CEN/TS 13649:2014
(Main)Stationary source emissions - Determination of the mass concentration of individual gaseous organic compounds - Sorptive sampling method followed by solvent extraction or thermal desorption
Stationary source emissions - Determination of the mass concentration of individual gaseous organic compounds - Sorptive sampling method followed by solvent extraction or thermal desorption
This Technical Specification specifies procedures for the sampling, preparation and analysis of individual volatile organic compounds (VOCs) in waste gas, such as those arising from solvent using processes. Sampling occurs by adsorption on sorbents, preparation by solvent extraction or thermodesorption and analysis by gas chromatography.
Examples of individual VOC are given in relevant industry sector BAT Reference documents (BREFs).
The results obtained are expressed as the mass concentration (mg/m3) of the individual gaseous organic compounds. This document is suitable for measuring individual VOCs whose ranges vary depending on compound and test method, refer to Annex B and C.
This Technical Specification may be used to meet the monitoring requirements of the Industrial Emission Directive (IED) and associated supporting documents.
This Technical Specification is not suitable for measuring total organic carbon (TOC). For the measurement of the mass concentration of total organic carbon then EN 12619 [3] is applicable.
Emissionen aus stationären Quellen - Bestimmung der Massenkonzentration von gasförmigen organischen Einzelverbindungen - Sorptive Probenahme und Lösemittelextraktion oder thermische Desorption
Diese Technische Spezifikation legt die Durchführung der Probenahme von einzelnen flüchtigen organischen Verbindungen (VOCs) aus Abgasen, sowie die Aufbereitung und Analyse der Proben fest. Quelle der Abgase können z. B. Prozesse sein, bei denen Lösemittel eingesetzt werden.
Beispiele von einzelnen VOC werden in den relevanten branchenspezifischen BAT-Referenzdokumenten (BREFs) genannt. Die in diesem Dokument beschriebenen Verfahren sind auf gaschromatographisch bestimmbare Verbindungen beschränkt.
Die Messergebnisse werden als Massenkonzentration (mg/m3) der gasförmigen organischen Einzelverbindungen angegeben. Die Messbereiche der VOCs, für die dieses Dokument anwendbar ist, variieren je nach Verbindung und Messverfahren (siehe Anhänge B und C).
Diese Technische Spezifikation kann angewendet werden, um die Anforderungen der Richtlinie über Industrieemissionen (IED) und zugehöriger Dokumente zu erfüllen.
Diese Technische Spezifikation ist nicht für die Messung des gesamten organisch gebundenen Kohlenstoffs (TOC) geeignet. Hierfür ist EN 12619 anzuwenden.
Emissions de sources fixes - Détermination de la concentration massique en composés organiques gazeux individuels - Échantillonnage par adsorption et extraction par solvant ou thermodésorption
La présente Norme européenne spécifie des modes opératoires pour l'échantillonnage, la préparation et l'analyse de composés organiques volatils individuels (COV) dans les effluents gazeux, tels que ceux issus des procédés utilisant des solvants. Elle constitue une méthode de référence.
Les résultats obtenus en utilisant la présente norme sont exprimés en concentration massique (mg/m3) de composés organiques gazeux individuels. La présente norme convient au mesurage des COV individuels dont la concentration avoisine les 0,5 mg/m3 (méthodes par adsorption sur/extraction par solvant) ou les 0,005 mg/m3 (méthodes de thermodésorption). La gamme supérieure varie selon la méthode sélectionnée.
Une autre méthode peut être utilisée à condition que l'utilisateur puisse démontrer l'équivalence de cette méthode, conformément à la Spécification technique CEN/TS 14793, à la satisfaction de l'organisme d'accréditation national ou de la loi en vigueur.
La présente norme peut être utilisée pour répondre aux exigences de surveillance des Directives CE applicables.
La présente norme peut être utilisée pour d'autres composés organiques, sous réserve de validation.
La présente norme ne convient pas au mesurage du carbone organique total (COT). Pour le mesurage de la concentration massique du carbone organique total, l'EN 12619 est applicable.
Emisije nepremičnih virov - Določevanje masne koncentracije posameznih organskih spojin v plinasti fazi - Vzorčenje z adsorpcijo in ekstrakcija s topilom ali termična desorpcija
Ta evropski standard določa postopke za vzorčenje, pripravo in analizo posameznih hlapnih organskih spojin (VOC) v odpadnem plinu, kot so spojine, ki nastanejo pri postopkih, pri katerih se uporablja topilo. To je referenčna metoda.
Rezultati, pridobljeni z uporabo tega standarda, so izraženi kot masna koncentracija (mg/m³) posameznih organskih spojin v plinasti fazi. Ta standard je primeren za merjenje posameznih hlapnih organskih spojin v koncentraciji od približno 0,5 mg/m³ (ekstrakcija z adsorbentom v trdni fazi/ekstrakcija s topilom) ali 0,005 mg/m3 (termična desorpcija). Zgornja meja se določi z izbrano metodo.
Alternativna metoda se lahko uporabi, če lahko uporabnik dokaže njeno enakovrednost s to metodo v skladu s tehnično specifikacijo CEN/TS 14793, ki jo priznava tudi nacionalni akreditacijski organ ali zakonodaja.
Ta standard se lahko uporablja za izpolnitev zahtev glede nadzora iz veljavnih direktiv ES.
Ta standard se lahko uporablja za druge organske spojine, kadar je to potrjeno.
Ta standard ni primeren za merjenje skupnega organskega ogljika (TOC). Za merjenje masne koncentracije skupnega organskega ogljika se uporablja standard EN 12619.
General Information
Relations
Overview
CEN/TS 13649:2014 specifies procedures for the sampling, preparation and analysis of individual volatile organic compounds (VOCs) in stationary source waste gases. The standard covers sorptive sampling (adsorption on sorbents), followed by solvent extraction or thermal desorption, with final determination by gas chromatography (GC). Results are reported as mass concentration (mg/m3) of individual gaseous organic compounds. The Technical Specification is intended to support monitoring requirements under the Industrial Emissions Directive (IED) and provides practical guidance for solvent‑using industrial processes.
