SIST-TS CEN/TS 15439:2009

SLOVENSKI STANDARD
01-september-2009
8SOLQMDQMHELRPDVH.DWUDQLQGHOFLYSURL]YRGQLKSOLQLK9]RUþHQMHLQDQDOL]D
Biomass gasification - Tar and particles in product gases - Sampling and analysis
Biomassevergasung - Teer und Staub in Produktgasen - Probenahme und analytische
Bestimmung
Gazéification de biomasse - Goudron et particules dans les gaz produits -
Échantillonnage et analyse
Ta slovenski standard je istoveten z: CEN/TS 15439:2006
ICS:
13.040.40 (PLVLMHQHSUHPLþQLKYLURY Stationary source emissions
75.160.10 Trda goriva Solid fuels
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

TECHNICAL SPECIFICATION
CEN/TS 15439
SPÉCIFICATION TECHNIQUE
TECHNISCHE SPEZIFIKATION
May 2006
ICS 13.040.40; 75.160.10
English Version
Biomass gasification - Tar and particles in product gases -
Sampling and analysis
Gazéification de biomasse - Goudron et particules dans les Biomassevergasung - Teer und Staub in Produktgasen -
gaz produits - Échantillonnage et analyse Probenahme und analytische Bestimmung
This Technical Specification (CEN/TS) was approved by CEN on 21 February 2006 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, 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.
EUROPEAN COMMITTEE FOR STANDARDIZATION
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. CEN/TS 15439:2006: E
worldwide for CEN national Members.

Contents Page
Foreword.3
Introduction.4
1 Scope .5
2 Normative references .5
3 Terms and definitions .5
4 Symbols and abbreviations .8
5 Principle of the measurement method .8
5.1 Introduction.8
5.2 Sampling.8
5.3 Analysis .8
6 Reagents.9
6.1 Solvent for tar collection and Soxhlet extraction.9
6.2 Carrier gas in gas chromatography.9
6.3 Calibration standards.9
7 Equipment .9
7.1 Equipment for sampling.9
7.2 Equipment for sample pretreatment and analysis . 13
8 Preparation of sampling equipment . 13
8.1 Preconditioning of filter thimbles . 13
8.2 Cleaning of equipment . 14
8.3 Preparation of impinger bottles or Petersen column. 14
8.4 Sampling train leak test . 14
9 Procedure for sampling . 15
9.1 Introduction. 15
9.2 Duration of sampling. 15
9.3 Sampling procedure . 16
10 Storage of samples. 16
11 Preparation for analysis. 17
11.1 Introduction. 17
11.2 Requirements for GC calibration standards and internal standards (ISTD) . 17
12 Analysis procedures . 18
12.1 Soxhlet extraction procedure. 18
12.2 Combination of solvents. 19
12.3 Determination of particle mass . 19
12.4 Determination of gravimetric tar mass. 19
12.5 Determination of individual tar compounds by GC–MS or GC-FID. 20
13 Calculation of GC results. 21
14 Performance characteristics . 21
14.1 Introduction. 21
14.2 Performance of the analysis methods (Round Robin tests) . 22
14.3 Performance of the whole Technical Specification (parallel tests). 23
15 Test report . 24
Annex A (informative) List of most abundant individual organic compounds in biomass gasification
product gases . 25
Annex B (normative) List of organic compounds for which precision data have been collected . 26
Annex C (normative) Dimensions of the Petersen column . 27
Annex D (informative) Additional information on Round Robin analysis . 28
Annex E (informative) Additional information on parallel tests . 34
Bibliography. 41
Foreword
This Technical Specification (CEN/TS 15439:2006) has been prepared by Working Group CEN/BT/TF 143
“Measurement of organic contaminants (tar) in biomass producer gases”, the secretariat of which is held by NEN.
According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following
countries are bound to announce this CEN Technical Specification: 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.

