EN 1948-1:2006

SLOVENSKI STANDARD
01-maj-2006
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SIST EN 1948-1:1999
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Stationary source emissions - Determination of the mass concentration of
PCDDs/PCDFs and dioxin-like PCBs - Part 1: Sampling of PCDDs/PCDFs
Emissionen aus stationären Quellen - Bestimmung der Massenkonzentration von
PCDD/PCDF und dioxin-ähnlichen PCB - Teil 1: Probenahme von PCDD/PCDF
Emissions de sources fixes - Détermination de la concentration massique en
PCDD/PCDF et PCB de type dioxine - Partie 1: Prélevement des PCDD/PCDF
Ta slovenski standard je istoveten z: EN 1948-1:2006
ICS:
13.040.40 (PLVLMHQHSUHPLþQLKYLURY Stationary source emissions
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

EUROPEAN STANDARD
EN 1948-1
NORME EUROPÉENNE
EUROPÄISCHE NORM
March 2006
ICS 13.040.40 Supersedes EN 1948-1:1996
English Version
Stationary source emissions - Determination of the mass
concentration of PCDDs/PCDFs and dioxin-like PCBs - Part 1:
Sampling of PCDDs/PCDFs
Emissions de sources fixes - Détermination de la Emissionen aus stationären Quellen - Bestimmung der
concentration massique en PCDD/PCDF et PCB de type Massenkonzentration von PCDD/PCDF und dioxin-
dioxine - Partie 1: Prélèvement ähnlichen PCB - Teil 1: Probenahme von PCDD/PCDF
This European Standard was approved by CEN on 23 January 2006.
CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European
Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national
standards may be obtained on application to the Central Secretariat or to any CEN member.
This European Standard exists in three official versions (English, French, German). A version in any other language made by translation
under the responsibility of a CEN member into its own language and notified to the Central Secretariat has the same status as the official
versions.
CEN members are the national standards bodies of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France,
Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania,
Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.
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COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: rue de Stassart, 36  B-1050 Brussels
© 2006 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 1948-1:2006: E
worldwide for CEN national Members.

Contents Page
Foreword . 3
Introduction. 7
1 Scope . 8
2 Normative references. 8
3 Terms and definitions. 9
4 Symbols and abbreviations. 11
5 Principle of the complete PCDD/PCDF measurement procedure. 12
6 Sampling device and materials. 15
7 Minimum requirements for sampling. 18
8 Safety measures and transport. 21
9 Preparations and sampling . 21
Annex A (informative)  Toxicity and toxic equivalency. 27
Annex B (informative)  Examples of operation. 30

Annex C (informative)  Examples of adsorbents and their preparations and cleaning. 58
Annex D (informative)  Sampling measurement record. 59
Annex E (informative)  Relations to EU Directives. 62
Bibliography. 63

Foreword
This European Standard (EN 1948-1:2006) has been prepared by Technical Committee CEN/TC 264 “Air
quality”, the secretariat of which is held by DIN.
This European Standard shall be given the status of a national standard, either by publication of an identical
text or by endorsement, at the latest by September 2006, and conflicting national standards shall be
withdrawn at the latest by September 2006.
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 European Standard supersedes EN 1948-1:1996.
This European Standard has been prepared under a mandate given to CEN by the European Commission
and the European Free Trade Association to support Essential Requirements of EU Directive 94/67/EC of
16 December 1994 [i] on the incineration of hazardous waste. This directive is now replaced by EU Directive
2000/76/EC of 4 December 2000 on the incineration of waste [ii] and this European Standard also supports
the Essential Requirements of the new EU Directive 2000/76/EC (see also Annex E).
The precision and the performance characteristics were determined between 1992 and 1995 in four
comparative and validation trials at waste incinerators sponsored by the European Commission, the European
Free Trade Association and the German Federal Environment Agency.
The revision of this EN between 2001 and 2004 only refers to the normative part. The information given in the
informative annexes as examples of operation are kept unchanged, as they represent the state of the art at
time of the validation measurements of EN 1948:1996 between 1992 and 1995.
This European Standard EN 1948:2006 consists of three parts dealing with the determination of the mass
concentration of PCDDs and PCDFs in stationary source emissions:
Part 1: Sampling of PCDDs/PCDFs;
Part 2: Extraction and clean-up of PCDDs/PCDFs;
Part 3: Identification and quantification of PCDDs/PCDFs.
All three parts are necessary for the performance of the dioxin measurements.
