robustness validation of methods developed by cen/tc 351 ......validation of cen/tc 351/wg 2 draft...

Validation of CEN/TC 351/WG 2 draft CEN/TS 16516 / 109

Robustness Validation of Methods developed by CEN/TC 351/WG 2

(Draft TS 16516 / WI351006)

–

Summary report issued by project consortium

29. November 2012

Issued after approval and revision by CEN TC351 WG2

by

Reinhard Oppl 1), Dr. Matthias Richter 2), Dr. Olaf Wilke 2), Dr. Frank Kuebart 3)

1) Eurofins Product Testing A/S, Galten, Denmark

2) BAM Bundesanstalt für Materialforschung und -prüfung, Berlin, Germany

3) eco-INSTITUTGmbH, Köln, Germany

Project ordered and funded by

European Commission via

NEN – Netherlands Standardization Institute

for CEN / TC 351 / WG2

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Table of Contents 1. Introduction .................................................................................................................................... 4

1.1 Background and objectives ........................................................................................................ 4

1.2 Scope ......................................................................................................................................... 4

1.3 This document ............................................................................................................................ 4

1.4 Structure of work and report ....................................................................................................... 5

2. Verification of Available Comparative Data for Robustness Validation ................................... 6

2.1 Sample History (see cl. 5 in draft TS 16516) ............................................................................. 6

2.2 Preparation of the Test Specimen (see cl. 6.2 in draft TS 16516) ............................................. 6

2.2.1 Film thickness (liquid products) ....................................................................................... 7 2.2.2 Sample sealing (solid products) ....................................................................................... 7 2.2.3 Test Specimen Dimension and Sample Homogeneity .................................................... 8

2.3 Test Chamber Size (see cl. 7 in draft TS 16516) ....................................................................... 8

2.4 Test Chamber Climate (see cl. 7 in draft TS 16516)................................................................ 10

2.5 Ventilation, Product Loading and Area Specific Air Flow Rate (see cl. 7 in draft TS 16516) .. 12

2.5.1 Ventilation rate (see cl. 7 in draft TS 16516) ................................................................. 13 2.5.2 Loading factor (see cl. 7 in draft TS 16516)................................................................... 13 2.5.3 Area specific air flow rate (see cl. 7 in draft TS 16516) ................................................. 13 2.5.4 Air velocity above test specimen (see cl. 7 in draft TS 16516) ...................................... 14 2.5.5 Conclusions ................................................................................................................... 14

2.6 Test Chamber – Intermediate Storage (see cl. 6.2.g) in draft TS 16516) ................................ 14

2.7 Capillary GC column for analysis (see cl. 8.2.2 in draft TS 16516) ......................................... 15

2.8 Tube Conditioning and Laboratory Blank Tubes (see cl. 8.2.3 in draft TS 16516) .................. 17

2.9 Sampling Test Chamber Air (see cl. 8.2.5 in draft TS 16516) ................................................. 18

2.10 Calibration and Analysis (see cl. 8.2.6 in draft TS 16516) ..................................................... 19

2.11 Reference material for validation of the procedure (see cl. 8.2.9 in draft TS 16516) ............ 20

2.12 Determination of Total Volatile Organic Compounds (see cl. 8.2.7 in draft TS 16516) ......... 21

2.13 Determination of Formaldehyde / Volatile Carbonyls (see cl. 8.3 in draft TS 16516) ............ 22

2.14 Conclusions ............................................................................................................................ 22

3. Robustness validation of draft horizontal VOC emissions testing standard ........................ 24

3.1 Project design and selection of test samples ........................................................................... 24

3.2 Homogeneity testing ................................................................................................................ 24

3.3 Testing program and test results.............................................................................................. 25

3.3.1 Work package 1: Temperature and humidity ................................................................. 25 3.3.2 Work package 2.1: Chamber sizes ................................................................................ 30 3.3.3 Work package 2.2 – 2.4: Loading factor and ventilation ................................................ 32 3.3.4 Work package 2.1 – 2.4: Age of sample at start of test ................................................. 36 3.3.5 Work package 1, and 2.2 – 2.4: Determination of hexanal ............................................ 37 3.3.6 Work package 1, and 2.2 – 2.4: Determination of the VVOC n-pentane ....................... 38 3.3.7 Work package 3: Techniques for sealing back and edges ............................................ 39 3.3.8 Work package 4: Reference material for method validation .......................................... 40 3.3.9 Work package 5: Tenax TA tubes and benzene artefact generation ............................ 41

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4. Repeatability of testing within one laboratory .......................................................................... 42

4.1 Study design ............................................................................................................................. 42

4.2 Findings .................................................................................................................................... 42

4.3 Conclusions on repeatability within one laboratory .................................................................. 43

4.4 Detailed findings per tested product ........................................................................................ 44

5. Project results – summary and interpretation .......................................................................... 48

5.1 Conclusions on robustness validation of draft CEN/TS 16516 ................................................ 48

5.2 Conclusions on comparability with other testing standards ..................................................... 48

5.3 Further improvements .............................................................................................................. 48

6. Bibliography ................................................................................................................................. 49

ANNEX: Data obtained by laboratory testing ................................................................................... 53

A.1 Introduction .............................................................................................................................. 53

A.2 Testing Samples ...................................................................................................................... 53

A.3 Homogeneity testing ................................................................................................................ 54

A.3.1 Testing plan ................................................................................................................... 54 A.3.2 Results ........................................................................................................................... 57

A.4 Testing program and data ........................................................................................................ 58

A.4.1 Work package 1: Temperature and humidity ................................................................ 58 A.4.1.1 WP 1 – Results: Wooden flooring type product ......................................................... 59 A.4.1.2 WP 1 – Results: Wood-based panel type product ..................................................... 61 A.4.1.3 WP 1 – Results: Mineral wool type product ............................................................... 63 A.4.1.4 WP 1 – Results: Flooring type product ....................................................................... 64 A.4.1.5 WP 1 – Results: Liquid type product .......................................................................... 66 A.4.1.6 WP 1 – Results: Foam type product ........................................................................... 68 A.4.2 Work package 2.1: Chamber sizes ............................................................................... 70 A.4.2.1 WP 2.1 – Results: Foam type product........................................................................ 71 A.4.2.2 WP 2.1 – Results: Liquid type product ....................................................................... 72 A.4.2.3 WP 2.1 – Results: Solid reference material ............................................................... 73 A.4.3 Work package 2.2 – 2.4: Loading factor and ventilation ............................................... 74 A.4.3.1 WP 2.2 – 2.4 – Results: Flooring type product ........................................................... 76 A.4.3.2 WP 2.2 – 2.4 – Results: Foam type product .............................................................. 82 A.4.4 Work package 3: Sealing technique for back and edges .............................................. 98 A.4.4.1 Results – Wooden flooring type product .................................................................... 99 A.4.4.2 Results – Solid product with high emissions from back ........................................... 100 A.4.5 Work package 4: Evaluate reference material for method validation .......................... 102 A.4.6 Work package 5: Tenax TA tubes and benzene artifact generation ........................... 105