Introduction
The main contaminants in the product gases of biomass gasification are dust and soot particles, tars, alkali
metals, acid gases and alkaline gases. Measuring techniques for these contaminants allow determination of the
functioning of the gasifier itself, of the efficiency of the gas cleaning process and of the quality of the cleaned gas
to be used in, for instance, a gas engine or gas turbine.
The development of this Technical Specification started out of the need for a reliable method for the
measurement of tars. For most contaminants in product gases of biomass gasification, well-developed
measurement techniques exist that are similar to techniques used for related technologies, such as coal
combustion and coal gasification. For tars, however, no well-developed and widely used measurement
techniques existed in these related technology fields. As some of the tars were (and are) seen as the major
problem causing contaminants in biomass gasification, manufacturers and other workers in this field used a
number of different sampling and analysis methods to determine the level of tars. As a result, comparison of data
and definition of clear maximum allowable concentrations for tars was problematic. This formed an obstacle for
market introduction of biomass gasification systems, as tars can cause damage or require an unacceptable level
of maintenance.
This Technical Specification gives methods for sampling and analysis of tars and particles in product gases from
biomass gasifiers operating under atmospheric or pressurised conditions. The sampling and analysis methods in
this Technical Specification differ from most of the methods used for sampling organic compounds present in the
gaseous emissions from various industrial processes such as flue gases or automobile exhaust gases. The
differences are related to the fact that the levels of the organic compounds present in the gasification product
gases exceed the levels found in flue gases generally by more than three orders of magnitude. Hence the
methods described in this Technical Specification are not intended to be applicable for sampling organic
compounds in trace concentrations (sub-ppm range).
The tar-containing biomass gasification product gas is formed by thermal decomposition of biomass at sub
stoichiometric conditions (pyrolysis, gasification) and is typically used to produce electricity, heat, or gaseous or
liquid biofuels. As tars from pyrolysis or gasification of coal are similar in nature compared to (high temperature)
biomass gasification tars, coal tars can also be sampled and analysed with this Technical Specification.
Biomass in this Technical Specification is defined as material of biological origin excluding material embedded in
)
geological formations and transformed to fossil . The Technical Specification is developed for uncontaminated
biomass, a term being defined in Clause 3 "Terms and definitions". Tests on accuracy and repeatability of the
Technical Specification have been performed with uncontaminated biomass. The Technical Specification may
also be used for tars produced from gasification of contaminated biomass and for tars produced from gasification
of fossil fuels, however, in this case it is up to the user to assess to what extent the concentration and
composition of the tars differ from gasification of uncontaminated biomass. Biomass gasifiers, as referred to in
this Technical Specification, can be updraft fixed bed gasifiers, downdraft fixed bed gasifiers, stage divided
gasifiers, fluidised bed gasifiers, entrained flow gasifiers and other types of gasifiers. Updraft and downdraft fixed
bed, fluidised bed and entrained flow gasifiers are described in more detail in a background Technical Report [1].

1)
This definition is the same as the definition of biomass in CEN TC 335 Solid Biofuels
1 Scope
This Technical Specification gives methods for sampling and analysis of tars and particles in order to determine
the load of these contaminants in flowing biomass gasification product gases. The Technical Specification is
applicable to sampling and analysis of tars and particles in the concentration range typically from 1 mg/m to 300
n
3 3 3
g/m (tars) and from 20 mg/m to 30 g/m (particles) at all relevant sampling point conditions
n n n
), ) 3
2 3
(0 °C to 900°C and 60 kPa to 6000 kPa (0,6 bar to 60 bar) ) . Particle concentrations lower than 20 mg/m
n
are outside the scope of this Technical Specification and can be measured according to EN 13284-1.