In addition for the sampling, extraction and analyses of dioxin-like PCBs the Technical Specification
CEN/TS 1948-4 is developed and will be transferred to a European Standard after corresponding validation
measurements or after an approval time of three years respectively.
Important changes made in the revision of EN 1948-1:
1. Title: Broadening of the title with regard to the future EN 1948-4 for the determination of dioxin-like
PCBs
2. Foreword:
) To be published.
• Deletion of all precursor documents which were basis for elaboration of EN 1948 as well as the
names of the standardisation bodies involved in the elaboration of EN 1948
• Update of the hint regarding mandate of the standardisation project and regarding fulfilment of
the Essential Requirements of EU Directives 94/67/EC and 2000/76/EC
• Addition of a hint, that the revision only refers to the normative parts of the standard. The
Informative Annex B “Examples of operation” is kept unchanged and represents the state of the
art at time of the validation measurements of EN 1948:1996 between 1992 and 1995
• Addition of hint with regard to the future document EN 1948-4 dealing with the analyses of dioxin-
like PCBs
3. Introduction: New hint that only skilled operators who are trained in handling highly toxic compounds
should apply the method described in this European Standard (identical to EN 1948-2 and EN 1948-3)
4. Scope:
• Addition of a hint, that EN 1948 can be applied for wide concentration ranges and various
emission sources
• Addition of a hint, that the described measurement methods are suitable for determination of
other low-volatile substances, e.g. of dioxin-like PCBs
5. Normative references:
• Update of the references to EN 1948-2:2006, EN 1948-3:2006
• Reference to EN 13284-1:2001 regarding determination of low range mass concentration of dust
instead of ISO 9096, therefore deletion of all references to ISO 9096 and replacement by
EN 13284-1:2001
• Additional normative reference to EN ISO/IEC 17025:2005
• Deletion of reference to ISO 4793:1980
6. Clause 3 Terms and definitions:
• Distinction between Clause 3 "Terms and definitions" and Clause 4 "Symbols and abbreviations"
resulting in a different numbering of the following chapters
• Corrected definition of "field blank" for clarification
• Corrected definition of "analytical blank" for clarification
• Corrected definition of "sampling standard": only furans
• "Syringe standard" renamed to read "recovery standard"
• Corrected definition of "recovery standard": only dioxins
• Additional definition of "dioxin-like PCBs"
• Additional definition of "flue gas sample volume"
• Additional definition of "measurement series" resp. "sampling campaign"
• Corrected definition and requirement of isokinetic sampling according to EN 13284-1:2001
• Additional definition and calculation of limit of detection
• Additional definition and calculation of limit of quantification
• Additional definition of WHO-TEF/WHO-TEQ
7. Clause 5.1 Sampling:
• Addition of a hint, that a higher temperature than 20°C/40°C (depending of the chosen sampling
method) can be used for the sample gas if it is demonstrated that the results obtained are
equivalent.
• Corrected clarification regarding the temperature falling below the dew point resp. regarding the
increase of the relative humidity
8. Clause 6.1 General sampling device:
• Extension of the general sampling devices, deletion of the old subclauses 5.1.1 to 5.1.4 dealing
with the single compilation of the devices for the different sampling methods, because all details
are listed in Annex B
• Additional note regarding oxygen concentration and its influence on the performance
characteristics
• Harmonisation of the sampling device requirements with other existing standards EN 13284-1,
EN 14790, EN 14789
9. Clause 6.2 Materials: Enlargement of the requirements for materials
10. Clause 6.3 Cleaning the sampling device: New subclause 6.3
11. Clause 7.1 Method validation criteria:
• a) Requirements for the plane filter efficiency according to EN 13284-1:2001
• c) Correction of the validation requirement regarding the flue gas sample volume
• c) Additional validation requirements with regard to the mean adsorber temperature
12. Clause 7.2 Requirements for sampling:
• Maximum sampling time of 8 h was deleted
• d) The field blank must be carried out according to the new subclause 7.3
• e) Addition of the requirement regarding quantification limit according to EN 1948-3, addition of
formula for calculation of the quantification limit according to EN 1948-3, addition of notes
regarding minimum flue gas sample volume and regarding minimum sampling time according
2000/76/EG
• f) Addition of the spiked parts of the equipment
13. Clause 7.3 Field blank requirements: Additional section dealing with a completed and corrected
compilation of all field blank requirements
14. Clauses 7.4, 7.5, 7.6 Additional sampling minimum requirements for the 3 different methods:
• Addition of a footnote, that a temperature limit of 125 °C is required for the filter of the
filter/condenser method to avoid chemical reactions on activated surfaces.
