27/06/2012 1 © 2011, VITO NV

27/06/2012

The importance of sampling strategy, sample handling and storage for emission testing

F. Maes

27/06/2012 2 © 2011, VITO NV

Summary

» Product emission testing: why – what? » Indoor air

» Construction Products Directive (CPD)

» Emission test chamber experiments - general

» Evaluation protocols – product labels

» Consumer products / electronic devices emission testing

» SVOC emission testing

27/06/2012 3 © 2011, VITO NV

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

27/06/2012 4 © 2011, VITO NV

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

27/06/2012 8 © 2011, VITO NV Evaluation

Sampling of the material

Transport of the sample

Storage of the sample before testing

Evaluation procedure

Testing age and conditioning of the test

specimen

Measuring technique

Analyses

Test specimen preparation

Reporting, labelling

ISO 16000-11

ISO 16000-3

-6

AgBB, Afsset,…

Building material emissions to indoor air, Opportunities/consequences for Belgian companies, M. Lor

27/06/2012 9 © 2011, VITO NV

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

» 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

27/06/2012 15 © 2011, VITO NV Evaluation

Sampling of the material

Transport of the sample

Storage of the sample before testing

Evaluation procedure

Testing age and conditioning of the test

specimen

Measuring technique

Analyses

Test specimen preparation

Reporting, labelling

ISO 16000-11

ISO 16000-3

-6

AgBB, Afsset,…

Building material emissions to indoor air, Opportunities/consequences for Belgian companies, M. Lor

27/06/2012 16 © 2011, VITO NV

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

27/06/2012 18 © 2011, VITO NV

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

27/06/2012 20 © 2011, VITO NV

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

27/06/2012 21 © 2011, VITO NV Evaluation

Sampling of the material

Transport of the sample

Storage of the sample before testing

Evaluation procedure

Testing age and conditioning of the test

specimen

Measuring technique

Analyses

Test specimen preparation

Reporting, labelling

ISO 16000-11

ISO 16000-3

-6

AgBB, Afsset,…

Building material emissions to indoor air, Opportunities/consequences for Belgian companies, M. Lor

27/06/2012 22 © 2011, VITO NV

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

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Testing consumer products

cleaning agents, personal care, air fresheners, … Use scenario’s, use conditions

27/06/2012 27 © 2011, VITO NV

Testing electronic equipment

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

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

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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.

27/06/2012 30 © 2011, VITO NV

SVOC emission testing – fogging device

Wensing M. Emissionen elektronischer Gerate. Neuere Entwicklungen bei der Messung und Beurteilung der Luftqualitat, VDI Berichte, vol. 1443. VDI-Verlag; 1999b. p. 765–74.

•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

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SVOC emission decay

» 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

Ref. 1

Ref. 2

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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

» frederick.maes@vito.be ; Boeretang 200, 2400 Mol, Belgium

» Thanks for your attention!

27/06/2012 36 © 2011, VITO NV

Interesting lecture - references

1. Plastics additives in the indoor environment—flame retardants and plasticizers, Wensing et al., science of the total environment 339 (2005) 19-40

2. Emissions of organophosphate and brominated flame retardants from selected consumer products and building materials, Kemmlein et al., Atmospheric environment 37 (2003), 5485-5493

3. Influence of molecular parameters on the sink effect in test chambers, Uhde et al., Indoor Air 2006; 16: 158-165

4. Emission of flame retardants from consumer products and building materials, BAM (http://www.umweltdaten.de/publikationen/fpdf-l/2386.pdf)

5. Organic indoor air pollutants, edited by Salthammer and Uhde,

ISBN 978-3-527-31267-2, 2009