Application of this Technical Specification allows determination of five different parameters:
A. The concentration of gravimetric tar in mg/m ;
n
B. The concentration of individual organic compounds in mg/m . This Technical Specification gives data on
n
repeatability and reproducibility for the compounds listed in Annex B. The Technical Specification is also
applicable for other organic compounds (e.g. those mentioned in Annex A), but repeatability and
reproducibility have not been assessed for compounds other than those in Annex B;
C. The sum of concentrations of identified GC-detectable compounds listed in Annex B;
D. The sum of concentrations of all GC-detectable compounds with retention times in the range of benzene to
coronene calculated as naphthalene (benzene excluded), given that this sum of concentrations can be
determined.
E. The concentration of particles in mg/m .
n
2 Normative references
The following referenced documents are indispensable for the application of this document. For dated references,
only the edition cited applies. For undated references, the latest edition of the referenced document (including
any amendments) applies.
ISO 9096 Stationary source emissions – Manual determination of mass
concentration of particulate matter
3 Terms and definitions
For the purposes of this Technical Specification, the following terms and definitions apply.
3.1
aerosol
suspension of solid or liquid particles in a gas
NOTE The term aerosol includes both the particles and the suspending gas. The particle size may range from about
0,002 µm to more than 100 µm.
3.2
biomass
material of biological origin, excluding material embedded in geological formations and transformed to fossil
NOTE This definition is the same as the definition of biomass in CEN TC 335 Solid Biofuels [7].

)
In fact it is not correct to give a concentration or to give concentration ranges for “tar” (see also its definition in Clause 3). This Technical
Specification is designed and has been evaluated for measurement of tar and particles in the following concentration ranges:
3 3
Gravimetric tar 500 mg/m to 300 g/m
n n
3 3
Sum of GC-detectable tars 1 mg/m to 300 g/m
n n
3 3
Particles 20 mg/m to 30 g/m
n n
The concentration range mentioned for gravimetric tar is a range based on a sampling time of 2 h. Lower concentration limits can be
attained with proportionally longer sampling times (e.g. 100 mg/m with a sampling time of 10 h). Due to the determination method, it is
n
recommended not to determine gravimetric tar below the concentration limit.
)
The performance characteristics in Clause 14 are determined under atmospheric conditions. Under pressurised conditions, the Technical
Specification as a whole has not been evaluated. However, sampling under pressurised conditions is based on relevant experience
(relevant construction details of probes are mentioned in a background document [1]) and the analysis of the liquid samples is identical for
atmospheric and pressurised gasification. Therefore, pressurised conditions are included in this Technical Specification.
3.3
contaminated biomass
biomass not being uncontaminated biomass
NOTE See 3.20.
3.4
downdraft gasification
gasification process in which a bed of solid carbon-based material moves slowly downward under gravity as it is
)
gasified, whilst the gasification agent (e.g. air) passes through the bed co-currently . The product gas leaves the
gasifier at the base
3.5
entrained flow gasification
gasification process in which carbon-based material is fed co-currently with the gasification agent (e.g. air,
oxygen or steam) and where the velocity of the gasification agent is sufficiently high to maintain entrainment of
the carbon-based material
3.6
fluidised bed gasification
gasification process in which carbon-based material is fed into a suspended (bubbling) or circulating hot bed of
inert particles (e.g. sand or ash), the suspension or circulation being created by the gasification agent (e.g. air,
oxygen or steam)
3.7
gasification
thermal conversion of carbon-based materials into a product gas composed primarily of CO, H , methane and
lighter hydrocarbons in association with CO , H O and N depending on the specific gasification process
2 2 2
considered
NOTE Gasification can be accomplished by direct internal heating provided by partial oxidation using e.g.
substoichiometric air or oxygen. Alternatively, concepts based on either indirect heating methods or autothermal methods
using exothermic reduction reactions may be applied.
3.8
GC detection limit
lowest concentration that can be detected by the GC equipment.
NOTE This concentration depends on the quality of the equipment and is defined as twice the noise level in the GC
chromatogram.
3.9
GC-detectable tar
tar that can be measured as a gaseous mixture of individual components according to standard (or state of the
art) gas chromatographic practice
3.10
gravimetric tar
evaporation/distillation residue from particle free sampling solution(s) determined by gravimetric analysis
3.11
isokinetic sampling
sampling at a flow rate such that the velocity and direction of the gas entering the sample nozzle are the same as
they are in the gas in the duct at the sampling point
3.12
normal conditions
conditions with a temperature of 273,15 K, pressure of 101 325 Pa (1,013 25 bar) and on a dry basis