• Deletion of the requirement to connect the sampling device according to figures in Annex B
• Deletion of the requirement to cool des sample gas temperature with a maximum of 20 °C resp.
40 °C
15. Additional requirement of leak check when changing
Clause 9.3.4.2 Changing sampling line:
sampling
16. Clause 9.3.5.1 Sample recovery from the sampling train: Additional requirements with regard to
rinsing the equipment, the rinsing solution becomes part of the sample
17. Clause 9.3.5.2 Sample storage: Deletion of the requirement to store the samples below 4 °C.
Additional requirement to use screw-caps with aluminium-lined seals for storing
18. Clause 9.4 Calculation of flue gas volume: Correction of the formula for conversion to standard
conditions
19. Clause 9.5 Sampling report:
• Addition of the content and the relevance of the sampling report
• e) Addition of requirement regarding the identification of the used parts of the sampling
equipment
• g) Harmonisation of the requirement regarding isokinetic sampling according to EN 13284-1:2001
20. Annex A: Revision/update of the Toxicity of PCDD/PCDF according to the requirements of the WHO
21. Annex B: Addition of bibliography references
22. Annex B 1.5b: Correction of filter position
23. Annex E / F: Deletion of annexes dealing with humidity and oxygen content determination
24. Annex E: Update of the hint regarding mandate of the standardisation project and regarding fulfilment
of basic requirements of EU Directives 94/67/EC and 2000/76/EC
25. Bibliography: Update
According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following
countries are bound to implement this European Standard: Austria, Belgium, Cyprus, Czech Republic,
Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden,
Switzerland and the United Kingdom.

Introduction
Two groups of related chlorinated aromatic ethers are known as polychlorinated dibenzodioxins (PCDDs) and
polychlorinated dibenzofurans (PCDFs); they consist of a total of 210 individual substances (congeners):
75 PCDDs and 135 PCDFs.
PCDDs and PCDFs can form in the combustion of organic materials; they also occur as undesirable by-
products in the manufacture or further processing of chlorinated organic chemicals. PCDDs/PCDFs enter the
environment via these emission paths and through the use of contaminated materials. In fact, they are
universally present in very small concentrations. The 2,3,7,8-chlorine substituted congeners are toxicologically
significant. Toxicologically much less significant than tetrachlorinated to octachlorinated dibenzodioxins/-
dibenzofurans are the 74 monochlorinated to trichlorinated dibenzodioxins/dibenzofurans (for toxicity
equivalent factors, see Annex A).
Only skilled operators who are trained in handling highly toxic compounds should apply the method described
in this European Standard.
1 Scope
This European Standard specifies the sampling of PCDDs/PCDFs. It is an integral part of the complete
measurement procedure. The use of the other two parts EN 1948-2 and
EN 1948-3 describing extraction and clean-up and identification and quantification, respectively, is necessary
for the determination of the PCDDs/PCDFs.
This European Standard has been developed to measure PCDD/PCDF concentrations at about
0,1 ng I-TEQ/m in stationary source emissions.
This European Standard specifies both method validation and a framework of quality control requirements
which shall be fulfilled by any PCDD/PCDF sampling.
The user has the possibility to choose between three different methods:
 "filter/condenser method"
 "dilution method"
 "cooled probe method"
Each sampling method is illustrated by some sampling systems described in detail in Annex B as examples of
proven procedures.
During comparison measurements of the three sampling methods on municipal waste incinerators at the level
of about 0,1 ng I-TEQ/m these methods have been deemed comparable within the expected range of
uncertainty. Validation trials were performed on the flue gas of municipal waste incinerators at the level of
3 3 3
about 0,1 ng I-TEQ/m and a dust loading of from 1 mg/m to 15 mg/m . Although this European Standard is
primarily developed and validated for gaseous streams emitted by waste incinerators, the practical experience
shows that it can be applied for wide concentration ranges and various emission sources.
The procedure described in the three parts of EN 1948 specifies requirements which shall be met in order to
measure the 17 congeners necessary to calculate the total I-TEQ (see Table A.1).
Besides the determination of PCDDs/PCDFs the described measurement methods are suitable for
determination of other low-volatile substances, e.g. of dioxin-like PCBs (details for sampling and analyses see
CEN/TS 1948-4), although no validated performance characteristics are available yet.
2 Normative references
The following referenced documents are indispensable for the application of this European Standard. For
dated references, only the edition cited applies. For undated references, the latest edition of the referenced
document (including any amendments) applies.