Key topics and technical requirements
- Three-step measurement principle: sampling → desorption/extraction → GC analysis.
- Sorbent tube types:
- Activated carbon (charcoal) tubes for solvent extraction.
- Stainless steel / inert-coated tubes packed with TD‑compatible sorbents for thermal desorption.
- Desorption methods:
- Solvent extraction of activated carbon.
- Thermal desorption of TD‑compatible sorbents with direct GC transfer.
- Sampling system and conditions: pumped sampling from stack/ducts; use of dilution sampling when condensation risk exists; prohibition of upstream drying agents that may cause VOC losses.
- Quality control elements: blanks (field, analytical, solvent), calibration procedures, determination of desorption efficiency, storage/transport instructions, leakage control, and uncertainty estimation.
- Documentation and validation: decision tree for selecting sampling procedure, alignment of sampling strategy with EN 15259, and informative Annexes (e.g., solvent extraction details, thermal desorption guidance, method validation).
- Scope limits: suitable for speciated VOCs (see Annex B & C for ranges); not suitable for total organic carbon (TOC) - EN 12619 applies for TOC.
Applications
- Compliance monitoring of VOC emissions from solvent‑using processes (paints, coatings, printing, chemical manufacturing, etc.).
- Emissions characterization and speciation for permit reporting, BAT assessments, and regulatory compliance under the IED.
- Method selection and validation for environmental laboratories performing stack gas VOC analysis.
Who uses this standard
- Environmental and emissions monitoring laboratories
- Plant emissions engineers and process operators
- Regulatory bodies and compliance officers
- Consultants performing air quality assessments and BAT studies
Related standards
- EN 15259 - measurement site/plan requirements (aligned sampling strategy)
- EN ISO 16017-1 - sorbent tube / thermal desorption pumped sampling
- EN ISO 14956 - assessment of measurement procedure suitability (uncertainty)
- EN 12619 - measurement of mass concentration of total organic carbon (TOC)
Keywords: CEN/TS 13649, VOC monitoring, sorptive sampling, thermal desorption, solvent extraction, gas chromatography, stationary source emissions, Industrial Emissions Directive.
Standards Content (Sample)
SLOVENSKI STANDARD
01-februar-2015
1DGRPHãþD
SIST EN 13649:2002
(PLVLMHQHSUHPLþQLKYLURY'RORþHYDQMHPDVQHNRQFHQWUDFLMHSRVDPH]QLK
RUJDQVNLKVSRMLQYSOLQDVWLID]L9]RUþHQMH]DGVRUSFLMRLQHNVWUDNFLMDVWRSLORPDOL
WHUPLþQDGHVRUSFLMD
Stationary source emissions - Determination of the mass concentration of individual
gaseous organic compounds - Sorptive sampling method followed by solvent extraction
or thermal desorption
Emissionen aus stationären Quellen - Bestimmung der Massenkonzentration von
gasförmigen organischen Einzelverbindungen - Sorptive Probennahme mit
Lösemittelextraktion oder thermischer Desorption
Emissions de sources fixes - Détermination de la concentration massique en composés
organiques gazeux individuels - Echantillonnage par adsorption et désorption des
solvants ou désorption thermique
Ta slovenski standard je istoveten z: CEN/TS 13649:2014
ICS:
13.040.40 (PLVLMHQHSUHPLþQLKYLURY Stationary source emissions
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
TECHNICAL SPECIFICATION
CEN/TS 13649
SPÉCIFICATION TECHNIQUE
TECHNISCHE SPEZIFIKATION
December 2014
ICS 13.040.40 Supersedes EN 13649:2001
English Version
Stationary source emissions - Determination of the mass
concentration of individual gaseous organic compounds -
Sorptive sampling method followed by solvent extraction or
thermal desorption
Emissions de sources fixes - Détermination de la Emissionen aus stationären Quellen - Bestimmung der
concentration massique en composés organiques gazeux Massenkonzentration von gasförmigen organischen
individuels - Échantillonnage par adsorption et extraction Einzelverbindungen - Sorptive Probenahme und
par solvant ou thermodésorption Lösemittelextraktion oder thermische Desorption
This Technical Specification (CEN/TS) was approved by CEN on 25 August 2014 for provisional application.
The period of validity of this CEN/TS is limited initially to three years. After two years the members of CEN will be requested to submit their
comments, particularly on the question whether the CEN/TS can be converted into a European Standard.
CEN members are required to announce the existence of this CEN/TS in the same way as for an EN and to make the CEN/TS available
promptly at national level in an appropriate form. It is permissible to keep conflicting national standards in force (in parallel to the CEN/TS)
until the final decision about the possible conversion of the CEN/TS into an EN is reached.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United
Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2014 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TS 13649:2014 E
worldwide for CEN national Members.