)
Co-current does not automatically mean downdraft but can also mean updraft, although co-current updraft designs are uncommon.
3.13
particles
solid residue collected by a particle filter after solvent extraction or solid residue from filtration of sampling
solution(s)
NOTE Solid residue may contain a small amount of insoluble polymerised tar.
3.14
Petersen column
alternative to impinger bottles in the sampling train. The Petersen column is a piece of glass equipment with two
containers for liquid, which act as washing stages to remove soluble compounds from a gas. The two containers
are separated by a glass frit. A description of the Petersen column is given in Annex C
3.15
product gas
gas resulting from gasification
NOTE The product gas from biomass gasification can be used as a fuel (then also named fuel gas, producer gas or
water gas) in internal and external combustion engines, fuel cells, and other prime movers for heat and mechanical or
electrical power. Alternatively, the product gas may be used as a feedstock (then also named synthesis gas or syngas) for the
petrochemical and refining industries, e.g. for the production of liquid fuels or chemicals.
3.16
pyrolysis
thermal decomposition in the absence of an oxygen source such as air, oxygen, H O or CO
2 2
3.17
sampling train
equipment used for sampling particles and tars, consisting of the particle filter, the impinger bottles or Petersen
column, the pump and flow measuring equipment and all connecting tubes
3.18
soxhlet extraction
batch extraction method at the boiling point of the used solvent and atmospheric pressure
3.19
tar
generic (unspecific) term for entity of all organic compounds present in the gasification product gas excluding
gaseous hydrocarbons (C1 through C6)
3.20
uncontaminated biomass
biomass from the following sources:
• Products from agriculture and forestry;
• Vegetable waste from agriculture and forestry;
• Vegetable waste from the food processing industry;
• Wood waste, with the exception of wood waste that may contain halogenated organic compounds or heavy
metals as a result of treatment with wood preservatives or coatings, and including in particular wood derived
from construction and demolition waste

NOTE This definition reflects the biomass categorised as “solid biofuels“ under the scope of CEN TC 335 Solid Biofuels [7].
3.21
updraft gasification
gasification process in which a bed of solid carbon-based material moves slowly downward under gravity as it is
)
gasified, whilst the gasification agent (e.g. air or oxygen) passes through the bed counter-currently , where the
product gas leaves the gasifier at the top