EN 1948-2:2006, Stationary source emissions — Determination of the mass concentration of PCDDs/PCDFs
and dioxin-like PCBs — Part 2: Extraction and clean-up of PCDDs/PCDFs
EN 1948-3:2006, Stationary source emissions — Determination of the mass concentration of PCDDs/PCDFs
and dioxin-like PCBs — Part 3: Identification and quantification of PCDDs/PCDFs
EN 13284-1, Stationary source emissions — Determination of low range mass concentration of dust — Part 1:
Manual gravimetric method
EN 14789, Stationary source emissions — Determination of volume concentration of oxygen (O ) —
Reference method — Paramagnetism
EN 14790, Stationary source emissions - Determination of the water vapour in ducts
EN ISO/IEC 17025, General requirements for the competence of testing and calibration laboratories (ISO/IEC
17025:2005)
3 Terms and definitions
For the purposes of this European Standard, the terms and definitions given in EN 1948-2:2006,
EN 1948-3:2006 and the following apply.
3.1
analytical blank value
value determined by a blank sample covering the complete analytical procedure including extraction, clean-up,
identification and quantification including all the relevant reagents and materials
3.2
congener
any one of the 210 individual PCDDs/PCDFs
3.3
dioxin-like PCBs
any PCB showing similar toxicity as the 2,3,7,8-substituted PCDDs/PCDFs according to WHO [iii]
3.4
extraction standard
C -labelled 2,3,7,8-chlorine substituted PCDDs/PCDFs, added before extraction. These standards are also
used for calculation of results
3.5
field blank value
value determined by a blank sample covering a specific procedure 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
3.6
flue gas sample volume
expressed at standard conditions of temperature and pressure on a dry basis and if required corrected to the
reference concentration of oxygen
3.7
isokinetic sampling
sampling at a flow rate such that the velocity and direction of the gas entering the sampling nozzle are the
same as the velocity and direction of the gas in the duct at the sampling point
[EN 13284-1:2001, definition 3.5 ]
3.8
keeper
high boiling point solvent added to the sampling standard solution
3.9
limit of detection (LOD)
minimum value of the measurand for which the measuring system is not in the basic state, with a stated
probability
NOTE 1 The limit of detection, also referred to as capability of detection, is defined by reference to the applicable basic
state. But it may be different from "zero", for instance for oxygen measurement as well as when gas chromatographs are
used.
[prEN ISO 9169:2004, definition 3.2.6 [iv]]
NOTE 2 The measurement value can be distinguished from the analytical blank value with a confidence of 99 %. The
limit of detection is expressed as the mean analytical blank value (b ) plus three times the standard deviation of the
ave
analytical blank (s ).
b
LOD =b + 3s (1)
ave b
where
LOD is the detection limit;
b is the mean analytical blank value;
ave
s is standard deviation of the analytical blank.
b
NOTE 3 In this European Standard the limit of detection should preferably be calculated from the analytical blank b .
ave
If this is not possible, the limit of detection can be calculated from the signal to noise ratio according to EN 1948-3:2006,
8.1.
3.10
limit of quantification (LOQ)
limit above which a quantification of the measurand is possible, expressed as the mean analytical blank value
plus, either, five to ten times the standard deviation of the analytical blank. The factor F depends to the
accepted measurement uncertainty.
LOQ =b + F s (2)
ave b
where
LOQ is the quantification limit;
b is the mean analytical blank value;
ave
s is standard deviation of the analytical blank
b
NOTE In this European Standard the limit of quantification should preferably be calculated from the analytical blank
b . If this is not possible, the limit of quantification can be calculated from the signal to noise ratio according to
ave
EN 1948-3:2006, 8.1 using the requirement of EN 1948-3:2006, 8.3e.
3.11
measurement series
sampling campaign
several successive measurements carried out at the same sampling site and at the same process operating
conditions (in this European Standard often the wording sampling campaign is used)
3.12
pattern
chromatographic print of any series of PCDD/PCDF isomers
3.13
PCDD/PCDF isomers
PCDDs or PCDFs with identical chemical composition but different structure
3.14
profile
graphic representation of the sums of the isomer concentrations of the PCDDs and the PCDFs
3.15
recovery standard
C -labelled 2,3,7,8-chlorine substituted PCDDs, added before GC injection
3.16
sampling standard
C -labelled 2,3,7,8-chlorine substituted PCDFs, added before sampling
3.17
spiking
addition of C -labelled PCDDs and PCDFs standards
3.18
standard pressure
101,3 kPa
3.19
standard temperature
273,15 K
3.16
WHO-TEF
toxic equivalent factor proposed by WHO [iii] (for detailed description see Annex A)
3.17
WHO-TEQ
toxic equivalent obtained by multiplying the mass determined with the corresponding WHO-TEF including
PCDDs, PCDFs and PCBs (for detailed description see Annex A)
NOTE WHO-TEQ , WHO-TEQ should be used to distinguish different compound classes.