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1. Introduction

1.1 Background and objectives

The draft CEN/TS 16516 "Construction products – Assessment of emissions of regulated dangerous substances from construction products" (Work Item WI351006 of CEN/TC 351) is a draft standard for the determination of emissions from construction products into indoor air. The determination is done by the use of emission test chambers [1] in combination with appropriate sampling and analysis meth-ods [2-5]. Robustness validation of this draft emission testing standard should show any impact on test result if relevant testing parameters are modified. This is a purely descriptive task. There is no criterion availa-ble for assigning robustness or no robustness to a testing method. Only the degree of robustness can be documented. Interpretation then can lead to confirmation or modification of the testing parameters and their accepted ranges of variation during testing. Based on this study, CEN/TC 351/WG 2 changed some details of draft CEN/TS 16516 compared to earlier work-ing drafts. 1.2 Scope

Draft CEN/TS 16516 as horizontal testing standard contains only very general specifications on taking samples for testing and preparation of test specimens, as these shall be specified later in product spe-cific standards for CE marking. Therefore sampling, and specific issues of making a test piece, were not part of the robustness validation of the horizontal testing standard. The following internal documents of CEN/TC 351/WG 2 formed the basis of this study:

N129 – draft testing standard, now as final version in draft CEN/TS 16516 N146 – List of testing parameters that needed to be evaluated, identifying the relevance for

robustness validation for each parameter with a ranking from "0 = not relevant", via "1 = rele-vant", to "2 = very relevant".

N157 – detailed working plan for this project (repeated here in the respective clauses). 1.3 This document

This document combines the internal documents N154, N173 and N174 of CEN/TC 351/WG 2. CEN/TC 351 supported the publication of this report under the provision that

Publisher is the consortium, not TC 351, All test samples were characterized such that it is not possible to conclude on any specific

products, Suppliers of the tested samples agreed with the publication in this form, It was made clear in the text that the tested samples were selected such that the expected

emissions were higher than average; this does not allow at all to use the test data for general-ized conclusions or data base entries presuming that the tested products were typical for emissions of the involved product groups, and any such misuse must not take place,

Any recommendations to CEN/TC 351/WG 2 given by the consortium were deleted from the original texts.

These requirements were fulfilled by the consortium with this present report. The combination of the three documents into one document required a number of editorial changes and refinements, and some references are updated in this document – e.g. the references to specific chapters in the draft TC 351 testing standard have been updated to the latest version, draft CEN/TS 16516, as in the version of 7th November 2012 (internal document N189 of CEN/TC 351/WG 2).

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1.4 Structure of work and report

In a first step available comparative data (both published data, and available but unpublished data) from emission chamber tests were evaluated for their relevance and consequences for robustness val-idation, with focus on those parameters that had been rated as category "2=very relevant" in CEN/TC 351/WG 2 document N 146. While reviewing the available literature it was found that there exists only little published work dealing with the systematic validation of emission chamber measurements. Most of the relevant data is based on results and conclusions of round robin tests, in which only partially comparison of chamber meas-urements under different testing conditions had been done or could be read from the reports. Document N154 of CEN/TC 351/WG 2 "Collection and Verification of Comparative Data available for Robustness Validation of Methods developed by CEN/TC 351/WG 2" summarized existing information on robustness of the involved testing methodology, see chapter 2 of this report, and resulted in a rough testing program for filling remaining knowledge gaps. This was discussed and approved by CEN/TC 351/WG 2 in its meeting on 18th May 2011 (see the minutes in document N156 of CEN/TC 351/WG 2). Document N157 of CEN/TC 351/WG 2 "Interim report on the details of testing plan for robustness validation of methods developed by CEN/TC 351/WG 2 – Version 2 (31 August 2011)" detailed the project plan in terms of testing and was confirmed by CEN/TC 351/WG 2. The following testing laboratories participated in the experimental part of the study:

Eurofins Product Testing A/S, Denmark BAM Bundesanstalt für Materialforschung und -prüfung, Germany eco-INSTITUT GmbH, Germany (eco) Fraunhofer WKI Institut, Germany (WKI) IDMEC, Portugal Mapei s.p.a., Italy Saint-Gobain Isover, France Teknologisk, Denmark (DTI) VTT, Espoo, Finland

This list included a large part of the leading VOC emissions testing laboratories in Europe. Document N173 of CEN/TC 351/WG 2 "Final presentation of test data for Robustness Validation of Methods developed by CEN/TC 351/WG 2" contains the final data of the robustness testing project, see the annex of this report. Document N174 of CEN/TC 351/WG 2 "Presentation and interpretation of the data obtained, and pro-posals to amend accordingly the draft horizontal standard N129" evaluates and interprets the test data and their implications for the draft testing standard, see chapter 3 of this report. CEN/TC 35

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2. Verification of Available Comparative Data for Robustness Validation

This chapter is divided into sub-chapters following the structure of document N 146. All considerations are based on the requirements marked with “relevance = 2”, meaning “very relevant” for robustness validation. A reference to the clauses or sub-clauses of the draft standard is also given. This chapter was taken from CEN/TC 351/WG 2 internal document N154 and updated editorially. 2.1 Sample History (see cl. 5 in draft TS 16516)

Representative sampling of product for testing is of essential importance for the significance of test re-sults. This is explored in detail in a technical report, CEN/TR 16220 [6]. It is common practice for US American low VOC specifications that testing is performed in the frame of a certification process where the selection of samples for testing is in the hand of a third-party certifier and performed by a third-party auditor. All steps of sample taking, dispatch and receipt at the testing laboratory are documented in a form sheet, the so-called chain-of-custody form. All this shall ensure that experts are involved in selection of samples who are experienced in making such choices. There was identified no further information or publication on this issue. Unpublished experience indi-cates that both products exist where emissions may vary strongly (with more than ± 50%), but also products with very low variation of emissions within and between production batches. Regarding the accepted time between sampling date and receipt at laboratory, and the time between receipt at laboratory and start of test, there were not found any data on the effect of both delays on test results. When ageing of the sample may influence emissions, then this is an important issue. The requirements for taking the sample in different test methods range from ‘immediately’ up to 8 weeks after sample is ready for distribution or up to three months for containerized products. The require-ments for starting the test may range from max 5 weeks up to max 8 weeks after sample is ready for distribution or up to max 4 months for containerized products, see e. g. [7-9]. All these considerations have been drafted when writing clause 5 of TC 351 draft standard. Sample age and history need to be specified having in mind the product specific characteristics and intended uses. Further specifications and possibly investigations should therefore be initiated by the product specific TCs when writing or expanding product performance standards for CE marking. At the moment no published data are available on the influence of sample age on emission test re-sults. 2.2 Preparation of the Test Specimen (see cl. 6.2 in draft TS 16516)

There is evidence that the preparation of the test specimen has an influence on the emission rates of VOCs and formaldehyde. The main aspects are sealing of edges (particle boards), backside sealing (flooring materials) or weight and thickness (liquids or adhesives). For this reason most round robin tests have been conducted using material with no or only a simple preparation of test specimens. Therefore not much useful data is available. CEN/TC 35