)
Counter-current does not automatically mean updraft but can also mean downdraft, although counter-current downdraft designs hardly
exist.
4 Symbols and abbreviations
BTX : Benzene, Toluene and Xylenes
GC-FID : Gas Chromatography – Flame Ionisation Detector
GC-MS : Gas Chromatography – Mass Spectrometer
id : Internal diameter
ISTD : Internal Standard
m : Cubic metre at normal conditions
n
M/z : Molar mass-to-charge ratio
MW : Mega Watt based on the thermal input of the biomass (lower heating value)
th
Pa : Pascal
PAH : Polycyclic Aromatic Hydrocarbons
PTFE : Polytetrafluoroethene
NOTE The designation of the variables RF, M and A is explained just below the equations in which they are used.
5 Principle of the measurement method
5.1 Introduction
The principle of the measurement method is based on the discontinuous extractive sampling of a representative
part of a gas stream containing particles and organic compounds (tar) under isokinetic conditions. The
determination of particles and tars in biomass gasification product gases is carried out in two steps: sampling and
analysis.
5.2 Sampling
Samples of tars and particles are taken at a gasifier sample port, which is gas tight so that neither can gas
escape from the system nor can oxygen enter it. The sampling train is configured as a heated probe with a
heated particle filter to remove solid matter. The volatile tars are trapped in heated or chilled impinger bottles
containing an organic liquid absorbent. The sampled gas volume is measured under dry conditions by means of a
gas meter. The samples are prepared on-site and are stored until they can be analysed.
5.3 Analysis
5.3.1 Introduction
The samples are analysed in a laboratory. The particle filter containing the particle sample is Soxhlet extracted in
order to remove adsorbed tars. Subsequently the amount of particles is determined gravimetrically. The tars from
the Soxhlet extraction are added to the liquid tar samples. If required, the liquid tar samples are filtered for
removal of solid matter.
For the analysis of tars two methods are given in this Technical Specification, analysing respectively gravimetric
tar and gas chromatographable tar. The user is free to choose either one or both methods, depending on the kind
of information needed. The users attention is drawn to the fact that the two resulting values are not
supplementary, but that there is an overlap between the two tar values. The user’s attention is also drawn to the
fact that the gravimetric method is not suitable for clean gases with low tar concentrations and that its
reproducibility is significantly poorer than the GC analysis method.
5.3.2 Gravimetric determination
Part of the homogeneous liquid sample is evaporated under well-defined conditions and the evaporation residue
is weighed. The result is then recalculated to give the amount of gravimetric tar in mg per m of product gas.
n
5.3.3 Gas chromatography
Part of the liquid sample is injected into a gas chromatograph (GC). This analysis results in concentrations of
individual tar compounds and of the sum of GC-detectable tars, both in mg per m of product gas.
n
Positive identification of the condensed material as biomass tar is performed using GC-MS. The presence of tar
is indicated typically by the presence of the US-EPA suite of PAH compounds, phenols and BTX. Quantitative
determination of each compound is performed either by GC-MS or GC-FID analysis using internal standards.
Please note that not all of the tar constituents are amenable to GC analysis because of the presence of high
molecular weight material, thermal labile or extreme polar compounds. GC analysis will usually determine more
than 80% of the tar, the remainder being e.g. high-molecular weight material of >350 g/mol. However, for updraft
gasifier tars the fraction determined may be considerably lower.
6 Reagents
6.1 Solvent for tar collection and Soxhlet extraction
Isopropanol (2-propanol) shall be used as the solvent for tar collection, for Soxhlet extraction and for sample
preparation and analysis. The minimum purity of the isopropanol is 99%. It shall be verified with a blank GC
determination that the solvent does not contain GC detectable amounts of relevant tar compounds.
Ethanol shall be used in gravimetric analysis procedure to remove trace water from evaporation residue
(gravimetric tar). The required minimum purity is 99%.
Other solvents like ethanol or dichloromethane shall only be used for rinsing of the glass and PTFE equipment
when cleaning with isopropanol leaves tar residues that can be visually observed.
6.2 Carrier gas in gas chromatography
The carrier gas shall be helium of acceptable purity or a suitable alternative as specified by the GC manufacturer.
6.3 Calibration standards
All reagents shall be of recognised analytical reagent quality, preferably analytical or "pro analysis" grade. The tar
compounds are named in Annex A and Annex B.
7 Equipment
7.1 Equipment for sampling
7.1.1 Description of the sampling equipment
The equipment for sampling consists of a heated probe, a heated particle filter, a condenser, a series of impinger
bottles containing a solvent for tar absorption, and equipment for pressure and flow rate adjustment and
measurement. Upstream of the condenser the tubes connecting these parts are heated in order to prevent tar
condensation. Temperatures for heating the probe, filter and tubes are specified to avoid both condensation of
tars and thermal decomposition of tars. Temperatures for the condenser and the impingers are specified to
ensure quantitative collection of the tars. An explanation for the choice of equipment and conditions is given in a
separate document entitled “Rationale for setup” [2].
The sampling equipment consists of four main modules and respective sub-modules. The main modules are gas
preconditioning, particle collection, tar collection and volume measurement. These modules are shown in Figure
1. The basic equipment of these modules is mentioned in the next paragraph in Table 1. A more detailed
description of each module is found in a background Technical Report [1].