PCB PCDD/PCDF
4 Symbols and abbreviations
4.1 General
HRGC
high resolution gas chromatography
HRMS
high resolution mass spectrometry
I-TEF
international toxic equivalent factor (for a detailed description, see Annex A)
I-TEQ
international toxic equivalent obtained by weighting the mass determined with the corresponding I-TEF (for a
detailed description, see Annex A)
LOD
limit of detection
LOQ
limit of quantification
PCB
polychlorinated biphenyl
PCDD/PCDF
polychlorinated dibenzo-p-dioxin/dibenzofuran
PTFE
polytetrafluoroethylene
PU foam
polyurethane foam
WHO-TEF
toxic equivalent factor of the World Health Organisation
WHO-TEQ
toxic equivalent of the World Health Organisation
4.2 Congeners of PCDD/PCDF
TCDD
Tetrachlorodibenzo-p-dioxin
PeCDD
Pentachlorodibenzo-p-dioxin
HxCDD
Hexachlorodibenzo-p-dioxin
HpCDD
Heptachlorodibenzo-p-dioxin
OCDD
Octachlorodibenzo-p-dioxin
TCDF
Tetrachlorodibenzofuran
PeCDF
Pentachlorodibenzofuran
HxCDF
Hexachlorodibenzofuran
HpCDF
Heptachlorodibenzofuran
OCDF
Octachlorodibenzofuran
5 Principle of the complete PCDD/PCDF measurement procedure
5.1 Sampling
5.1.1 General
Gas is sampled isokinetically in the duct. The PCDDs/PCDFs, both adsorbed on particles and in the gas
phase, are collected in the sampling train. The collecting parts can be a filter, a condensate flask and a solid
or liquid adsorbent appropriate to the sampling system chosen. There is the choice between three different
sampling systems:
 filter/condenser method;
 dilution method;
 cooled probe method.
Schematic representations of the sampling methods are given in Figures 1 to 3.
The main collecting parts are spiked with C -labelled PCDDs/PCDFs before sampling to determine the
sampling recovery rate of the congeners. The sample gas is brought to a temperature specific to the sampling
system and the gaseous and particulate PCDDs/PCDFs are trapped.
Sampling shall be carried out according to EN 13284-1. Exceptions with their justification shall be reported.
The minimum requirements of the sampling procedure to be met are described in this European Standard.
Examples of operation are listed in Annex B. The described systems meet the minimum requirements of
Clause 7, but differ in their approach.
5.1.2 Filter/condenser method
The principle of the method is shown in Figure 1. Different variants for this system are possible (see Figures
B.1, B.2 and B.5).
Figure 1 — Schematic representation of the filter/condenser method
The filter is placed downstream of the nozzle (in the stack) or after the probe (out of the stack). The filter shall
be kept below 125 °C ), but above the flue gas dew point. When a high dust loading is expected, a quartz
wool filter or a cyclone may be incorporated into the sampling train before the filter to prevent the filter from
being overloaded. Downstream, a condenser is attached to cool the sample gas below 20 °C. An upper
temperature can be used if it is demonstrated that the results obtained are equivalent. The gaseous and
aerosol parts of the PCDDs and PCDFs are captured by impingers and/or solid adsorbents.
In a variant of this sampling system the solid adsorber unit can be linked between condenser and condensate
flask (see Figure B.5).
) In order to avoid chemical reactions on activated surfaces the temperature limit of 125 °C is required.
The system with division of flow differs in the way that after filtering there is a flow divider. The main stream
with a high volume flow to handle the isokinetic conditions passes the filter. The side stream after flow division
is identical to the device with condenser and adsorber unit described above (see Figure B.2).
5.1.3 Dilution method
The principle of the method is shown in Figure 2. Differences in the details of this system are possible (see
Figures B.6 and B.8).
Figure 2 — Schematic representation of the dilution method
The sample gas is collected via a heated probe. The waste gas is cooled very rapidly in a mixing channel
below 40 °C using dried, filtered and, if appropriate, cooled air. An upper temperature can be used if it is
demonstrated that the results obtained are equivalent. The dilution avoids the relative humidity of the sampling
gas rising to 100 %.