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2.2.1 Film thickness (liquid products)

The amount of material in test chamber (expressed as mass or volume) should correlate with the emission source strength and thus with the emission rate. On the other hand, when a liquid product starts drying, it will form a film on the surface. From then on, emissions are no longer determined mainly by evaporation from the surface, but by diffusion of volatiles through this surface film. Several unpublished studies showed that there is some correlation between film thickness and emis-sion rate after 3, 7 and 28 days, but this was not linear in all cases. If two layers are applied then the waiting time before application of the second layer impacts the emissions test results. Sometimes there was even observed no change of emission rate with change of thickness at all. The total surface seems to influence the emission rate – as is relevant for e.g. those adhesives where not the whole surface is covered, or where the adhesive is applied as structured surface. Time until formation of this film is decisive for how many volatiles have evaporated, meaning how many volatiles still are available for being emitted before this change of emission mechanism oc-curred, respectively. This may influence the duration during which emission can occur [10]. In a study carried out by deBortoli et al. [11], the possible influence of paint film thickness on the spe-cific emission rate values has been investigated, attempting to correlate values of Texanol specific emission rate after 48 h with the reported coating density of the paint specimens. However, no correla-tion could be identified. But the study showed large deviations of test results, which might have cov-ered any effect of film thickness.

2.2.2 Sample sealing (solid products)

Some cases have been seen (but not in published studies) where front and back of a product showed extremely different emissions – especially when recycled material was used which cannot be con-trolled easily for their potential emissions. If only the upper surface is relevant for emissions, then in those cases the tightness of sealing technique for edges and back may impair test results [10]. If samples are cut and the fresh edges are showing different emissions than normally treated surfaces also then the tightness of sealing technique for edges and back may impair test results [10, 12]. Available sealing techniques are:

Mechanical tightening of surfaces: o Pressing a flexible flooring into a tray

Japanese seal box (e. g. JIS A 1901, Annex 2, cl. 2.2) Coverage (complete, or partial coverage if some open edges are typical for real application,

e.g. for tiles) o with aluminum foil o with aluminum tape o by placing two test pieces back-to-back in test chamber

Several studies have been performed by different test laboratories but no data were published. Results were used just to identify a tape that seals efficiently, but with very low emissions, not impair-ing the chamber test results. CEN/TC 35

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2.2.3 Test Specimen Dimension and Sample Homogeneity

According to TC 351 draft standard the size of the test specimen has to be adjusted in accordance with clauses 4.2.1 "Dimensions and loading factors in the reference room" and 7 "Test chamber condi-tions" of the testing standard. The intended use shall be taken into consideration. German DIBt testing protocol prescribes a minimum test chamber size of 0,225 m³ for testing solid floorings such as laminates and parquets – larger than for other products, to ensure a sufficient size of the test piece, for ruling out material inhomogeneity. The same testing protocol also specifies the fraction of joints between flooring tiles as well as a prepa-ration of test specimens that is close to the intended use [9]. For the validation study, material homogeneity is of high importance to ensure comparability of the dif-ferent sub-samples. Inhomogeneity may influence the evaluation of emissions from a product. This is also supported by recent inter-laboratory comparisons [13-17]. Main problem in these tests was a var-iability of chamber testing results that might have been caused either by sample inhomogeneity caus-ing different emissions of the test specimens, or by differences of the applied analytical proce-dures[18]. Solid products made from natural based raw materials, such as wood, cork or vegetable oils, may show considerable variation of emissions over surface due to inhomogeneous raw material. All solid materials may show variation of emissions over surface due to variations in production pro-cess (e.g. drying time, temperature, or drying duration). Any documentation on material inhomogeneity has to consider the uncertainty of the testing method itself. Only variation of emissions that are significantly higher than method uncertainty can be assigned to the tested material. In an inter-laboratory comparison organized by FCBA [19] a particle board glued with UF resin was conditioned unwrapped during 4 weeks in a climatic chamber at 23 ± 2 °C and 50 ± 5 % RH at 1 air change per hour. So treated samples showed relative standard deviations of emission of TVOC: 13 %, alpha-pinene: 21 %, and formaldehyde: 10 %. It should be noted that fresh samples might show much higher variation of emissions. In the GUT round robin test 14 sub-samples of PA6 carpet tiles with bitumen backing were tested for homogeneity of emissions of 32 VOCs by direct thermal desorption [20]. Variation was between 10% and 60%, with higher relative variability if the emissions were very low. Caprolactam showed even higher variability of emissions – this was later correlated with specific analytical challenges. 2.3 Test Chamber Size (see cl. 7 in draft TS 16516)

The question was whether test chamber size has an impact on emissions test result even with equiva-lent area specific air flow rate. Some less volatile products were suspected to re-condense on surfac-es – and the higher available surface in larger test chambers could reduce air chamber concentrations compared to smaller test chambers. For any test chamber comparison only test results in terms of specific emission rate per surface area and time should be used. If different loading factors or ventilation rates were applied in different test chambers, then this fact alone will give different chamber air concentrations, even when the area spe-cific rate remains constant: In theory, double the emission source should give 100% higher air concen-tration, and double ventilation rate should give 50% lower air concentration. This would be consistent with stating no impact of test chamber size on the test result. Therefore emission rates, rather than air concentrations, must be compared if different loading factors or different ventilation rates are applied. GEV round robin tests did not show any impact of test chamber size on test result [13].