Key
1 Gasflow
2 Module 1
3 Module 2
4 Module 3
5 Module 4
6 Sub-module 4.1
7 Sub-module 4.2
8 Sub-module 4.3
Figure 1 — Concept of the modular sampling train
The equipment needed for sampling is mentioned in Table 1. Examples and details on construction are described
in a background Technical Report [1], including the adaptations needed for module 1 if tars and particles have to
be sampled from pressurised gasifiers.
Table 1 — General description of modules and sub-modules with purpose and equipment used
Function Main equipment
Module 1 Gas cooling, pressure Nozzle, valves, sampling lines
(Gas preconditioning) reduction
Module 2 Separation and collection Heated filter (high temperature)
(Particle collection) of solids
Option 1 Option 2
Module 3
(Tar collection) Moisture collection and Condenser with solvent
partial tar condensation (1 impinger bottle)
Tar collection Impingers with solvent (4 impinger Petersen column
bottles, some with glass frits) (see Annex C)
Drop collection Empty impinger (1 bottle with a
glass frit)
Module 4
(Volume registration)
Sub-module 4.1 Gas suction Gas drying, pump
Sub-module 4.2 Gas volume integration Gas meter, needle valve (adjustment and control of flow
rate), rotameter (flow indication), indicators for
temperature and differential pressure, barometer
Sub-module 4.3 Off-gas handling Outdoor ventilation

7.1.2 Requirements for sampling equipment
The sampling equipment shall meet the following functional requirements:
• When using impinger bottles of standard design (NS 29/32-250), flow rates through the impinger bottles shall
3 3
be between 0,1 m /h and 0,6 m /h. For high gas velocities, requiring a flow rate through the nozzle higher
n n
than 0,6 m /h to meet isokinetic conditions, this requirement plus the requirements on the minimum nozzle
n
diameter and on isokinetic sampling shall be met by splitting the gas flow between the nozzle and the
impinger bottles.
• The sampling equipment allows isokinetic sampling according to ISO 9096. If only tars are analysed, isokinetic
sampling is still required in all cases with the following exceptions: (1) for pressurised gasifiers; (2) for large-
scale gasifiers with large pipe diameters (for example in ISO 9096 duct diameter shall be < 0,35 m for only
one sampling point); and (3) if only tar is sampled and the temperature of the gasification product gas at the
sampling site exceeds 350 °C. Isokinetic sampling demands an undisturbed gas flow. Recommendations on
how to measure isokinetically according to ISO 9096 are given in a background Technical Report [1].
• For pressurised gasifiers, the product gas temperature at the location of sampling shall exceed 350 °C.
• The equipment shall be gas tight.
• The minimum nozzle diameter shall be 4 mm according to ISO 9096. For isokinetic sampling, the nozzle shall
be designed according to ISO 9096.
• Temperatures of the sampling line and the particle filter shall be:
– between 100 °C and 125 °C for updraft gasification;
– between 300 °C and 350 °C for downdraft, fluidised bed and entrained flow gasification.
• Gas velocities from the nozzle to the particle filter shall be higher than 25 m/s to avoid particle deposition.
• The filters (absolute filters) shall be manufactured from quartz and shall have a retention capacity of at least
)
99,998 % for particles of size 0,3 µm (DOP standard ).
• Thimble filters shall be used. The dimensions of filter thimbles shall be selected to be suitable for subsequent
Soxhlet extraction. The recommended dimensions for the filter thimble are a diameter of 30 mm and a length
of 77 mm or 100 mm. As a general indication, a filter surface area of 100 cm allows the collection of several
grams of particles without significant increase in pressure drop over the filter. This is valid for sample flows of
0,6 m /h and for gasification product gases containing high temperature tar.
n
• The probe and filter holder shall be manufactured from 310 or 316 grade stainless steel or, when using
another material, the user shall verify that the material does not affect the composition of tar compounds. Any
material used shall endure a temperature 50 °C higher than the operating temperature.
• A thermocouple shall be placed either on the surface of, or inside, the filter holder to measure the gas
temperature at the filter.
• Tar collection shall be performed either with six impinger bottles (A) or with a Petersen column (B). The user
shall decide to use either a Petersen column (B) or one of the setups with impinger bottles (A1 or A2).

(A) Impinger bottles
Standard impinger bottles (NS 29/32) of 100 ml or 250 ml can be used. Standard dimensions are a length of
200 mm and an outer diameter of 40 mm (100 ml impinger bottle) or 55 mm (250 ml impinger bottle). For gas
flow rates higher than 0,3 m /h, impinger bottles of 250 ml shall be used. The first impinger bottle acts as a
n
condenser for water. For high moisture gas or for sampling times longer than 1 h, the first impinger bottle shall
have a size of 250 ml as a large amount of condensate will be generated. Impinger bottles 1, 2, 3, 4 and 5
shall contain solvent, impinger bottle 6 shall be empty.