After dilution a filter is used to collect the particulate PCDDs/PCDFs contained in the waste gas stream. For
the separation of the gaseous PCDDs/PCDFs a solid adsorbent is linked downstream.
5.1.4 Cooled probe method
The principle of the method is shown in Figure 3.

Figure 3 — Schematic representation of the cooled probe method
Different systems of this variant are possible (see Figures B.9 and B.11). The sample gas passes the nozzle
and a water-cooled probe, in which it is cooled below 20 °C. An upper temperature can be used if it is
demonstrated that the results obtained are equivalent.
The condensate is caught in a condensate flask. Downstream, impingers/bubblers and/or solid adsorber units
are linked in order to collect the gaseous PCDDs/PCDFs. Before the last impinger/bubbler or solid adsorbent,
there is a filter to separate small particles and to break aerosols.
5.2 Extraction and clean-up
Extraction is necessary to isolate the PCDDs/PCDFs from the sample and to collect them in an appropriate
solvent volume. Extraction procedures are normally based on soxhlet extraction of filters and adsorbents, and
liquid extraction of condensates. Sample clean-up is usually carried out by multi-column chromatographic
techniques using a range of adsorbents. The main purpose of cleaning the raw sample extracts is to remove
sample matrix components, which may overload the separation method, disturb the quantification or otherwise
severely impact the performance of the identification and quantification method. In principle any clean-up
method can be used which recovers the analytes in sufficient quantities. Furthermore, the final sample extract
should not affect adversely the performance of the analytical system or the quantification step. Methods shall
have been tested thoroughly and comply with a set of method validation criteria before being employed. In
addition, the verification of the method performance for each single sample shall be part of a validated quality
assurance protocol.
In EN 1948-2 the minimum requirements for extraction and clean-up to be met are described as well as
examples of operation. Examples of operation are given in Annex A of EN 1948-2:2006.
5.3 Identification and quantification
This European Standard is based on the use of high resolution gas chromatography/high resolution mass
spectrometry (HRGC/HRMS) for separation and detection, combined with isotope dilution of samples at
different stages for quantification of PCDDs/PCDFs in emission samples. At present, this technique is the only
analytical technique that can provide sufficient sensitivity, selectivity and specificity for the determination of
minute amounts of PCDDs/ PCDFs in emission samples. The gas chromatographic parameters offer
information which enables the identification of isomers (position of Cl substituents) whereas the mass
spectrometric parameters enable the differentiation between congeners with different numbers of chlorine
substituents and between dibenzo-p-dioxins and furans.
In EN 1948-3 the minimum requirements for identification and quantification to be met are described as well
as examples of operation. Examples of operation are given in Annex A of EN 1948-3:2006.
6 Sampling device and materials
6.1 General sampling device
See Annex B for detailed description of examples of sampling devices which can meet the minimum
requirements. However, this can depend on the experimental conditions and each user still shall prove that
the minimum requirements for sampling are met during sampling.
6.1.1 General
The requirements of the sampling devices follow EN 13284-1.
6.1.2 Sampling system
All parts of the system in contact with the flue gas: nozzle, probe, glass tubes, filter holder, filter casing,
condenser, bubbler, solid adsorber cartridge etc.
6.1.3 Pitot tube with a differential pressure gauge (alternatively a micromanometer)
For measuring the static and dynamic pressure in the waste gas channel (for calculating the gas pressure
gauge/flow velocity).
6.1.4 Moisture measuring device
To determine the moisture in the waste gas in accordance with EN 14790.
6.1.5 Micromanometer
To measure the flue gas pressure in the duct.
6.1.6 Oxygen measurement system
To determine the oxygen content in accordance with EN 14789.
NOTE If the oxygen concentration exceeds 19 %, the uncertainty of the oxygen-related measurement result is
greater than given in EN 1948-3:2006, Clause 14 Performance characteristics.
6.1.7 Syringe or micro-pipettes
To add the C -labelled standard solution (sampling standards).
6.1.8 Volume measurement device
To determine the sample gas volume, the accuracy of the volume measurement device shall be ± 2 %.
6.1.9 Flow rate measurement device
To measure the volume flow rate to allow isokinetic conditions to be maintained.
6.1.10 Barometer and pressure gauge
To determine the pressure, the absolute measurement uncertainty shall be ± 1 % [EN 13284-1].