Contents Page
Foreword .4
1 Scope .5
2 Normative references .5
3 Terms and definitions .5
4 Principle .6
5 Apparatus and materials .6
5.1 Method of measurement .6
5.2 Sampling system .8
5.3 Sampling tubes .8
5.3.1 Sampling tubes for solvent extraction .8
5.3.2 Sampling tubes for thermal desorption.8
5.4 Pumps and other devices for sampling .8
5.5 Gas volume meter .9
5.6 Analytical reagents .9
5.6.1 General .9
5.6.2 Extraction solvent (for solvent extraction) .9
5.6.3 Reference materials for calibration of the analytical procedure .9
5.7 Analytical apparatus . 10
5.7.1 Capillary gas chromatograph (GC) . 10
5.7.2 Thermal desorber (for thermal desorption) . 10
6 Sampling procedure . 10
6.1 General . 10
6.2 Sampling conditions . 10
6.3 Measurement of waste gas sample volume . 11
6.4 Control of leakage. 11
6.5 Handling, storage, transport of sampled tubes . 11
6.5.1 General . 11
6.5.2 Activated carbon (charcoal) tubes . 11
6.5.3 Thermal desorption tubes . 12
6.6 Blanks . 12
6.6.1 Field blanks . 12
6.6.2 Analytical (laboratory) blanks . 12
6.6.3 Solvent blank . 12
7 Analytical procedure . 12
7.1 Calibration of the GC analysis . 12
7.1.1 GC calibration for analysis of solvent extracts . 12
7.1.2 Calibration for thermal desorption analysis . 13
7.2 Sample preparation (desorption/extraction) . 13
7.2.1 Solvent desorption . 13
7.2.2 Thermal desorption . 14
7.3 Analysis . 14
7.3.1 GC analysis of extract from activated carbon tubes. 14
7.3.2 Thermal desorption / GC analysis of sorbent tubes . 14
7.4 Quantification of individual organic compound concentrations . 15
8 Calculation of results . 16
8.1 Concentration . 16
8.2 Uncertainty . 16
9 Quality control . 16
9.1 General . 16
9.2 Performance requirements . 17
9.2.1 Sampling. 17
9.2.2 Analytical . 17
10 Report . 18
Annex A (normative) Sample trains . 19
Annex B (informative) Solvent extraction of activated charcoal tubes . 23
Annex C (informative) Additional information on flue gas sampling using thermal desorption
tubes . 24
Annex D (informative) Validation of monitoring methods for speciated organic substances in
stack gas . 27
Annex E (informative) Safety measures . 45
Bibliography . 46
Foreword
This document (CEN/TS 13649:2014) has been prepared by Technical Committee CEN/TC 264 “Air quality”,
the secretariat of which is held by DIN.
Attention is drawn to the possibility that some of the elements of this document may be the subject of patent
rights. CEN [and/or CENELEC] shall not be held responsible for identifying any or all such patent rights.
This document supersedes EN 13649:2001.
Significant technical changes between this Technical Specification and the previous edition of EN 13649 are:
a) the status of the document has been changed from European Standard (EN) to Technical Specification
(TS);
b) the scope has been clarified regarding the use of the TS and its applicability;
c) a decision tree for the determination of the sampling procedure has been included;
d) the sampling strategy has been aligned with EN 15259;
e) the thermal desorption technique has been added;
f) comprehensive information on the validation of monitoring methods for speciated organic substances in
stack gas is given.
According to the CEN-CENELEC Internal Regulations, the national standards organizations of the following
countries are bound to announce this Technical Specification: Austria, Belgium, Bulgaria, Croatia, Cyprus,
Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany,
Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland,
Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom.
1 Scope
This Technical Specification specifies procedures for the sampling, preparation and analysis of individual
volatile organic compounds (VOCs) in waste gas, such as those arising from solvent using processes.
Sampling occurs by adsorption on sorbents, preparation by solvent extraction or thermodesorption and
analysis by gas chromatography.
Examples of individual VOC are given in relevant industry sector BAT Reference documents (BREFs).
The results obtained are expressed as the mass concentration (mg/m ) of the individual gaseous organic
compounds. This document is suitable for measuring individual VOCs whose ranges vary depending on
compound and test method, refer to Annex B and C.
This Technical Specification may be used to meet the monitoring requirements of the Industrial Emission
Directive (IED) and associated supporting documents.
This Technical Specification is not suitable for measuring total organic carbon (TOC). For the measurement of
the mass concentration of total organic carbon then EN 12619 [3] is applicable.
2 Normative references
The following documents, in whole or in part, are normatively referenced in this document and are
indispensable for its application. For dated references, only the edition cited applies. For undated references,
the latest edition of the referenced document (including any amendments) applies.
EN 15259, Air quality - Measurement of stationary source emissions - Requirements for measurement
sections and sites and for the measurement objective, plan and report
EN ISO 14956, Air quality - Evaluation of the suitability of a measurement procedure by comparison with a
required measurement uncertainty (ISO 14956)
EN ISO 16017-1, Indoor, ambient and workplace air - Sampling and analysis of volatile organic compounds by
sorbent tube/thermal desorption/capillary gas chromatography - Part 1: Pumped sampling (ISO 16017-1)
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1
desorption efficiency
ratio of the mass of the recovered organic material to the mass of organic material collected by the adsorbent
expressed as a percentage
3.2
sampling tube for solvent extraction
glass tube filled with activated carbon as the adsorbent
3.3
sampling tubes for thermal desorption
stainless steel, inert-coated steel or glass tube-form samplers supplied capped and packed with one or more
conditioned, thermal desorption compatible sorbents
3.4
uncertainty
parameter associated with the result of a measurement, that characterizes the dispersion of the values that
could reasonably be attributed to the measurand
[SOURCE: ISO/IEC Guide 98-3:2008 [2]]
3.5
volatile organic compound
VOC
any organic compound having at 293,15 K a vapour pressure of 0,01 kPa or more, or having a corresponding
volatility under the particular conditions of use
3.6
field blank
value determined by a specific procedure used to ensure that no significant contamination has occurred
during all steps of the measurement and to check that the operator can achieve a quantification level adapted
to the task
4 Principle
There are three steps in the measurement of individual gaseous organic compounds: sampling, desorption
and analysis.
Sampling approaches vary depending on waste gas conditions. Suitable sorbent shall be selected. This
document specifies solvent extraction or thermal desorption. Analysis is by gas chromatography.
Other methods may also be applicable e.g. canister, as an alternative to sorbent sampling for very volatile
compounds, or condensate trap (catchpot) sampling systems, as an alternative to dilution sampling, providing
their suitability can be demonstrated, e.g. according to CEN/TS 14793 [1].
Figure 1 shows the decision tree for determining the sampling procedure.
5 Apparatus and materials
5.1 Method of measurement
The sample gas is extracted from the waste gas exhaust duct via a sampling system and onto a solid sorbent
tube using a pump. The solid sorbent tube is then solvent extracted or thermally desorbed and the compounds
are determined by gas chromatography.