One of the following two setups for the 6 impinger bottles shall be chosen. The alternative setup shall only be
used when the pressure drop over the impinger bottles is too high or when, for safety reasons, the pressure
drop must be kept low. When using the alternative setup, the user shall verify the collection efficiency over the
impinger bottles.
(A1) Standard setup with impinger bottles
− Impinger bottles 2, 3, 5 and 6 shall be fitted with glass frits located either as a filter at the end of the
inner tube or around the inner tube covering the rest of the diameter of the impinger bottle. G3 frits shall
be used, if this results in a too high pressure drop over module 3, G2 frits may be substituted and/or the
frit in impinger bottle 2 may be replaced by a G1 frit.
− The temperature of impinger bottles 1, 2, and 4 shall be between 35 °C and 40 °C, the temperature of
impinger bottles 3, 5 and 6 shall be between –15 °C and –20 °C.
(A2) Alternative setup with impinger bottles
− Impinger bottles 1, 5, and 6 contain glass beads. The outside diameter of the glass bead is 6 mm.
− The temperature of impinger bottles 1, 2, 3 and 4 shall be between 35 °C and 40 °C, the temperature of
impinger bottles 5 and 6 shall be between –15 °C and –20 °C.
(B) Petersen column
− The Petersen column shall be constructed according to the dimensions given in Annex C.
− The temperature in the cooling jacket of the Petersen column shall be between –3 °C and +3 °C,
preferable 0 °C.
• The solvent in the liquid impingers shall be isopropanol.