6.1.11 Thermometer
To determine the temperature, absolute measurement uncertainty shall be ± 1 %, Temperature in Kelvin [EN
13284-1].
6.2 Materials
6.2.1 General
For detailed description of adsorbents and filter and their purification, see Annex C and Annex A of
EN 1948-2:2006. The reagents shall be of high purity to meet the criteria of blank analysis to have a low
PCDD/PCDF background concentration.
6.2.2 Sampling system
All parts of the sampling system coming in contact with the flue gas which constitutes the sample including
the last adsorption stage, shall be made from glass, quartz or titanium.
6.2.3 Sealings (in contact with flue gas)
Made of PTFE.
6.2.4 Filter
Made of quartz or glass fibre, meeting the minimum requirements (see Clause 7).
6.2.5 Quartz wool (if used)
May be used as a pre-filter in high dust concentrations.
6.2.6 Solid adsorbent
XAD-2 ), polyurethane foam (PU foam), other solid adsorbents (e.g. Porapak PS )) meeting the minimum
requirements (see Clause 7). See Annex A of EN 1948-2:2006, for examples on material specification.
6.2.7 Cooling fluid
To cool the condenser or the cooled probe.
6.2.8 Ice bath (if used)
To cool the impingers and condensate flasks.
6.2.9 Silica gel
For the drying towers.
6.2.10 Reagents
acetone;
methyl alcohol (methanol);
toluene;
methylene chloride (dichloromethane);
2-methoxyethanol, 2-ethoxyethanol or 2,2’-oxydiethanol (diethylene glycol);
distilled water.
6.3 Cleaning the sampling device
The cleaning procedure shall be suitable to meet the requirement of the blanks. Several methods for cleaning
the sampling devices, which is coming, or have been, in contact with the flue gas, is described in Annex B and
in Annex A of EN 1948-2:2006.
Three procedures for cleaning the sampling devices are given as examples:
1) Cleaning of the sampling equipment in the laboratory. Normally rinsing with water and detergent,
followed by rinsing with solvent and/or treatment in a muffle oven preferably at 400 °C to 450 °C (not
higher than 380 °C for titanium) for several hours, to remove any traces of organics.
2) Rinsing with solvent prior to sampling (can be done either in the laboratory if parts are carefully
wrapped in aluminium foil, or at sampling site when connecting the sampling train).
3) Rinsing the equipment being in contact with the flue gas with solvents after the sampling. This
rinsing solution is an important part of the sample.
Rinsing with solvents normally include two different solvents, where one of them is miscible with water (e.g.
acetone and/or methanol followed by toluene). When rinsing equipment wetted by condensate, it is very
important to use the water miscible solvent first, to remove the water.

) XAD-2 and Porapak PS are examples of suitable commercially available products. This indication is only made for
information of the user of this European Standard and does not mean any approval of the named products by CEN.
7 Minimum requirements for sampling
7.1 Method validation criteria
a) Plane filter efficiency better than 99,5 % on a test aerosol with a mean particle diameter of 0,3 µm, at the
maximum flow rate anticipated (or 99,9 % an a test aerosol of 0,6 µm mean diameter). This efficiency
shall be certified by the filter supplier [EN 13284-1:2001, 6.2.7]. The filter is upstream of the sampling
train in case of the filter/condenser method and the dilution method, or before the last adsorption stage in
case of the cooled probe method.
b) An adsorption stage e.g. solid adsorbents or impingers for collecting gaseous PCDDs/PCDFs is part of
the sampling train. A minimum absorption/adsorption efficiency of 90 % for the gaseous PCDDs/PCDFs
(that are filter passing PCDDs/PCDFs) of this absorbent/adsorbent shall be shown in a separate test.
c) A validation trial shall be carried out at least once with each design of sampling equipment. In this
validation trial the last absorption/adsorption stage shall be duplicated by placing an additional
absorption/adsorption stage in series.
 Sufficient sample volume shall be collected during the validation trial so that the quantification
limit is less than 5 % of the total amount collected (expressed in I-TEQ).
 The original sampling train and the additional absorption/adsorption stage shall be analysed
separately. More than 90 % of the total I-TEQ shall be found in the original sampling train.
 The average adsorber temperature during validation of the method shall not be exceeded during
the sampling campaign. Otherwise, an additional validation for an accordingly higher
temperature shall be performed.
