prEN 17505
(Main)Soil and waste characterization - Temperature dependent differentiation of total carbon (TOC400, ROC, TIC900)
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
General Information
Standards Content (Sample)
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
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.---------------------- Page: 3 ----------------------
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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
600 900A5.6 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 36.8 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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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.---------------------- Page: 5 ----------------------
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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 validationMaterial 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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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
400e.g. lignite (brown coal), hard coal, charcoal, black carbon, soot) and the inorganic carbon (TIC ) which
900is 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 oxygenNote 1 to entry: TOC is the carbon black free portion of TOC measured e.g. by ISO 10694 or EN 15936. This
400carbon fraction is important regarding the hazard potential for disposal and/or recycling.
3.2residual 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)
3.3residual 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
900Aquantity 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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3.5
total inorganic carbon which is released up to 900 °C during non-oxidizing conditions - TIC
900Bquantity 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
900B8.5)
3.6
total carbon
quantity of carbon present in the sample representing the sum of organic (TOC ), inorganic (TIC and
400 900ATIC ) 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 900inorganic carbon (TIC and TIC ) in solids is affected by means of thermal oxidation or
900A 900Bdecomposition 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 900calculation 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 600presence 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
900Acarbonates on the TOC analysis can be determined by stripping with acid (e.g. Scheibler method
400EN 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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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
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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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
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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 900Apeak (see Figure 6), the influence of carbonates on the ROC analysis or of ROC on the TIC
600 600 900Ameasurement 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
900Aequipment 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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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 900Ahomogenize 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 3the 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 900Ashall 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 900Bhomogenize 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 3microcrystalline 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 3The 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 900Bshall fulfil the quality requirements in Chapter 9.2.
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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.---------------------- Page: 14 ----------------------
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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
400minimum 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 %
400of 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, thesample 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 2is 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
400minimum 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.---------------------- Page: 16 ----------------------
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...
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.
---------------------- Page: 1 ----------------------oSIST prEN 17505:2020
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oSIST prEN 17505:2020
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
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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
9005.6 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 36.8 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.
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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 validationMaterial 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
400e.g. lignite (brown coal), hard coal, charcoal, black carbon, soot) and the inorganic carbon (TIC ) which
900is 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 oxygenNote 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.
3.2residual 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 oxygenNote 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 900carbon (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 900carbon (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
900of 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 900calculation 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
400presence 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
900carbonates 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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