)
The test method was developed in USA during World War II. DOP is Bis(2-ethylhexyl) Phthalate and is (like other Phthalates) an
undesirable compound according to National and EU environmental rules. The most common test aerosols nowadays are Latex particles
or DEHS Di (2-ethylhexyl) Sebacate or DOS Dioctyl Sebacate. The term ‘DOP test’ is used in everyday language, but the reagent DOP is
no longer used.
• The gas suction pump shall be oil-free and air-tight with minimal pulsation. It shall be able to displace at least
1 m /h at an absolute pressure of 50 000 Pa.
n
• A calibrated dry-gas meter fitted with a thermocouple shall be used. The pressure drop over the volume-
measuring device shall not exceed 250 Pa. An absolute pressure indicator is required at the outlet of the dry
gas meter covering the range of 0 kPa to 120 kPa (1,2 bar). Alternatively a differential pressure indicator that
can measure ± 20 kPa (± 0,2 bar) may be used in combination with an accurate measurement of local
atmospheric pressure.
7.2 Equipment for sample pretreatment and analysis
7.2.1 Equipment for gravimetric analysis
The following equipment is required for gravimetric analysis:
• Soxhlet apparatus
• Standard rotary evaporator with temperature control and pressure indicator
• Desiccator
• Calibrated analytical balance with a resolution of at least 0,1 mg, 0,01 mg is preferable
• General laboratory equipment, such as volumetric flasks and measuring cylinders.
7.2.2 Equipment for gas chromatography
The following equipment is required for gas chromatographic analysis:
• Soxhlet apparatus
• A high resolution Gas Chromatograph – Mass Spectrometer (GC-MS), incorporating a mass spectrometer with
a mass range of 20 M/z to 400 M/z, or a high resolution Gas Chromatograph – Flame Ionisation Detector (GC-
FID).
• Integration software package (usually included with GC)
• Non-polar capillary GC column packed with, for example, DPDM-siloxane (5 % diphenyl + 95 % dimethyl)
copolymer phase. Dimensions are typically 30 m to 60 m length, 0,25 mm id. and a film thickness of 0,25 µm
• Calibrated analytical balance with a resolution of at least 0,1 mg, 0,01 mg being preferable
• General laboratory equipment, such as volumetric flasks, measuring cylinders, syringes and pipettes, all
calibrated according to relevant National Standards
• If there is any risk that ferrules may be in contact with the sample gas, ferrules made up of no more than 49 %
graphite (e.g. 60 % polyimide/40 % graphite) shall be used at the GC column injection inlet to avoid possible
adsorption of tar compounds.
8 Preparation of sampling equipment
8.1 Preconditioning of filter thimbles
Filter thimbles shall be pre-calibrated as follows:
a) The quartz thimble filter shall be dried in an oven at 110 °C at atmospheric pressure overnight (according to
ISO 9096).
b) An aluminium foil shall be weighed using an analytical balance with an accuracy of ± 0,1 mg.
c) The filter shall be removed from the oven and shall be wrapped directly in the aluminium foil.
d) The filter shall be allowed to acclimatise in a desiccator at room temperature.
e) The filter plus aluminium foil shall be weighed on the same analytical balance and the weight of the filter
shall be calculated.
f) The aluminium foil shall be removed from the filter, the filter shall be mounted and the filter holder shall be
heated to its set value.
8.2 Cleaning of equipment
Laboratory glassware shall be cleaned according to good laboratory practice, for example by using a cleaning
agent (laboratory detergent) followed by an annealing treatment at 500 °C for 2 h. An example of such a cleaning
method is given in a background Technical Report [1].
The efficiency of the treatment shall be randomly verified experimentally using blank determinations to ensure
that no interfering contamination has occurred.
8.3 Preparation of impinger bottles or Petersen column
8.3.1 Impinger bottles
Impinger bottles shall be prepared as follows:
a) An amount of 50 ml of isopropanol shall be added to 100 ml impinger bottles and an amount of 100 ml of
isopropanol shall be added to 250 ml impinger bottles. For sampling times longer than 1 h only, a 250 ml bottle
shall be used for the first impinger bottle and this shall be filled with 150 ml isopropanol to avoid the evaporation
of all isopropanol during the sampling.
b) The drop-collecting bottle shall be placed after the impingers.
c) The impinger bottles shall be cooled or heated to the appropriate temperature. Cooling shall be performed by
a mixture of ice/salt/water, by a mixture of isopropanol/dry ice or by cryostatic cooling of isopropanol. When using
an ice/salt/water cooling mixture, make sure that the mixture is wet. At least 30 min shall be allowed for cooling of
the impinger bottles from room temperature to the sampling temperature of –20 °C.
8.3.2 Petersen column
Approximately 200 ml isopropanol shall be added through the filling stubs to both washing stages of the Petersen
column, above and below the glass frit. In total, approximately 400 ml of isopropanol shall be used.
The isopropanol shall be circulated in the same direction as the gas flow (co-currently) through the cooling jacket
of the column and the liquid cooling unit until the isopropanol has reached a temperature of approximately 0 °C.
After sampling, the first washing stage shall be emptied by opening the lower valve of the column. The second
washing stage above the glass frit shall then be emptied by applying suction below the frit (achieved by use of
the sampling train vacuum pump). The flash back of solvent through the frit will keep the frit clean. The solvent
from both washing stages shall be collected in the same storage bottle.
8.4 Sampling train leak test
8.4.1 Introduction
Prior to sampling a leak test shall be performed. This can be carried out by either pressurising or evacuating the
entire sampling train. The user shall select which of these procedures to follow.
8.4.2 Pressurising the entire sampling train
The method for leak testing by pressurisation of the sampling chain is as follows:
a) Nitrogen or compressed air from a cylinder shall be gently fed into the particle filter inlet and the rest of the
sampling train, up to 20 kPa (0,2 bar) above the maximum sampling pressure achieved during sampling. The exit
of the gas pump shall be isolated by a ball valve adjusted to a closed position. When the excess pressure has
reached 20 kPa (0,2 bar), the gas supply from the cylinder shall be stopped.
b) The pressure in the sampling line shall be monitored by a pressure indicator. The pressure shall stay
constant. Possible leaks are detected as gas bubbles in the impingers, by a decreasing pressure or by leak
indicators.
c) The shutoff valves after the pump shall be carefully opened. This pressure release procedure shall be
undertaken with utmost care and over a period of at least one minute.
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