Many of the solvent using processes covered by the Industrial Emissions Directive produce waste gases
which do not have a high water content. This document requires the use of a dilution sampling system when
the concentration of water or solvent is high enough to cause the risk of condensation.
NOTE The limit values of EU Directives are expressed in mg/m , on a wet basis, for non-combustion process and on
a dry basis, for combustion processes, at the reference conditions of 273 K and 101,3 kPa.
Figure 1 — Decision tree for determination of sampling procedure
Liquid water interferes with the sorption process and shall not be allowed to reach the sorbent material
(activated carbon or thermal desorption compatible sorbents). There shall be no visible condensation within
the tube.
Drying tubes, e.g. sodium sulfate, shall not be used upstream of the sorbent because of the risk of VOC
losses.
Sorbent sampling methods (activated carbon or thermal desorption-compatible) are only compatible with the
vapour-phase fraction of semi-volatile compounds. Any particulates in the sample gas shall be entrained on
filters before the sample is allowed to reach the sorbent bed.
5.2 Sampling system
The set-up of a suitable sampling system is shown in Annex A.
The sampling system shall be made of materials which are chemically and physically inert to the constituents
of the gaseous effluent. Glass, PTFE and polypropylene fluoride or any other material for which it has been
shown that they do not absorb or react with compounds present in the sample gas at the temperature
considered, are suitable. To avoid contamination from particulate, a dust filter shall be used. This should be
heated if necessary, depending on application.
5.3 Sampling tubes
5.3.1 Sampling tubes for solvent extraction
The sorbent tube, filled with activated carbon as the adsorbent, shall have the following characteristics:
— a main adsorbent layer containing 100 mg of activated carbon with a glass wool plug at the front of the
tube;
— a security adsorbent layer to detect breakthrough, containing 50 mg of activated carbon separated from
the front layer.
Sorbent tubes shall be used in accordance with the manufacturer’s instructions to avoid leakage and sample
loss. Open or used carbon tubes shall not be reused.
NOTE A suitable type of tubes is NIOSH type B with closed melted ends.
5.3.2 Sampling tubes for thermal desorption
Stainless steel, inert-coated steel or glass samplers supplied capped and packed with one or more
conditioned, thermal desorption compatible sorbents shall be used for organic vapour sampling and
subsequent thermal desorption analysis. See Annex C and EN ISO 16017-1 for more details. The sampling
end of an identical, secondary (back-up) tube can be connected to the outlet of the primary sampling tube as a
check on breakthrough. See 6.3 and Annex C for more information. Unions for connecting the two tubes in
series shall comprise inert materials such as stainless steel, coated stainless steel or PTFE and shall not
damage tube ends.
NOTE Stainless steel (or inert-coated steel) compression couplings fitted with combined PTFE ferrules have been
found to be effective for connecting sample tubes together in series.
Thermal desorption sampling tubes can be re-used many times (typically > 100 thermal cycles).
Conditioned tubes shall be considered sufficiently clean if individual artefact masses do not exceed 10 % of
the mass retained when sampling flue gases at the lowest concentration of interest. See also 6.6.
5.4 Pumps and other devices for sampling
A sampling pump or some alternative means of pulling a controlled flow or volume of waste gas through the
sampling system and onto the sampling tube is required. The pump or alternative flow controlled sampling
system shall have an adjustable flow rate (e.g. up to 0,1 l/min for thermal desorption tubes or up to 0,5 l/min
for charcoal tubes); typical flow rate and sample volume ranges for activated carbon and thermal desorption
tubes are given in Annex B and Annex C respectively.
As thermal desorption typically offers three orders of magnitude more sensitivity than solvent extraction, it also
allows the option of collecting small sample volumes. For example, if individual organic compounds are
present above 500 µg/m , a sample volume of 100 ml is usually sufficient for thermal desorption/GC analytical
sensitivity. Such small aliquots can be accurately drawn onto the sorbent tubes using simple bellows-type
pumps or even by slowly withdrawing the plunger of a large gas syringe.
NOTE Such ‘grab’ sampling methods are only suitable for steady-state emissions. They are not suitable for time
weighted average monitoring of variable waste gas concentrations e.g. when monitoring emissions throughout the
duration of a specific batch process, unless multiple sequential emission samples are collected.
The pump or alternative sampling mechanism shall be placed downstream of the sorbent tube and coupled to
the non-sampling end of the sorbent tube or sorbent tube assembly. See Annex B and Annex C for more
information.
5.5 Gas volume meter
The volume of the gas sampled shall be measured using a calibrated device, e.g. gas volume meter or
calibrated pump, providing the volume is measured with a relative uncertainty not exceeding 5 % at actual
conditions. The uncertainty of the measurement of the temperature and the pressure, shall be less than 2,5 °C
and less than 1,0 % respectively.
5.6 Analytical reagents
5.6.1 General
Only reagents of analytical grade or better quality shall be used unless otherwise stated.
5.6.2 Extraction solvent (for solvent extraction)
Extraction solvents, for solvent extraction, shall be of chromatographic quality and free from compounds co-
eluting with the compounds of interest.
NOTE Carbon disulphide (CS ) is a suitable extraction solvent for most of the compounds likely to be encountered in
solvent using processes.
Beware of low and variable recovery rates for polar compounds. Use of additional or alternative extraction
solvents may improve recovery in these cases.
5.6.3 Reference materials for calibration of the analytical procedure
The chromatographic system shall be calibrated with those reference materials which correspond to the
compounds likely to arise in the process under investigation.
For calibrating solvent extraction methods the reference materials shall be prepared in a solution of the
extraction solvent to be used. The extraction solvents are highly volatile and fresh reference standards shall
be prepared regularly.
For calibrating thermal desorption methods, liquid or gas phase standards may be used. See 7.1.2 and
EN ISO 16017-1 for more information.
Liquid standards for thermal desorption should be prepared in a ‘carrier’ solvent that is free from interfering
artefacts. Choose a solvent that can either be selectively purged from tube during the standard loading
process (see 7.1.2) or that can be chromatographically resolved from the compounds of interest during
analysis.
