27/06/2012
The importance of sampling strategy,
sample handling and storage for emission
testing
F. Maes
27/06/2012
© 2011, VITO NV
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Summary
» Product emission testing: why – what?
»
»
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Indoor air
Construction Products Directive (CPD)
Emission test chamber experiments - general
Evaluation protocols – product labels
Consumer products / electronic devices emission testing
SVOC emission testing
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Indoor air pollution
» Indoor air pollution is the presence in
buildings of toxic or other substances
which may directly or indirectly be a
cause of occupant ill health or
discomfort.
» Sources of pollution: contaminants in
the outdoor air and those released
from products or by activities of
occupants
» Formaldehyde and VOCs are key
pollutants emitted from construction
products
D. Crump,
European concepts to identify and limit emissions from construction products
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Construction Products Directive
» CPD (European Council Directive 89/106/EEC)
» Recently: Regulation (EU) No 305/2011, replaces CPD from July 2013
» Goal: removing trade barriers for construction products in the common
market of the European Union and permitting the free movement of goods,
if they are “fit for their intended use”
» Products have to fulfill essential requirements (Annex I CPD)
1.
Mechanical resistance and stability
2.
Safety in case of fire
3.
Hygiene, health and the environment
4.
Safety in use
5.
Protection against noise
6.
Energy economy and heat retention
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Construction Products Directive
1.
Mechanical resistance and stability
2.
Safety in case of fire
3. Hygiene, health and the environment
4.
Safety in use
5.
Protection against noise
6.
Energy economy and heat retention
» “The construction work, must be designed and built in such a way that it will
not be a threat to the hygiene or health of the occupants or neighbours, in
particular as a result of any of the following:
»
»
»
»
»
the giving-off of toxic gas,
the presence of dangerous particles or gases in the air,
the emission of dangerous radiation
pollution or poisoning of the water or soil,
faulty elimination of waste water, smoke, solid or liquid wastes,
» the presence of damp in parts of the works or on surfaces within the works.”
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Beginning of emission measurements
» To promote development of low emitting building materials
» 1990: GuT – association of environmentally friendly carpets, voluntary
labelling system with respect to VOC emissions
» 1995: DICL (Danish Indoor Climate label), products representing large
surface areas in indoor environment
» 1995: Finnish emission classification
» …
» 1997: European collaborative action: IAQ and its impact on man
Report No 18: “Evaluation of VOC emissions from building products”
=basic testing scheme for flooring materials
=basis for German AgBB, French AFSSET,…
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Standardisation of emission testing
» 1999: EN 13419
» -1: test chamber
» -2: test cell
» -3: sample preparation
» Revised and published as EN ISO 16000 Indoor Air standards
»
»
»
»
ISO 16000-3: Formaldehyde and other carbonyl compounds in air analysis
ISO 16000-6: Volatile organic compounds in air analysis (VOC: C6-C16)
ISO 16000-9: Operation of emission test chamber
ISO 16000-10: Operation of emission test cell - FLEC
» ISO 16000-11: Preparation of test specimens
» ISO 16000-25: Determination of the emission of semivolatile organic compounds
(SVOC: > C16) by building products — Micro-chamber method
» WD: ISO 16000-31: Measurement of flame retardants and plasticizers based on
organophosphorus compounds -- Phosphoric acid ester
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Sampling of the material
Transport of the sample
Storage of the sample before testing
ISO 16000-11
Test specimen preparation
Testing age and conditioning of the test
specimen
Measuring technique
ISO 16000-3
-6
Analyses
Evaluation procedure
AgBB, Afsset,…
Reporting, labelling
Building material emissions to indoor air, Opportunities/consequences for Belgian companies, M. Lor
27/06/2012
© 2011, VITO NV
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Evaluation