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Only little data originating from within laboratory validation work is available. Wilke et al. [21] conduct-ed emission tests with rubber flooring in test chambers and cells of different volume (0,035 l (FLEC; 1 l; 20 l; 1 m³). The area specific air flow rate q was kept constant at 1,25 m³/m²h in all these cases. The comparative measurements of the emission from the rubber flooring showed an overall maximum standard deviation of 16 % for TVOC. A larger deviation was found between the FLEC test cell and the 1 m³ test chamber early during the test. Although a good comparability resulted for TVOC, single compounds showed some differences. For example styrene emission was much higher in the 1 liter cell, whereas highest emissions of sesquiterpenes were determined in the 20 liters chamber. But in contrast to this finding the other VOCs showed a very good correlation in all four test chambers. The authors saw a certain inhomogeneity of the material as a possible reason for the differences, even though a good homogeneity of the rubber flooring had been determined by headspace analysis. It also has to be taken into account that a proper sealing of the backside of the flooring material is very important for achieving good comparability between different chambers and cells (compare to chap-ters 2.2.2 and 3.3.7 of this reportError! Reference source not found.). BAM performed a comparison of measurements in two 1 m³ and one 20 liters test chambers where equivalent results were obtained [22]. Here, a good comparability between the emission test results in the two test chambers of different size was found. The BAM round robin test with a lacquer had to be performed by the participants with an area specific air flow rate q = 1 m³/m² h [15]. When comparing two classes of test chamber sizes (1 m³, and 20 - 255 liters) the test results from both test chamber types were statistically not equivalent for six out of seven compounds. Only for styrene equivalence could be demonstrated, probably because it showed the lowest standard deviation of all compounds in the test. Another comparison was made between the test results of measurements in large (450 - 1000 liters) and small (20 - 250 liters) test chambers used in the BAM round robin test with a sealant as test mate-rial and an area specific air flow rate q = 44 m³/m² h [16]. Both groups of test chambers showed the same variation of test results. This did not allow clear conclusions on the influence of the test chamber size on test results. Investigations on the emission of diisobutyl phthalate (as an example for a SVOC) in test chambers with different volume showed an impact of the test chamber size on the test result [21]. The emission rate in a 1 m³ test chamber was three times higher than in a 20 m³ test chamber. When comparing test results of TVOC with those of TSVOC in small test chambers (0,035 - 20 liters), it turned out that the standard deviation for TSVOC was higher, probably due to sink effects. Sollinger et al. [23] investigated the influence of test chamber volume on the initial emissions of a car-pet under dynamic (ventilated) conditions. Different pieces of the same carpet were tested in parallel in 30 l, 1 m³ and 38 m³ test chambers. The product loading factor used in the 30 l and in the 1 m³ test chambers was 0,8 m²/m³, the product loading factor in the 38 m³ test chamber was 0,4 m²/m³. The au-thors explained this difference with the geometry of the 38 m³ test chamber. The authors reported that after multiplying the measured concentrations in the 38 m³ test chamber by a factor of two (for the difference between the product loading factors – in fact then comparing the ar-ea specific emission rates), the comparability between the three test chambers was confirmed. They concluded that the maximum concentrations in the gas phase of a compound emitted from the tested textile flooring depend on the chamber loading. Furthermore it was found that the test chamber vol-ume has only little influence on the determined maximum concentration. This was supported by deBortoli et al. [18]. Based on test results obtained in an inter-laboratory com-parison they concluded that the wide range of test chamber volumes (0,035 l to – 1.5 m³) does not in-troduce any systematic difference of test results. This conclusion was supported by the fact that no significant correlation was found between test results and test chamber volume (with a probability P > 0,95) for n-dodecane (when expressed as relative difference between expected and observed emis-sion rate) and PVC tile (as emission factors).

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However, larger test chambers showed a tendency to give less scattered test results than smaller test chambers for a PVC tile. This may be explained by the heterogeneity of the material, which is more important for test results with a smaller test specimen in a smaller test chamber. With respect to the test chamber material they found that glass and stainless steel appear to be equal-ly suitable for test chamber measurements. Katsoyiannis et al. came to different results as reported above [24]. Emissions of VOCs and carbonyls from carpets of different type (wool, synthetic) over a time period of three days at T = 23 °C, RH = 45 %, n = 0,5 h-1 and L = 0,4 m²/m³ were measured and kept constant. The measurements were car-ried out in test chambers with different volume (0,02; 0,28; 0,45 and 30 m³). All carpet samples were tested in a 0,02, 0,28 and 0,45 m³ test chamber, two samples additionally in a 30 m³ test chamber. Large differences between the emission behaviour of the carpet samples in the different test cham-bers were observed, but it should be considered that the concentrations for most of the measured substances were far below 10 µg/m³ or even could not be detected because falling below the detec-tion limit. The highest concentrations were measured for 4-phenylcyclohexene (4-PCH, c = 170 µg/m³) and 2,2-butoxyethoxy-ethanol (2,2-BEE, c = 320 µg/m³) in the 30 m³ test chamber. This is also valid for the area specific emission rates, as a constant area specific air flow rate q had been applied (0,8 m³/m² h). Information about emission tests performed with the same area specific flow rate q in different emis-sion test chambers can also be read from reports on round robin tests. However, these tests were normally not performed with the aim to validate robustness and are not systematic in this sense. Thus, the comparability of emission chamber testing in test chambers of different size is given only excep-tionally. The most frequent explanation for this incomparability read from literature is inhomogeneity of the test specimens as well as huge variation of the analytical methods between different laboratories [14, 17, 19, 25-27]. Therefore, these data were not taken into consideration here. The examples mentioned above indicate that comparability between test results obtained with test chambers of different size sometimes could be demonstrated and sometimes not. But no publication of a systematic validation work could be found. Therefore, comparative tests were performed, see chapter 3.3.2 of this report. 2.4 Test Chamber Climate (see cl. 7 in draft TS 16516)

Temperature and relative air humidity in the test chamber are the most relevant climate parameters during emission test chamber measurements. The draft TC 351 standard starts from the specifications in ISO 16000-9 [1], but with further specifications, resulting in Temperature: 23 °C ± 1 °C (compare to ± 2 °C in ISO 16000-9) Relative humidity: 50 % ± 5 %. Both parameters may have a significant impact on emissions, so they cannot be varied for any type of product or test equipment without impairing the comparability of emission test data. The draft TC 351 standard incorporates the specifications of the testing standards ISO 16000-3, -6, -9 and -11. During the robustness validation process the comparability between measurement results was evaluated. This also included investigating the comparability between ISO 16000 standard series and the specifications for the measurement of the emission of formaldehyde given in EN 717-1 [18], which slightly differs from the ISO 16000 standard series: Temperature: 23 °C ± 0,5 °C Relative humidity: 45 % ± 3 %.

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EN 717-1 is the reference standard for formaldehyde emission testing for a number of products with urea-formaldehyde binder. But that test method was created for determining an equilibrium concentra-tion for the special case where formaldehyde is created continuously by chemical reaction of the bind-er with water from air humidity (hydrolysis). This reaction and the resulting emissions can be very sen-sitive to variation of temperature and relative humidity. Wilke et al. investigated the influence of temperature, relative humidity and air change rate on VOC emissions [29]. They loaded beech veneered particleboard coated with an UV-curable acrylate lacquer containing benzophenone as photo initiator into 1 m³ emission test chambers. The test series started after a conditioning time of 10 weeks in the test chambers under standard conditions, so that stable concentrations and emission rates could be expected. The compounds of interest were the higher boiling benzophenone and the lower boiling butyl acetate. During the 31 days lasting test series parameters were set as follows: Temperature [°C]: 18; 23; 28 Relative humidity [%]: 33; 45; 65 Air change rate [h-1]: 0,3; 0,5; 1,3; 2,0 Only one parameter each was changed per experiment, the others were kept at standard conditions (in this study: 23 °C, 50 % RH, 1,3 h-1). A change of the climate parameters gave different results when comparing butyl acetate and benzo-phenone concentration:

When increasing the temperature from 23°C to 28°C, the benzophenone concentration and emission rate showed a disproportional increase by a factor of 2,7. This is different from the more volatile butyl acetate where the concentration and emission rate increased by a factor of only 1,6.

Changing the relative humidity had about the same impact on both substances. Both concentra-tions and emission rates increased with higher humidity.

Under worst case conditions (n = 0 h-1, RH = 50 %, T = 28 °C), butyl acetate emission increased extremely by a factor of nearly 50 whereas benzophenone emission increased only by a factor of 6.

