................................................. 12

8.2 Sample preparation and processing ..................................................................................................... 12

8.3 Weighed portion ........................................................................................................................................... 12

8.4 Calibration ...................................................................................................................................................... 12

8.5 Measurement ................................................................................................................................................. 12

9 Evaluation ....................................................................................................................................................... 13

9.1 General ............................................................................................................................................................. 13

9.2 Control measurements ............................................................................................................................... 14

10 Expression of results ................................................................................................................................... 14

11 Test report ...................................................................................................................................................... 15

Annex A (informative) Performance characteristics ................................................................................... 16

Annex B (informative) Alternative carrier gases........................................................................................... 18

Bibliography ................................................................................................................................................................. 20

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European foreword

This document (prEN 17505:2020) has been prepared by Technical Committee CEN/TC 444 “Test

methods for environmental characterization”, the secretariat of which is held by NEN.

This document is currently submitted to the CEN Enquiry.
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Introduction

Carbon occurs in soils and materials similar to soil in a variety of compounds and forms. When

determining carbon in soils or soil-like materials, an overall determination of the different mass fractions

is most feasible. The summarized declaration of carbon is yet done by differentiating organic and

inorganic carbon (EN 15936, ISO 10694). In the proportion classified as “organic carbon”, a fraction of

very stable highly aromatic and highly condensed carbon compounds can be present, sometimes in

significant mass fractions. Since this black (pyrogenic) carbon is only very slowly decomposed and

released, its environmental relevance has to be differently evaluated than the proportions of organic

carbon which are faster chemical-biologically decomposed. The environmental relevance is estimated if

e.g. the suitability of soils and soil-like materials for disposal in landfill is assessed. For a differentiated

assessment, a separate declaration of the different mass fractions of organic, black (pyrogenic) and

inorganic carbon is necessary. Using the specified temperature-gradient method and utilizing the

combustion characteristic(s), the various bond types of carbon in soil and soil-like materials can be

differentiated.

In respect of the hazard potential, the content of solely organically bonded carbon in solids determined

with the described method can be important for disposal and/or recycling.

The method has been validated with the materials listed in Table 1, see also Annex A.

Table 1 — Materials used for validation
Material type Materials used for validation
soils from natural material mineral soils
soil with anthropogenic admixtures
tailing material (tailings) tailing material from coal mining
sludge dredged sludge
sediment sediment
waste waste incineration ash
foundry sands
recycling material
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1 Scope

This document specifies a method for the differentiated determination of the organic carbon content

(TOC ) which is released at temperatures up to 400 °C, the residual oxidizable carbon (ROC) (including

400

e.g. lignite (brown coal), hard coal, charcoal, black carbon, soot) and the inorganic carbon (TIC ) which

900
is released at temperatures up to 900 °C.

The basis is the dry combustion to CO in a in the presence of oxygen using temperatures ranging from

150 °C to 900 °C in dry solid samples of soil, soil with anthropogenic admixtures and solid waste (see

Table 1) with carbon contents of more than 1 g per kg (0,1 % C) (per carbon type in the test portion).

Alternatively, the method specified in Annex B may be applied.
2 Normative references
There are no normative references in this document.
3 Terms and definitions
No terms and definitions are listed in this document.

ISO and IEC maintain terminological databases for use in standardization at the following addresses:

— ISO Online browsing platform: available at http://www.iso.org/obp
— IEC Electropedia: available at http://www.electropedia.org/
3.1
total organic carbon which is released up to 400° C
TOC
400

carbon which is determined in the range between 150 °C to the 1st signal minimum at (400 ± 20) °C, in

the case of dry combustion in the presence of oxygen

Note 1 to entry: The TOC400 corresponds to the content of organically bonded carbon excluding ROC. This

carbon fraction is important regarding the hazard potential for disposal and/or recycling.

3.2
residual oxidizable carbon
ROC

carbon which is determined between the signal minima at (400 ± 20) °C and at (600 ± 20) °C, in the case

of dry combustion in the presence of oxygen

Note 1 to entry: When using the alternative normative method according to Annex B, then the ROC is defined as

the carbon determined during dry combustion in a current of oxygen after the TIC measurement at

900
(900 ± 20) °C.
Note 2 to entry: The black carbon is part of the ROC.
3.3
total inorganic carbon which is released up to 900° C
TIC
900

quantity of carbon present in the sample in the form of organic (TOC ), inorganic (TIC ) and black

400 900
carbon (ROC)
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3.4
total carbon

quantity of carbon present in the sample in the form of organic (TOC ), inorganic (TIC ) and black

400 900
carbon (ROC)
4 Principle

The determination of organic carbon (TOC ), residual oxidizable carbon (ROC) and inorganic carbon

400

(TIC ) in solid is effected by means of thermal oxidation or decomposition of the different bond types

900

of carbon at different temperatures to CO , if necessary, supported by changing between oxidizing and

non-oxidizing carrier gases.

The application of the gradient method with a suitable temperature program allows the determination of

organic carbon (TOC ), residual oxidizable carbon (ROC) and inorganic carbon (TIC ) and the

400 900
calculation of total carbon (TC) by totalling these contents.

The final analysis of CO can be performed with different methods, e.g. by means of infrared detection or

CO sensitive sensors.
5 Interferences
5.1 Interference due to carbides
Several carbides can interfere with this method.
5.2 Interference due to sulfur and nitrogen compounds

Depending on the measuring technique used, high contents of sulfur or nitrogen compounds can result

in overestimations or underestimations. This can be controlled by means of selected standard samples

(e.g. potassium sulfate, potassium nitrate). Furthermore, the information provided by the equipment

manufacturer shall be considered.
5.3 Interference due to carbonates

The thermal stability of carbonates exhibits a great bandwidth (for examples see Figures 1, 2 and 3).

Therefore, carbonates might be detected in both the TOC peak range and the ROC range. In the

400

presence of certain carbonates or carbonate mixtures which decompose at low temperature ranges, the

identification of the TIC peak is sometimes difficult or impossible. Alternatively, the impact of

900
carbonates on the TOC analysis can be determined by stripping with acid.
400

For samples containing the more thermally stable carbonates, e.g. barium carbonate, the liberation of

carbon dioxide can be improved by increasing temperature or using additives such as tungsten oxide.

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Key
X time
Y1 signal intensities
Y2 temperature in °C
Figure 1 — Example diagram FeCO
Key
X time
Y1 signal intensities
Y2 temperature in °C
Figure 2 — Example diagram MnCO ·fH O
3 2
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Key
X time
Y1 signal intensities
Y2 temperature in °C
Figure 3 — Example diagram PbCO
5.4 Peak does not reach the baseline
...

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