5.7 Analytical apparatus
5.7.1 Capillary gas chromatograph (GC)
Laboratory apparatus suitable for capillary column gas chromatography shall be used.
5.7.2 Thermal desorber (for thermal desorption)
The thermal desorber is connected to the GC (or GC-MS). It is used for the two stage thermal desorption of
sorbent tubes and transfer of the desorbed vapours via an inert gas flow into a gas chromatograph. A typical
apparatus contains a mechanism for holding the tubes to be desorbed while they are heated and purged
simultaneously with inert carrier gas. The desorption temperature and time is adjustable, as is the carrier gas
flow rate. The apparatus should also incorporate additional features such as leak testing, a cold trap in the
transfer line to concentrate the desorbed sample and at least one, preferably two quantitative sample split
points. The desorbed sample contained in the purge gas, is routed to the gas chromatograph and capillary
column via a heated transfer line.
Optional features to be considered include internal standard addition, automatic dry purging for simplifying the
analysis of humid samples and re-collection of split flow for repeat analysis and validation of compound
recovery (see Annex C).
6 Sampling procedure
6.1 General
The requirements of EN 15259 shall be met.
NOTE The homogeneity tests specified in EN 15259 can be performed using direct read-out FID instruments in
accordance with EN 12619 [3] providing the FID signal obtained is representative of the compound of interest.
6.2 Sampling conditions
The test laboratory shall have a documented procedure, to describe how to determine an appropriate
sampling volume and time. The temperature of the sample gas reaching the sorbent tube shall not be allowed
to exceed 40 °C. The sampling time and volume shall be calculated using
— the estimated concentration and/or limit value,
— the lower limit of detection of the analysis method,
— the safe sampling volume or capacity of the tube for the compounds of interest at the relevant sampling
temperature, i.e. a volume of not more than 70 % of the 5 %-breakthrough volume or 50 % of the
retention volume,
— the process time e.g. batch process time.
NOTE 1 Sample time and duration may be specified by the regulatory authority.
NOTE 2 If information on total VOC concentration in the waste gas is available from FID or some other stack
monitoring device, this can be useful in determining suitable sampling volumes.
Typical sample flow rates and sample volumes for charcoal tubes and thermal desorption are described in
Annex B and Annex C respectively.
In all cases, the volume, duration and frequency of sampling shall be sufficient to ensure that the quantitative
data obtained is representative of the mean compound concentration in the waste gas for the duration of the
process being monitored or over the period of sampling. To ensure representative sampling when collecting
small volumes of waste gas, the volume of the sampling system shall be taken into account and flushed with
waste gas immediately before the start of sampling.
A continuously flushed sampling system with a ‘Tee-ed’ bypass line can also be used. If compound
breakthrough or sample overload are particular concerns due to high compound volatility or high flue gas
concentrations; sampled volumes should be minimised. In the case of monitoring steady-state emissions with
thermal desorption tubes this can be achieved using simple grab-sampling apparatus (see 5.4). However, for
time weighted average monitoring and whenever using pumps or similar flow-controlled apparatus, sampling
small waste gas volumes may be subject to higher error – depending on the respective flow rate range of the
pump/device selected. In this case, gas dilution should be used to maintain sampling flow rates and volumes
at a constant level while minimising risk of sample overload and breakthrough. Dilution can be either static or
dynamic (see Annex A).
Sample overload or breakthrough shall be controlled by separate analysis of the second section (activated
carbon tubes) or secondary back-up tubes (thermal desorption). See 5.3.2 and Annex B and Annex C for
more information. Maximum breakthrough allowed is 5 % of the overall concentration (see Clause 9).
If analytical data obtained from the second layer or secondary (back-up) tube is below the detection limit, it is
accepted that there is no breakthrough.
6.3 Measurement of waste gas sample volume
The volume of the gas sampled shall be determined using a calibrated sampling device, see 5.5. See Annex A
for details of sample train components.
The sample temperature and pressure at the gas meter shall be measured unless automatically compensated
for by the sampling device.
The sample time shall be noted (refer to Clause 10).
6.4 Control of leakage
Leakage contributes significantly to sampling errors and shall be controlled by appropriate check procedures
before each sampling run. A suitable procedure for control of leakage is given in Annex A. The leak check
shall be carried out before and after sampling.
6.5 Handling, storage, transport of sampled tubes
6.5.1 General
Containers and materials emitting (outgassing) VOC, e.g. wood, certain plastics and sealing tape, shall not be
used for sample storage and transport. Tube storage containers shall be clean.
If sampled tubes cannot be analysed within 7 days they shall be stored in an air-tight container at < 4 °C
(refrigerated).
All tubes stored under refrigerated conditions, shall be allowed to equilibrate with room temperature before
they are removed from their storage container and uncapped for analysis. Allowing the tubes to equilibrate
with room temperature prevents ambient humidity condensing inside cold tubes.
6.5.2 Activated carbon (charcoal) tubes
Sampled tubes shall be capped then stored and transported in an airtight VOC free container without
exposure to direct sunlight and below 25 °C.
6.5.3 Thermal desorption tubes
Thermal desorption tubes shall be sealed using long term storage caps before and immediately after sampling
as specified in EN ISO 16017-1. Once capped, sorbent thermal desorption tubes shall be stored and
transported in a VOC free air-tight container without exposure to direct sunlight and below 25 °C.
If sampled thermal desorption tubes are stored under refrigerated conditions, caps shall be retightened after
the tubes have reached their minimum storage temperature.
6.6 Blanks
6.6.1 Field blanks
Field blank tubes comprise conditioned sorbent tubes, taken from the same batch as those used for field
monitoring, opened and handled in the same manner at the sample location as the sampling tubes but without
putting them in the stack or pulling the waste gas through them. They are subsequently analysed with the
sampled tubes to determine the average blank level for each compound of interest.