For the results regarding ventilation rate, please see chapter 2.5.1. Sollinger et al. came to similar conclusions [30]. They performed experiments under static conditions with ten types of floor coverings using two chambers under static (meaning not ventilated) conditions: A 33 liters glass chamber and a 1 m³ stainless steel chamber. The purpose of the static conditions was to identify initially emitted compounds and to determine their dependence on temperature and relative humidity. The temperature dependence of the emissions was studied by determining the static equilibrium con-centrations at 23, 30, 40, 50, 61 and 71°C. Based on their results the authors stated that with lower volatility of a compound its temperature dependence increases. The influence of the relative humidity on the emission process was also investigated. Samples of tex-tile floorings were exposed to relative humidity of 0 % and 45 %. Explicit results were not published, but it was reported that the equilibrium concentrations of these samples do not correlate with relative humidity. The authors concluded that for textile floorings it will not be necessary to maintain a constant and well-defined humidity of the test chamber air. In contrast to that, Gene Tucker [31] reported that test results may be affected by relative humidity in correlation with the molecular polarity of the compounds. He concluded that products containing highly polar compounds require good control of relative humidity. Non-polar compounds were only slightly af-fected by changing relative humidity of test chamber air.

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DeBortoli et al. [11] also reported temperature effects on the emission rate in the context of an inter-laboratory comparison. In this case they studied the emission of Texanol from a paint. One participat-ing laboratory ran its emission test chamber in a first test at 24,9 °C, deviating from the instructions of the test protocol. In a second test they repeated the measurements at 23,4 °C. The temperature in-crease by 1,5 °C caused an average increase of emission rate by 11,7 %, which was statistically sig-nificant (p < 0,05). This result confirms that temperature is a very important factor when determining the emission rate of Texanol from that paint. Wolkoff reported that both temperature and relative humidity affect emission rates, but with a strong dependence on the type of building product and type of VOC [32]. In this study the emissions of ten VOCs of concern from five building products were tested with the field and laboratory emission cell (FLEC) during up to 250 days. The following climate conditions were applied: Three different tempera-tures (23, 35 and 60 °C) and two different relative humidities (0 % and 50 % RH). Some of the VOC emissions were clearly influenced by different relative humidity and by different temperature, but the correlations were different per different type of emitted VOC. For example, while the emission / time profile was unchanged for Texanol with different relative humidity, the emission / time profile of propanediol reached a zero concentration at 0 % RH in less than one day. The author assumed that the low relative humidity may either have resulted in a different film structure due to a faster drying process, or alternatively the water vapor carried polar substances away from the surface when humidity was present in test chamber air. For most of the emitted VOCs, either a modest or a negligible effect was seen when increasing tem-perature from 23°C to 35 °C, while large effects were observed if increasing temperature to 60 °C. An increase up to 35 °C did not appear to have a clear influence on the (primary) source emission, but the temperature effect was higher for VOC emissions of a liquid building product than of a vinyl flooring. The author came to the conclusion that control of temperature and relative humidity for the studied VOCs could be maintained within an interval of ± 2 °C and ± 5 % RH without impairing validity of the test results. The test results given in the above cited literature showed that temperature and humidity may have a significant impact on the emissions from materials, depending on their physical and chemical proper-ties. All test results show the same basic effects, although with different characteristics that probably are related to different matrices and different involved VOCs. Therefore, systematic test series were performed with different matrices to obtain information about the influence of climate parameters on products with different composition and in different matrices (solid, porous and liquid), see chapter 3.3.1 of this report. 2.5 Ventilation, Product Loading and Area Specific Air Flow Rate (see cl. 7 in draft TS 16516)

Any identified documentation was based on change of several parameters (e.g. loading factor and ventilation) at the same time and most often simultaneously. A comparison of the emission rate where these parameters were changed separately and one by one (e.g. the loading factor, but not the ventilation rate), had not yet been published. Such an investigation is essential for making tests more affordable, especially if tests have been performed for other pur-poses (e.g. for EN 717-1, or for US specifications) with different loading factors or with different venti-lation rates than specified in the draft testing standard of TC 351. In these cases, it could be an ad-vantage if available test results obtained with one testing standard could be interpreted for other test-ing standards without new testing, just by recalculation to the deviating specifications.

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2.5.1 Ventilation rate (see cl. 7 in draft TS 16516)

Only little exploitable published work could be identified. Sollinger et al. [23] investigated the influence of the air change rate on the emission of 2,2,6,6-tetramethyl-4-methylideneheptane from a rubber flooring with a test chamber loading factor of 0,4 m²/m³ in a 1 m³ test chamber with three different air exchange rates (0,45; 0,9 and 1,9 h- 1). An increase of the air change rate from 0,45 to 1,9 h-1, i. e. by a factor of 4,2, reduced the concentra-tion only by a factor of 2,5. It was assumed that the material transfer from the rubber phase into the gas phase at the highest air change rate is enhanced, due to the increased concentration gradient with increasing air exchange. A comparison of emission rates had not been made and could not be calculated for this study because no detailed data were published, but only diagrams. In the study of Wilke et al. [29] mentioned above in chapter 2.4 with beech veneered particleboard coated with an UV-curable acrylate lacquer containing benzophenone as photo initiator in 1 m³ emis-sion test chambers, the test series started after a conditioning time of 10 weeks in the test chambers under standard conditions, so that stable concentrations and emission rates could be expected: Air change rate [h-1]: 0,3; 0,5; 1,3; 2,0

Climate: 23 °C; 50 % RH A modification of the air change rate gave different results when comparing butyl acetate and benzo-phenone concentration:

Decreasing the air change rate increased the butyl acetate concentration more than the concen-tration of benzophenone - the increase of the butyl acetate concentration was almost propor-tional to the decrease of the air change rate (as expected), which was not the case for benzo-phenone.

In parallel, it could be found that any change of the air change rate had no significant influence

on the emission rate of butyl acetate, whereas the emission rate of benzophenone showed con-siderable impact of the ventilation rate.

2.5.2 Loading factor (see cl. 7 in draft TS 16516)

In the context of an inter-laboratory comparison organized by de Bortoli et al. [18] it was found that the loading factor did not seem to have a significant impact on the test results. Three participating labora-tories with the smallest test chambers were using test specimen sizes which resulted in a loading fac-tor higher than prescribed. Even in the case of a 4 liters test chamber, where the loading factor was more than ten-fold higher than specified, the test results were comparable to those of the other labora-tories who worked in compliance with the testing protocol.

2.5.3 Area specific air flow rate (see cl. 7 in draft TS 16516)

Jann et al. tested a PU lacquer on solid alder wood in three different test chambers (20 m³, 1 m³, FLEC) and a UV lacquer on beech veneered particle board in four different test chambers (20 m³, 1 m³, 20 l, FLEC) with different loading factors and different air change rates but always with the same area specific air flow rate q of 1 m³/m² h [33]. TVOC results for the PU lacquer showed a good compa-rability. TVOC results of a UV lacquer showed larger differences, especially for the 20 m³ test cham-ber. The reason was interpreted as a sink effect impairing the main compound benzophenone. The evaluation of recent round robin tests organized by BAM where a constant area specific air flow rate was prescribed also showed good comparability for the tests in different test chambers, partly with different absolute loading factors. The concentrations of the main compounds showed standard devia-tions in the range between 20 and 30 % [15, 16].