7.2 Minimum requirements for sampling
a) The isokinetic sampling shall be carried out according to EN 13284-1.
b) Sampling shall be carried out at representative positions in the duct according to EN 13284-1.
c) A leak check shall be carried out before and after every sampling procedure. The sampling train with
plugged nozzle is evacuated to the minimum pressure used during sampling and the volume flow rate
shall be less than 5 % of the normal flow rate.
d) A field blank shall be taken before each sampling campaign (see 7.3 for details).
e) The permissible limits of quantification (LOQs) for the individual congener i shall be as follows:
0,5 pg/m
LOQ ≤ (3)
i
I-TEF
i
LOQ limit of quantification;
I-TEF international toxic equivalency factor.
NOTE 1 A flue gas sample volume of at least 4 m is recommended to reach the quantification limit of the analytical
laboratories.
NOTE 2 According to the EU Council Directive 2000/76/EC on incineration of waste [ii] the minimum sampling time
is 6 h, the maximum sampling time is 8 h. The validation of this standard was performed for a sampling time of 6 h.
f) The sampling train is spiked with C -labelled PCDDs/PCDFs as follows:
Method Spiked part of the equipment
Filter/condenser method: Filter and/or adsorbents;
Dilution method: Filter;
Cooled-probe method: Condensate flask and/or filter and/or adsorbents.
g) The C -labelled standards are used as follows (see Table 1):
Table 1 — Mass of labelled sampling standards to be added
Congeners added Total amount in pg added:
(Solution (e.g. toluene): Minimum volume 100 µl with
4 % tetradecane as keeper)
C-1,2,3,7,8-PeCDF 400
C-1,2,3,7,8,9-HxCDF 400
C-1,2,3,4,7,8,9-HpCDF 800
The masses of the labelled standards to be added are 400 pg for PeCDF and HxCDF and 800 pg for
HpCDF each on the basis of 10 m flue gas sample volume (dry gas) and to measure the concentration of
0,1 ng I-TEQ/m . The sampling standard solution shall be at least 100 µl. If a considerably higher or lower
mass of native PCDDs/PCDFs is expected in the sample, the masses of the C -labelled standards to
be added should be adapted accordingly.
h) The sampling standard solution contains 4 % tetradecane as keeper.
i) If during sampling a change of the spiked part becomes necessary, the new part shall be spiked with the
same sampling standard solution. This shall be taken into account for the calculation of the sampling
standard recovery.
j) The sampling flow rate shall be in the range the method is validated for.
k) The recovery rate of each sampling standard shall be greater than 50 % calculated on the basis of the
relevant extraction standard (see EN 1948-3).
7.3 Field blank requirements
The field blank is taken at the operator’s site according to the following procedure:
- the sampling train is mounted at the same location as the flue gas samples of the measurement
series;
- the probe is not inserted into the stack;
- no gas is drawn through the sampling train;
- a leak check is performed;
- the sampling train is dismounted.
A field blank procedure shall be performed at least before each measurement series.
If parts of the sampling train are cleaned at site before being reused, a final rinse of all surfaces reused which
are in contact with the sample shall be performed. The rinsing solution shall be stored. It shall be analysed
when the concentration of the following sample exceeds the emission limit value.
If several measurements are performed during the same sampling campaign and according to the same
procedure, and if the measurements are performed on the same industrial process or on several lines of the
same industrial process, then a single field blank shall be performed.
The field blank shall not be deducted from the measured value.
The value of this field blank shall not exceed 10 % of the emission limit value assuming the same volume as
for sampling. If the calculated value measured is less than the preceding field blank value, the reported result
is defined as less or equal to the blank.
NOTE In case of monitoring dioxin emissions significantly lower than 0,1 ng I-TEQ/m³, the field blank may be in the
same range as the measured concentration.
All field blanks shall be reported with the corresponding measured values.
7.4 Additional sampling minimum requirements for the filter/condenser method
For schematic representation, see Figure 1.
4)
a) The filter is run below 125 °C inside or outside the stack . The sample gas temperature in the filter
holder, however, shall be above its dew point.
b) Impingers or solid adsorbents are used as absorbents/adsorbents.
c) If a variant with flow division is chosen, the ratio of the main and side streams shall be kept constant
(± 10 %).
7.5 Additional sampling minimum requirements for the dilution method
For schematic representation, see Figure 2.
a) Condensation on the filter shall be avoided.
b) A solid adsorber stage is downstream from the filter.
c) The sampling device shall contain a dilution air verification adsorption stage (i.e. a filter and adsorbent)
which shall be replaced and stored after each measurement. It shall be analysed if the measurement
result exceeds the emission limit value. In other cases it c
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