Every measurement campaign shall include at least one field blank per day. When taking more than 6
samples in one day then 2 field blanks are required. For greater than 10 samples in one day then 3 field
blanks are required.
In the case of activated carbon tubes it is only necessary to analyse the main adsorption layer of any field or
analytical blank.
6.6.2 Analytical (laboratory) blanks
Analytical (laboratory) blanks comprise conditioned samplers (sorbent tubes), taken from the same batch as
those used for field monitoring. They shall remain in the laboratory and shall be analysed as a check on
inherent sampler cleanliness (see 5.3) and the level of background contamination of the analytical system.
6.6.3 Solvent blank
The cleanliness of any solvent shall be determined prior to use, refer to 5.6.2.
7 Analytical procedure
7.1 Calibration of the GC analysis
7.1.1 GC calibration for analysis of solvent extracts
Calibration solutions shall be prepared using the same extraction solvent that is used for the sample tubes.
The range of concentration of the calibration solutions shall cover the concentrations of the sample extracts to
be analysed (see 5.6.3). At least five different concentration levels shall be used for calibration.
Calibration solutions with low concentrations of organic compounds can be prepared by first making a stock
solution and then by diluting the stock solution to various concentrations. However, extraction solvents are
highly volatile and evaporative losses should be minimised by using vessels closed with septa. The amount of
the evaporative losses can be determined by weighing the vessels before adding the first organic compound
to the extraction solvent and after adding the last organic compound to the extraction solvent. The least
volatile organic compound should be added to the extraction solvent first and the most volatile organic
compound should be added last. The evaporative losses are the difference between theoretical final weight
and real final weight and should be less than 1 % of the theoretical final weight.
Typically 1 µl of each calibration solution should be injected into the GC, operating under the same conditions
as for the sample analysis. A calibration graph should be prepared for every organic compound by plotting the
area of the compound peaks, on the vertical scale against the mass of the compound, in micrograms,
corresponding to the concentration in the calibration solutions.
The calibration Formula (1) shall be determined using linear regression:
A= f ⋅m+b (1)
i i i i
where
A is the measured area of organic component i;
i
f is the slope of the calibration line for organic component i;
i
m is the mass of organic component i in the injected aliquot of sample extract;
i
b is the intercept on the ordinate of the calibration line of organic component i.
i
7.1.2 Calibration for thermal desorption analysis
Thermal desorption methods are normally calibrated by introducing liquid or gas phase standards to the
sampling end of blank sorbent tubes in the vapour phase in a stream of carrier gas as described in
EN ISO 16017-1.
Liquid standards can alternatively be introduced directly to the sorbent sampling surface within the tube
provided care is taken not to dislodge the gauze or other sorbent support mechanism. This approach is
particularly suitable for reactive or high boiling compounds. A short purge of pure carrier gas (e.g. 5 min at
30 ml/min) should be applied to the sorbent tube, in the sampling direction, immediately after direct
introduction of liquid standards in order to sweep target compound into the sorbent bed and selectively
eliminate a significant proportion of the carrier solvent, if applicable (see 5.6.3). The range of compound
masses introduced to blank sorbent tubes to make standards shall cover the range of compound masses
expected to be retained during sampling (see 5.6.3). At least five different concentration levels shall be used
for calibration.
Prepared standard tubes shall be capped and sealed unless they are to be analysed immediately.
The thermal desorption/GC-MS analytical system shall be calibrated over the required concentration range by
desorbing sorbent tubes loaded with known masses of target compounds prepared as described above. Plot
the calibration curve (peak area vs. mass of compound) for each compound of interest as described in 7.1.1.
7.2 Sample preparation (desorption/extraction)
7.2.1 Solvent desorption
A suitable procedure for desorbing the collected sample is as follows:
— open the sorbent tubes, using a glass cutter if appropriate;
— place the main adsorbent layer with the glass wool plug into a glass vial and the security adsorbent layer
into separate glass vial; the foam plug between the two layers may be discarded;
— close the vials with a septum using a screw cap or a crimp cap;
— inject a known volume of CS , or another suitable extraction solvent through the septum using a syringe.
An amount of 1,0 ml of CS per 100 mg of carbon is sufficient in most cases. The desorption efficiency
can be determined as shown in Annex C;
— agitate the vials in an ultrasonic bath for 10 min at a temperature not exceeding 25 °C;
— separate the carbon particles by centrifugation for 10 min; the carbon particles are now at the bottom of
the vial. The extract is above and can be taken out by a syringe via the septum of the vessel manually or
automatically by a GC sampling system.
NOTE Any unused sample extract can be stored, for example in flame sealed glass Pasteur pipettes in a freezer.
Appropriate safety precautions shall be followed throughout, see Annex E.
7.2.2 Thermal desorption
Uncap the sample tubes and place them in the thermal desorption/GC system sequentially (manual systems)
or as a batch with appropriate analytical caps (automated systems). Tubes shall be orientated such that the
flow of inert carrier gas used for thermal desorption passes through the tube in the opposite direction to the
flow of waste gas during sampling. Sampled tubes shall be interspersed with blanks, mid-level calibrant
(standard) tubes and any back-up tubes (used to check for breakthrough during sampling (see 5.3.2)).
Tubes which have been used to sample waste gases with a high moisture content may require purging, in the
sampling direction, before analysis in order to remove residual moisture, e.g. with a flow of 50 ml/min to
100 ml/min of pure (>99,999 %) dry air or carrier gas for 15 min, Some commercial thermal desorption auto-
samplers allow this dry purging to be carried out automatically as part of the two-stage thermal desorption
process. Alternatively, batches of sampled tubes can be dry purged off-line using a suitable apparatus.
Care shall be taken that the sum of sampled and dry purge volumes passing through the sample tube does
not exceed the breakthrough volume of any target compound.