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2.5.4 Air velocity above test specimen (see cl. 7 in draft TS 16516)

In the context of a round robin test with a paint, deBortoli et al. [34] addressed the issue of surface air velocity above the surface of the test specimen by requesting its measurement, prescribing a meas-urement position and urging the participants to arrange air circulation in such a way that the average air speed, at the point of measurement were as close as possible to 10 cm/s. The reported values of surface air velocity did not show any correlation with the emission test results. Therefore, apparently, the surface air velocity did not have a significant impact on test results. Howev-er, the measured air velocities showed large fluctuations, could not be controlled well in many test chambers, and it is uncertain how representative the values measured in the prescribed position are for the average air velocity. Moreover, the measurements were started when a solid film had already been formed at the paint sur-face in order to reduce the influence of surface air velocity – this limits the validity of the conclusions significantly, as the draft testing standard of TC 351 requires immediate transfer of liquid applied test specimens into the test chamber. Therefore, the impact of air velocity above the test specimen on the test result was further investigat-ed, see chapter 3.3.3 of this report.

2.5.5 Conclusions

No study could be identified investigating the impact on the emission rate of the single parameters (ventilation, loading, area specific air flow rate) separately. Therefore specific tests were needed to ob-tain such information. The work plan specified investigations in test chambers of four different volumes,

0,02 m³ 0,1 m³ - 0,2 m³ 1 m³ much larger than 1 m³;

with the following test plan, all with the same product in test chambers of the same volume:

Application of 3 different loading factors L at constant air change rate n Application of 3 different air change rates n at constant loading factors L Application of a constant area specific air flow rate q with simultaneously changing air change

rates n and loading factors L on three different levels 2.6 Test Chamber – Intermediate Storage (see cl. 6.2.g) in draft TS 16516)

Draft standard of TC 351 requires storage of test specimen in test chamber during the whole testing period. One of the reasons were data reported by BAM showing an increase of SVOC concentrations of up to ten days after loading the test chambers. An intermediate storage of the test specimen outside the test chamber (but with re-loading into the test chamber three days before air sampling) could therefore lead to lower test results [35]. The other reason is the risk of cross-contamination during storage together with other test materials. An example is given by Wilke et al. [29]. A beech veneered particleboard (covered with an UV cured acrylate lacquer) was stored together with untreated wood over 27 days and was tested on the 28th day under standard conditions in a 1 m³ test chamber. The consequence was a contamination with pinene, carene and phenol, when compared with a test without storage of the test specimen outside the test chamber.

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2.7 Capillary GC column for analysis (see cl. 8.2.2 in draft TS 16516)

Different gas chromatographic capillary columns for analysis of Tenax tubes after thermal desorption will give different separation of complex mixtures into its constituents, resulting in different identifica-tion and then different quantification. While ISO 16000-6 proposes a non-polar column (made of 100% poly dimethyl siloxane), the draft standard of TC 351 specifies a slightly polar column (made of 5% phenyl / 95% methyl polysiloxane) for achieving a better separation and analysis for more polar sub-stances than it is possible on the non-polar column. Today the involved testing laboratories make different selections of the column. TC 351 WG2 consid-ered it to be essential that this practice is harmonized for reducing variability of test results between laboratories. While ISO 16000-6 allows selection of another column than the specified one, the draft TC 351 standard requires use of the one specified column only. The use of a slightly polar column is rational with respect to today’s analytical requirements. An in-creasing number of polar compounds (e.g. alcohols, aldehydes, carbonic acids, esters and glycols) appear as emissions from interior construction products in the last few years, which can only be poorly chromatographed using a non-polar column. In a round robin test reported by Wilke et al. [16], detailed information on the analysis method that each participant used was collected. This included data on the capillary separation column (length, polarity), so that a comparison of the chromatography could be made. Figure 1 compares the test results using of butyldiglycol on a non-polar column and on a moderately polar column. It showed that the variation of the test results obtained with a non-polar column is signif-icantly larger. The mean value of the results of the slightly polar column (red line) is in better agree-ment with the target value (54,5 ng).

Figure 1: Results of the participants for butyldiglycol depending on the GC column used (DB1: non-polar type column, DB5: moderately polar type column). Red line: general mean value, dashed and solid lines: 1 and 2 sigma (standard deviation of the mean value and expanded uncertainty).

Also less polar components such as styrene (Figure 2) show a slight tendency to reach the target val-ue easier when using the slightly polar column.

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Figure 2: Results of the participants for styrene depending on the GC column used (DB1: non-polar column, DB5: slightly polar column). Red line: general mean value, dashed and solid lines: 1 and 2 sigma (standard deviation of the mean value and expanded uncertainty).

The advantage of using a moderately polar column can easily be seen from Figure 3, containing the standardized values (content normalized to the respective target value) for the two main column types. The mean values of the results of the slightly polar columns marked by pink squares show a good agreement with the respective target values and nearly all are close to 1. The values of the non-polar column are on average significantly lower (circa 0,85) than the target value.

Figure 3: Overview of the results of the participants depending on the GC column used (DB1: non-polar column, DB5: slightly polar column); the values are normalized to the target value.

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A comparable picture has also been obtained for the relative standard deviations: the results provided by the non-polar columns showed higher fluctuations than those obtained by the slightly polar columns (Figure 4).

Figure 4: Standard deviation of the participant results depending on the GC column used (DB1: non-polar column, DB5: slightly polar column). Since 9 participants used non-polar columns and 18 participants used polar columns, a fairly high con-fidence level in the statement can be assumed, although there were laboratories that used non-polar columns and nevertheless provided results well near the target value. A remaining challenge is that the definition of the VOC range is related to retention times on a non-polar column. Retention times may be different on a slightly polar column, which can be relevant for considering a substance as VOC or not with a retention time close to the borders of the VOC range. In other words, on one column type a substance may be within the VOC range and on the other column type outside of this range In real testing this happens only in very rare cases and with few substances. TC 351 WG 2 therefore decided to rate this as a non-significant problem and to accept assignment of a substance as VOC or not on basis of analyses on a slightly polar column: "Any change in component elution order … is min-imal and can be ignored." (cl. 8.2.2 of draft CEN/TS 16516). The existing knowledge obtained from the round robin test reported by Wilke et al. [16] allowed such a decision, and no further tests were necessary. 2.8 Tube Conditioning and Laboratory Blank Tubes (see cl. 8.2.3 in draft TS 16516)

The specified air sampling tubes filled with Tenax TA can generate blank values during air sampling. This can affect the detection limits of benzene, octanal and nonanal [36]. Other information from users of Tenax TA tubes with thermal desorption indicated decomposition of the Tenax TA material giving acetophenone, benzaldehyde and benzoic acid.