Standardisation of emission testing
» 1999: EN 13419
» -1: test chamber
» -2: test cell
» -3: sample preparation
» Revised and published as EN ISO 16000 Indoor Air standards
» ISO 16000-3: Formaldehyde and other carbonyl compounds in air analysis
» ISO 16000-6: Volatile organic compounds in air analysis
» ISO 16000-9: Operation of emission test chamber
» ISO 16000-10: Operation of emission test cell
» ISO 16000-11: Preparation of test specimens
» EN 717-1: formaldehyde emission testing for wooden products
» US: California section 1350 and ASTM D5116
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Emission test chamber operation
R. Oppl, New draft harmonized CEN standard on emissions from construction products principles common with ISO 16000 and
EN 717-1 and differences
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Emission test chamber operation
R. Oppl, New draft harmonized CEN standard on emissions from construction products principles common with ISO 16000 and
EN 717-1 and differences
» Started from ISO 16000, addition of specifications for improving reliability of
testing when more than one lab is involved
» Pending validation project
» Differences: tried to find compromise
» Allows integrating several testing purposes into one test setup
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Emission test chamber operation
»
»
»
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Test chamber simulates reference room conditions
ISO 16000-9: 7 m² surface; 2.49 m high
New CEN standard: 3 x 4 m surface, 2.5 m high, one door and one window
These dimensions determine loading factors
» Flooring material: 12 m² / 30 m³ = 0.4 m²/m³
» …
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Different sizes of test chambers
» ISO 16000-9
» ISO 16000-10
ISO 16000-25 Determination of the
emission of semi-volatile organic compounds by
building products -- Micro-chamber method
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Emission test results
» Result of an emission test: compound in µg/m³
» Different sizes, different loading factors,…
» => specific emission rate
• AER = 0.5 h-1 ; ASAFR = AER/loading factor [m³/hm²]
• SER = concentration [µg/m³] x ASAFR; [µg/hm²]
» Comparison of results possible between emission tests in different test chambers
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Sampling of the material
Transport of the sample
Storage of the sample before testing
ISO 16000-11
Test specimen preparation
Testing age and conditioning of the test
specimen
Measuring technique
ISO 16000-3
-6
Analyses
Evaluation procedure
AgBB, Afsset,…
Reporting, labelling
Building material emissions to indoor air, Opportunities/consequences for Belgian companies, M. Lor
27/06/2012
© 2011, VITO NV
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Evaluation
ISO 16000-11
» Sampling of test material
» Preparation of test material
» Building material emissions to indoor air, Opportunities/consequences
for Belgian companies, M. Lor
International Conference „Construction Products
and Indoor Air Quality“, W. Misch
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Sampling and analysis
» Active air sampling: actively drawing air (pump – mass flow controller) through
sorbent-filled tube
=sampling followed by offline analysis
» Aldehydes ISO 16000-3: active air sampling on DNPH cartridges, followed by
HPLC-UV
» VOC: ISO 16000-6: active air sampling on Tenax tubes, followed by TD-GC-MS
» Online analysis: THC analyser, no identification, just sumparameter
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Sampling and analysis
» Active air sampling: actively drawing air (pump – mass flow controller) through
sorbent-filled tube
=sampling followed by offline analysis
» Aldehydes ISO 16000-3: active air sampling on DNPH cartridges, followed by
HPLC-UV
» VOC: ISO 16000-6: active air sampling on Tenax tubes, followed by TD-GC-MS
» Online analysis: THC analyser, no identification, just sumparameter
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Sampling and analysis
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Sampling and analysis
» PM sampling
» Offline: sampling on filters and weighing
» Online: Grimm monitor – optical measurement
» SVOC sampling
» PUF – Soxhlet extraction…: high flow – long sampling time
» High flow: test chambers have flow restrictions!