7.3 Analysis
7.3.1 GC analysis of extract from activated carbon tubes
The analysis of the sample shall be carried out by capillary gas chromatography (GC) with a flame ionization
detector or a mass selective detector. Typically 1 µl of the sample extract should be injected into the GC. The
masses m of the compounds shall be calculated from peak areas of the chromatogram. The sample extract
i
from the main adsorbent layer and the back adsorbent layer are analysed separately.
7.3.2 Thermal desorption / GC analysis of sorbent tubes
The process of thermally desorbing a tube is fully automated on commercial thermal desorption systems, and
involves multiple stages. Once the sorbent tube has been placed in a compatible thermal desorption
apparatus it is normally pressurized and sealed to check for leaks without compromising sample integrity. The
air inside the tube shall then be purged to vent using carrier gas in order to avoid chromatographic artefacts
arising from the thermal oxidation of the sorbent or GC stationary phase. It is usually necessary to use
10 × the tube volume (i.e. 20 ml to 30 ml) of inert gas to completely displace the air in a tube prior to
desorption. A larger volume of purge gas may be required to purge the strongest sorbents such as carbon
molecular sieves. The tube shall then be heated with carrier gas flowing in the opposite direction to the gas
flow during sampling.
NOTE 1 Typically 30 ml/min to 50 ml/min carrier gas flow optimises desorption efficiency.
The desorbed sample occupies a volume of several millilitres of gas so that pre-concentration is essential
prior to capillary GC analysis. This can be achieved using a small, moderately- (typically electrically-) cooled,
secondary sorbent trap, which can be desorbed sufficiently rapidly at low flow rates (<5 ml/min) to minimize
band broadening and produce capillary-compatible peaks.
NOTE 2 When thermal desorption of a solid sorbent sampling tube (primary trap) is used in conjunction with refocusing
and thermal desorption of a secondary focusing trap, this is called 2-stage thermal desorption.
NOTE 3 Alternative cryofocusing methods of pre-concentration are available but these typically require cooling to
–100 °C or below with liquid cryogen. Cryofocusing also requires tubes to be stringently dry-purged before analysis to
prevent ice forming in the cryo-trap and blocking the flow of gas.
Desorption conditions (temperatures, times and carrier gas flows) should be chosen such that desorption from
the sample tube, pre-concentration trap and thermal desorption system as a whole is complete (>95 %) (see
Annex C). More details of thermal desorption parameter selection are given in EN ISO 16017-1.
To minimize broadening of the chromatographic peaks during analysis, the part of the sample flow path
between the focusing trap and the capillary column (or the fused silica retention gap connected to the
analytical column), should be short, low-volume and uniformly heated. Various configurations of low volume
valving with narrow-bore tubing and/or using minimum dead volume unions have been found to be effective. A
split valve is conveniently placed at the inlet and/or outlet of the secondary trap (see 5.7.2). Selected split
ratios will vary from several thousand: 1 to zero depending on the mass of target analytes retained on the tube
during sampling.
NOTE 4 Most capillary GC columns and detectors work optimally with individual analyte masses of 200 ng or less.
Splitting options allow sorbent tubes containing much higher masses of compounds (e.g. several milligrams) to be
analysed without overloading the analytical column and detector.
NOTE 5 Some commercial TD systems offer the ability to re-collect all of the split flow thus facilitating repeat analysis
and validation of recovery through the TD system (see Annex C).
7.4 Quantification of individual organic compound concentrations
Sampled tubes, back up tubes (where applicable), calibration standards and blanks shall be analysed as
described in Annex B or A
...
Frequently Asked Questions
CEN/TS 13649:2014 is a technical specification published by the European Committee for Standardization (CEN). Its full title is "Stationary source emissions - Determination of the mass concentration of individual gaseous organic compounds - Sorptive sampling method followed by solvent extraction or thermal desorption". This standard covers: This Technical Specification specifies procedures for the sampling, preparation and analysis of individual volatile organic compounds (VOCs) in waste gas, such as those arising from solvent using processes. Sampling occurs by adsorption on sorbents, preparation by solvent extraction or thermodesorption and analysis by gas chromatography. Examples of individual VOC are given in relevant industry sector BAT Reference documents (BREFs). The results obtained are expressed as the mass concentration (mg/m3) of the individual gaseous organic compounds. This document is suitable for measuring individual VOCs whose ranges vary depending on compound and test method, refer to Annex B and C. This Technical Specification may be used to meet the monitoring requirements of the Industrial Emission Directive (IED) and associated supporting documents. This Technical Specification is not suitable for measuring total organic carbon (TOC). For the measurement of the mass concentration of total organic carbon then EN 12619 [3] is applicable.
This Technical Specification specifies procedures for the sampling, preparation and analysis of individual volatile organic compounds (VOCs) in waste gas, such as those arising from solvent using processes. Sampling occurs by adsorption on sorbents, preparation by solvent extraction or thermodesorption and analysis by gas chromatography. Examples of individual VOC are given in relevant industry sector BAT Reference documents (BREFs). The results obtained are expressed as the mass concentration (mg/m3) of the individual gaseous organic compounds. This document is suitable for measuring individual VOCs whose ranges vary depending on compound and test method, refer to Annex B and C. This Technical Specification may be used to meet the monitoring requirements of the Industrial Emission Directive (IED) and associated supporting documents. This Technical Specification is not suitable for measuring total organic carbon (TOC). For the measurement of the mass concentration of total organic carbon then EN 12619 [3] is applicable.
CEN/TS 13649:2014 is classified under the following ICS (International Classification for Standards) categories: 13.030.40 - Installations and equipment for waste disposal and treatment; 13.040.40 - Stationary source emissions. The ICS classification helps identify the subject area and facilitates finding related standards.
CEN/TS 13649:2014 has the following relationships with other standards: It is inter standard links to EN 13649:2001. Understanding these relationships helps ensure you are using the most current and applicable version of the standard.
You can purchase CEN/TS 13649:2014 directly from iTeh Standards. The document is available in PDF format and is delivered instantly after payment. Add the standard to your cart and complete the secure checkout process. iTeh Standards is an authorized distributor of CEN standards.