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BAM made the experience that nonanal is likely to be a reaction product of Tenax TA in the presence of ozone (which should not be present in test chamber air due to cleaning of the supply air). The main challenge is benzene. Benzene as artifact can be close to the limit value if this is required to be 1 µg/m³ due to its carcinogenic properties. The provided internal information from several laborato-ries did not give a clear picture [10]. Therefore the benzene artifact level on exposed Tenax TA sam-pling tubes was documented by further investigations, see chapter 3.3.9 of this report. 2.9 Sampling Test Chamber Air (see cl. 8.2.5 in draft TS 16516)

ISO 16017-1 specifies maximum safe sampling volumes for air sampling sorbents, among that Tenax TA. Within these limits theory would expect no correlation between both air sampling volume and ve-locity, and completeness of air sampling, and thus the emissions test result. The BAM round robin test in 2008 investigated any possible influence of air sampling volume and air sampling flow rate on test results [16]. Questionnaires supplied by the participants were evaluated for the parameters air sampling flow rate and air sampling volume. With most participants air sampling flow rate was l00 ml/min, its smallest value being 40 ml/min and the highest value 200 ml/min. No impact of air sampling flow rate on test results could be established from Figure 5 within this range. No influence of air sampling volume on test results could be established in the range between 1 and 9 liters. Figure 6 did not provide any tendency or dependence of the measured value on the air sampling volume. It can nevertheless happen that very volatile components break through and show false low test results if the sampling volume is too large.

Figure 5: Measured value as a function of air sample flow rate

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Figure 6: Measured value as a function of air sample volume

As shown in Figure 5 and Figure 6, no significant differences could be seen with different air sample flow rate and air sample volume. 2.10 Calibration and Analysis (see cl. 8.2.6 in draft TS 16516)

Horn et al. investigated the limit of quantification (LOQ) of all compounds listed on German LCI list and of 38 carcinogenic compounds [37]. An LOQ of ≤ 1 µg/m³ was confirmed for 78 % of the VOC with LCI limit value, assuming a sample volume of five liters. 18 % of the VOC had an LOQ of ≤ 5 µg/m³ and 4 % had an LOQ above 5 µg/m³. The carcinogenic substances were analyzed using the selected ion mode and an LOQ of less than 1 µg/m³ was confirmed for 34 out of 38 substances (89 %). Ethylene glycol showed to be a major component of VOC emissions from a special test adhesive for GEV round robin test 2003 [13]. The result for both ethylene glycol and TVOC depended heavily on whether this VOC was identified correctly and then quantified with its specific response factor. The lat-ter was important because the analytical response factor of ethylene glycol is very different from that of toluene (which is used for quantification of non-identified compounds). 14 out of 20 participants identified ethylene glycol, but only 6 out of 20 used the correct response factor for quantification. This means that correct analysis can be decisive for the test result. In this case this made the differ-ence whether the test result was above or below the acceptable TVOC level (at that time 500 µg/m³). A further step towards better reproducibility of emission testing could be the application of a uniform temperature program for gas chromatography. This would also standardize the evaluation of chroma-tograms since the separation of substances in the chromatogram would be more harmonized through-out Europe, increasing reproducibility of test results between different testing laboratories. For quality control reasons, draft CEN/TS 16516 recommends that testing laboratories regularly partic-ipate in round robin tests and/or use certified standard materials for calibration. Another possibility for a better and comparable analysis would be the use of the same standard solution for calibration by all test laboratories. Such a solution could be offered and distributed by an independent institute, e.g. by HSL within the WASP program.

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Further it would be an advantage to use a gas mixing and exposure system for sampling compounds on Tenax TA from a gas atmosphere with known and traceable concentration, see e. g. [38, 39]. The most efficient way of checking the complete test chamber method would be the use of a reference material for emission testing, see next chapter. . 2.11 Reference material for validation of the procedure (see cl. 8.2.9 in draft TS 16516)

NIST and Virginia Tech University now have available the know-how to produce a reference material for emission test chambers with toluene in a polymethylpentene (PMP) film. This was presented dur-ing a workshop at NIST in Gaithersburg (Maryland, USA) in April 2011 [40, 41]. Emission rate of that film is not constant over time after unpacking; but emission rate during the first days follows astonishingly well a mathematical model that relies on film properties (loading, diffusion properties) and chamber dimensions and ventilation. Some variation occurs with testing after 24h, but reliable results were obtained with different laboratories involved after 48h and 72h. This reference material is suitable to validate performance of the whole chamber testing procedure, including

ventilation, mixing and sink effects of test chamber, air sampling, analytical determination of toluene in air samples.

Until now these elements of emission chamber testing could be determined only separately; now the whole procedure can be checked against an independent standard that can be traced back to a prima-ry unit – the weight increase of the PMP film during loading. This makes this new material unique and relevant. This reference material until now is NOT suitable to validate test chamber testing performance with re-spect to

simulation of re-adsorption/re-desorption of once emitted VOCs on surface of test specimen made from real product samples (e.g. porous products with high surface),

simulation of the impact of drying / curing / ageing of real samples on emission rate, interaction of less volatile and of reactive VOCs with test chamber walls and sinks,

and their impact on emission rate. Therefore use of the reference material cannot substitute a validation of the whole test method with specific types of real samples. Nevertheless it can test the performance of the testing procedure as such, with the non-polar VOC toluene,

without taking into account the performance of the procedure for VOCs that are more polar and/or less volatile than toluene;

o this could be overcome with the development of similar reference materials made of some 2 – 4 additional VOCs representing classes of such VOC (e.g. n-butanol, do-decane, glycols, formaldehyde), which was reported to be planned by Virginia Tech University.

without taking into account product specific aspects;

o this is no problem for a method validation, as the method should be generic, and then it should be adapted later to specific product groups if necessary.

CEN TC 351 WG2 tested this reference material by including it in some comparisons, e.g. for compar-ing any impact of test chamber size on emission rate once for real samples, and once for reference material. And CEN TC 351 WG2 made use of this new development by including a test run with this reference material for toluene including all involved laboratories. In conclusion, this was included as an option in clause 8.2.9 on quality control of draft TS 16516.

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2.12 Determination of Total Volatile Organic Compounds (see cl. 8.2.7 in draft TS 16516)

TVOC is the total of all volatile organic compounds. This can be calculated in different ways:

as sum of all individual VOCs above a certain threshold (e. g. 5 µg/m³), each calibrated with its own response factor, with all non-identified VOCs calibrated as toluene equivalent (with the response factor of toluene).

as sum of o all individual VOCs on a target list (e. g. German LCI list), each calibrated with its own

response factor; o plus all identified VOCs NOT on that target list, calibrated as toluene equivalent (with

the response factor of toluene); o plus all non-identified VOCs, calibrated as toluene equivalent (with the response fac-

tor of toluene); o in any case VOCs are included only if above a certain threshold (e.g. 5 µg/m³); o this is the procedure in use for German DIBt testing.

as sum of all individual VOCs above a certain threshold (e.g. 5 µg/m³), each calibrated as tol-uene equivalent (with the response factor of toluene) - this is the procedure specified in draft CEN/TS 16561.

as total area of the chromatogram calibrated as toluene equivalent (with the response factor of toluene) - this is the procedure in use for ISO 16000-6.