» PDMS/Tenax:
»
»
»
»
Low flow (indoor air – test chamber air (flow restriction) – personal sampling)
gaseous and on PM fraction
No sample preparation
Validated for PAHs, exploration ongoing for other
SVOCs
Improved accuracy in the determination of polycyclic aromatic hydrocarbons in air
using 24 h sampling on a mixed bed followed by thermal desorption capillary gas
chromatography–mass spectrometry, Eric Wauters, VMM
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Sampling of the material
Transport of the sample
Storage of the sample before testing
ISO 16000-11
Test specimen preparation
Testing age and conditioning of the test
specimen
Measuring technique
ISO 16000-3
-6
Analyses
Evaluation procedure
AgBB, Afsset,…
Reporting, labelling
Building material emissions to indoor air, Opportunities/consequences for Belgian companies, M. Lor
27/06/2012
© 2011, VITO NV
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Evaluation
AgBB evaluation protocol
Mandatory
for flooring
materials
1st step:
identification
and
assessment
of chemical
composition
2nd step:
testing of
VOC and
SVOC
emissions
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Afsset evaluation protocol
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Products may only be
made available on the
market if they are
accompanied by a label,
applied to the product or
its packaging, indicating
their emissions of volatile
pollutants
1st september 2011 for
products placed on the
market
1st september 2013 for all
products
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Evaluation schemes and labels
Building material emissions to indoor air, Opportunities/consequences for Belgian companies, M. Lor
27/06/2012
© 2011, VITO NV
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Testing consumer products
cleaning agents, personal care,
air fresheners, …
Use scenario’s, use conditions
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Testing electronic equipment
ISO 16000-9: general requirements for emission test chamber measurements
Electronic devices: ‘active’ emissions sources => special aspects taken into consideration:
Duration of testing, sampling times and testing parameters
Electrical power => heat => higher levels of emissions
Equipment using consumables: printers (ink,…)
Equipment not using consumables: PC, TV,…
Size of equipment => 1 m³ test chamber
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SVOC emission testing
» No special emission measurements have been standardized for investigating
SVOC emissions of electronic devices
» Sink effect: released components partially adsorb at chamber walls =>
determined emission rate is incorrect
» Caused by chamber itself => use of appropriate materials (stainless steel)
» Also from sample itself: materials are good sinks for the substances emitted by
them e.g. porous building materials or foams
Uhde et al.,
Influence of molecular parameters on the sink effect in test
chambers, Indoor Air 2006; 16: 158–165
Time to reach equilibrium
concentration in the test chamber can
be considerably higher compared
with VOC measurements
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SVOC emission testing
» Principal compound analysis (PCA) reveals that sink effect essentially depends
on a compound’s boiling point (Uhde et al., 2006)
» Assessment of sink effects: introduction of pure standards of high boiling
compounds into test chamber = recovery test (as described in ISO 16000-25
for the micro-chamber)
» Assessment of SVOC in chamber testing:
» Sampling during test itself; then
» Device out of chamber and
» Heating of test chamber and simultaneously sampling, or
» Rinsing of the test chamber walls with appropriate solvent
» In addition: use of a cooled ‘fogging plate’ for the deposition of SVOC
emissions from electronic devices.
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SVOC emission testing – fogging device
•First used in testing of automobile interiors:
SVOC condense as a ‘fogging’ film on the
inner side of the windscreen
•After sampling, film is washed of wtih
solvent and analysed
•Value in µg is characteristic for SVOC
quantity to condense on cold indoor surfaces
Wensing M. Emissionen elektronischer Gerate. Neuere
Entwicklungen bei der Messung und Beurteilung der
Luftqualitat, VDI Berichte, vol. 1443. VDI-Verlag; 1999b. p.
765–74.
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SVOC emission decay
Ref. 2
Ref. 1
» SVOC emissions increase with increasing operating time (> 1 week)
 These emissions cannot be measured using short-time measuring
methods
» Due to sink effects and material properties of the studied device
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VOC emission decay
Wensing et al., Emissions from electronic devices: examination of computer monitors and laser printers in a 1 m³ emission
test chamber, proceedings of the 9th international conference on indoor air and climate
» VOC emissions:
» rapid increase in emission strength after turn-on
» Then slow decay over time
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PANDORA, prof. Marc Abadie, Univ. La Rochelle, France
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To conclude
» ESR3 Borislav Lazarov: start October
» Research work: determination of emission factors of FR
» Input for ESR4 (modelling indoor emissions)
» ESR2 secondment to VITO, ESR3 secondment to UB
» Visits to IVL, SU, VU, UA
» Questions?
» Now or
» [email protected] ; Boeretang 200, 2400 Mol, Belgium
» Thanks for your attention!
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Interesting lecture - references
1.
2.
3.
4.
5.
Plastics additives in the indoor environment—flame retardants and
plasticizers, Wensing et al., science of the total environment 339 (2005)
19-40
Emissions of organophosphate and brominated flame retardants from
selected consumer products and building materials, Kemmlein et al.,
Atmospheric environment 37 (2003), 5485-5493
Influence of molecular parameters on the sink effect in test chambers,
Uhde et al., Indoor Air 2006; 16: 158-165
Emission of flame retardants from consumer products and building
materials, BAM (http://www.umweltdaten.de/publikationen/fpdfl/2386.pdf)
Organic indoor air pollutants, edited by Salthammer and Uhde,
ISBN 978-3-527-31267-2, 2009
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