The article discusses CEN/TS 13649:2014, which is a technical specification that outlines procedures for sampling, preparation, and analysis of individual gaseous organic compounds in waste gas. The sampling is done through adsorption on sorbents, and the preparation involves either solvent extraction or thermodesorption. The analysis is conducted using gas chromatography. The results are expressed as the mass concentration of the individual compounds in units of mg/m3. This specification is suitable for monitoring the emissions of these compounds in accordance with the Industrial Emission Directive and associated supporting documents. However, it is not designed for measuring total organic carbon, for which EN 12619 is recommended.
기사 제목 : CEN/TS 13649:2014 - 정지원자원 배출 - 개별 기체 유기 화합물 농도의 결정 - 흡착 샘플링 방법 다음 용매 추출 또는 열 탈착 기사 내용 : 이 기술 사양은 폐가스에서 개별 휘발성 유기 화합물 (VOC)의 샘플링, 준비 및 분석 절차를 명시합니다. 샘플링은 흡착제에 의한 흡착으로 이루어지며, 준비는 용매 추출 또는 열 탈착에 의해 이루어지고, 분석은 가스 크로마토그래피로 수행됩니다. 해당 산업 분야 BAT 참조 문서(BREFs)에서는 개별 VOC의 예시가 주어집니다. 얻은 결과는 개별 기체 유기 화합물의 농도(mg/m3)로 표시됩니다. 본 문서는 화합물 및 시험 방법에 따라 범위가 달라지는 개별 VOC의 측정에 적합하며, 부록 B 및 C를 참조하십시오. 이 기술 사양은 산업 배출 지시사항(IED) 및 관련 지원 문서의 모니터링 요구 사항 충족을 위해 사용될 수 있습니다. 이 기술 사양은 총 유기 탄소 (TOC)의 질량 농도 측정에는 적합하지 않습니다. 전체 유기 탄소의 질량 농도 측정은 EN 12619 [3]을 사용하십시오.
記事のタイトル：CEN/TS 13649:2014 - 静的源排気 - 個別揮発性有機化合物の質量濃度の決定 - 吸着サンプリング方法に続く溶媒抽出または熱脱離 記事の内容：この技術仕様は、廃気などでの個別揮発性有機化合物（VOC）のサンプリング、準備、および分析手順を指定しています。サンプリングは吸着剤による吸着で行われ、溶媒抽出または熱脱離による準備、ガスクロマトグラフィーによる分析が行われます。 個別のVOCの例は、関連する産業セクターのBAT参照文書（BREF）に記載されています。 得られた結果は、個別の気体有機化合物の質量濃度（mg/m3）として表されます。この文書は、化合物および試験方法によって範囲が異なる個別のVOCの測定に適しており、付録BおよびCを参照してください。 この技術仕様は、産業排出指令（IED）および関連する支援文書のモニタリング要件を満たすために使用することができます。 この技術仕様は、総有機炭素（TOC）の質量濃度測定には適していません。総有機炭素の質量濃度を測定する場合は、異なる仕様であるEN 12619を使用してください。
기사 제목: CEN/TS 13649:2014 - 정지원자원 배출물 - 개별 기체 유기 화합물의 질량 농도 결정 - 흡착 샘플링 방법 다음에는 용매 추출 또는 열탈착 기사 내용: 이 기술 사양은 폐기물 가스 등에서 개별 휘발성 유기 화합물 (VOC)의 샘플링, 준비 및 분석 절차를 규정합니다. 샘플링은 흡착물에 흡착하는 것으로 이루어지며, 용매 추출 또는 열탈착을 통한 준비 및 가스 크로마토그래피를 통한 분석이 이루어집니다. 개별 VOC의 예시는 관련 산업 부문에 해당하는 BAT 참고 문서 (BREF)에서 제공됩니다. 얻은 결과는 개별 기체 유기 화합물의 질량 농도 (mg/m3)로 표현됩니다. 이 문서는 화합물 및 시험 방법에 따라 범위가 다르므로 부록 B 및 C를 참조하십시오. 이 기술 사양은 산업 배출 지침 (IED) 및 관련 지원 문서의 모니터링 요구 사항을 충족하기 위해 사용될 수 있습니다. 이 기술 사양은 총 유기 탄소 (TOC)의 질량 농도 측정에는 적합하지 않습니다. 총 유기 탄소의 질량 농도를 측정하기 위해서는 EN 12619 [3]를 사용하십시오.
The article discusses the procedures for determining the mass concentration of individual gaseous organic compounds in waste gas. This involves sampling through adsorption on sorbents, preparation through solvent extraction or thermodesorption, and analysis through gas chromatography. The results are expressed as the mass concentration of the compounds in milligrams per cubic meter. This specification can be used to meet monitoring requirements for the Industrial Emission Directive, but it is not suitable for measuring total organic carbon. For that, a different specification called EN 12619 should be used.
記事タイトル：CEN/TS 13649:2014 - 定常源排出物 - 個別揮発性有機化合物の質量濃度の決定 - 吸着サンプリング法に続く溶媒抽出または熱脱離 記事内容：この技術仕様では、廃気中の個別揮発性有機化合物（VOC）のサンプリング、準備、分析手順を規定しています。サンプリングは吸着剤による吸着によって行われ、準備は溶媒抽出または熱脱離によって行われます。分析はガスクロマトグラフィーを用いて行われます。 関連する業界セクターの最良技術適用文書（BREFs）で、個別のVOCの例が示されています。 得られた結果は、個々の揮発性有機化合物の質量濃度（mg/m3）として表されます。この文書は、化合物や試験方法によって範囲が異なる個別のVOCの測定に適しており、付録BおよびCを参照してください。 この技術仕様は、産業排出指令（IED）および関連する支援文書のモニタリング要件を満たすために使用することができます。 しかしながら、この技術仕様は総有機炭素（TOC）の質量濃度の測定には適していません。総有機炭素の質量濃度の測定にはEN 12619 [3]が適用されます。
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