The threshold of 5 µg/m³ was selected for including only VOCs that can be determined with a reason-able accuracy. Traces of VOC generate very weak signals during analysis which is much more vul-nerable to analytical errors than higher VOC amounts. Table 1 shows how TVOC values, obtained with MS or with FID. 27 pairs of TVOC test results were compared, taken from unpublished studies on floorings, coatings and glues in different laboratories. TVOC test results were available either as toluene equivalent, or calculated as for German DIBt regu-lation. Table 1: Correlation of TVOC calculated as for DIBt regulation or obtained as toluene equivalent. Measurements were done with MS or with FID. Range of ra-tio TVOC (DIBt) / TVOC (TE)

Total <0,9 0,9 - <1 = 1 >1 - 1,5 >1,5 - 2 >2

Number of values

27 2 3 2 15 2 3

In Table 1 a ratio of 1 means that both TVOC values are identical. A ratio x larger than 1 means that TVOC as in above DIBt option is x times larger than a TVOC, expressed as toluene equivalent. In 5 cases TVOC results obtained with the DIBt method were lower than those obtained as TVOC equiva-lent. In 2 cases TVOC the results were identical. In the majority of cases TVOC results obtained with the DIBt method was higher than those obtained as TVOC equivalent.

This shows that each of these calculation methods gives different results. It is necessary to select one of these options to make sure that results are comparable. Further testing was not needed. The same applies to total SVOC determinations.

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2.13 Determination of Formaldehyde / Volatile Carbonyls (see cl. 8.3 in draft TS 16516)

ISO 16000-3 standard is the state-of-the-art for the determination of formaldehyde and other volatile carbonyl compounds. Data on precision and uncertainty is summarized in Annex A of that standard. Another exercise for validation was performed during development of a reference material within a Eu-ropean project [40]. This method is validated regularly in ring trials organized by Health and Safety Laboratory (UK) within its program WASP [41].

Yrieix et al. and Salthammer et al. reported an underestimation of pentanal and hexanal when using DNPH cartridges compared to Tenax thermal desorption [19, 42].

2.14 Conclusions

From the review of literature about the impact of different test chamber parameters (chamber size, loading, air change rate, climate, and details of air sampling and analysis) it can be seen that only little systematic research has been performed for validation of the test chamber method (ISO 16000-9, -3, -6). Although the first inter laboratory comparison on test chamber measurements for VOC was per-formed in 1997 [11] no validation of this test method was established until today.

The following conclusions for the experimental validation work were drawn from the collected available data.

Preparation of test specimen

No data was available comparing the effect of different sealing techniques for the test of flooring and other materials having cutting edges. Therefore a systematic study of the impact of sealing techniques on test result was performed within the experimental part of the robustness validation program, see chapter 3.3.7.

Test chamber conditions (chamber size)

Only little data originating from tests in different chambers within one laboratory are available. Most of these data are only from round robin tests. Therefore a systematic study of the impact of chamber size on test result was performed within the experimental part of the robustness validation program, see chapter 3.3.2.

Test chamber conditions (climate conditions)

Some studies had been done on the impact of temperature and relative test chamber air humidity with contradictory results depending on volatility and polarity of compounds. Therefore a systematic study of the impact of test chamber climate parameters on test result was performed within the experimental part of the robustness validation program with a solid, a porous and a liquid product, see chapter 3.3.1.

Test chamber conditions (ventilation, loading and area specific air flow rate)

No study had been done investigating separately the impact of ventilation, loading, and area specific air flow rate on the emission rate. Therefore a systematic study was performed within the experimental part of the robustness validation program, see chapter 3.3.3.

Test chamber conditions (intermediate storage)

There is data available showing that intermediate storage can cause contamination if different sam-ples are stored together. There is also an influence on SVOC concentration when samples are placed in the test chambers only three days before testing and else stored outside the test chamber. No fur-ther tests are needed, see chapter 2.6.

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Tube conditioning and laboratory blank tubes

Some artefacts are known to be generated from Tenax TA tubes which affect the tube blank value. The most problematic one is benzene. To improve the detection limit for benzene a systematic study on significance and control of benzene artifact generation was performed within the robustness valida-tion program, see chapter 3.3.9.

Sampling test chamber air

Available data did not show any influence of air sampling volume or air sampling flow within the speci-fied range. No further tests are needed, see chapter 2.9.

Capillary GC column

The available data can be regarded as sufficient. Use of a slightly polar column is rated as beneficial. No further tests are needed, see chapter 2.7.

Calibration and analysis

The analytical procedures as specified in document N 129 and ISO 16000-6, -9 and -11 allow a num-ber of free selections regarding details of analysis procedure for VOCs sampled on Tenax TA and analyzed by thermal desorption, gas chromatography and mass spectroscopy. A harmonized analyti-cal procedure as prescribed in clause 8 of draft CEN/TS 16516 is expected to help achieving smaller differences between test results obtained by different testing laboratories. Nevertheless, no further tests are needed.

Increased use of reference material for validating elements of the testing procedure is recommended in draft CEN/TS 16516. Furthermore, establishment of applicability of a new reference material for val-idating the whole emissions testing procedure with known emissions of toluene is recommended, see chapter 3.3.8.

It was also deemed necessary to harmonize the interpretation/integration of chromatograms.

Determining the emissions of total volatile organic compounds

There are different definitions for the determination of TVOC. One of these had to be selected for achieving comparable results. No further tests are needed, see chapter 2.12.

Determination of formaldehyde and some other carbonyl compounds

For formaldehyde, butanal, propanal, acetone and crotonaldehyde ISO 16000-3 can be used. For some other carbonyl compounds, such as pentanal and hexanal, underestimation is reported, when compared to ISO 16000-6. No further tests are needed, see chapters 2.13 and 3.3.5.

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3. Robustness validation of draft horizontal VOC emissions testing standard

3.1 Project design and selection of test samples

Robustness validation of the draft emission testing standard, now draft CEN/TS 16516, had been per-formed by investigation of the impact on test result if selected testing parameters were modified one by one. Test samples were acquired from industry. The samples were selected in such a manner that they would represent different product types and different emissions mechanisms, and that they were ex-pected to show measurable emissions even after 28 days. One sample even was spiked with some VOCs for better use within this validation project. This means that the test results do not represent the whole group of products at all. The test results reported here only represent the especially selected testing samples. 3.2 Homogeneity testing

The samples were acquired from industry and then tested by BAM for homogeneity. Any effect of test-ing parameters observed in this report needs to show larger differences than the reported inhomoge-neity for being rated as relevant. Homogeneity tests were run earlier and thus with fresher samples than all other tests. They had been performed before the test samples were dispatched to the laboratories for characterizing the samples sent.

Findings

Homogeneity testing showed variation of emissions within the test samples between less than 10% and some 20% relative standard deviation of 4 or 6 test results for most products. Only one product (wooden flooring type products, "D") showed higher variation – and this only because one out of 6 test results was twice the other test results. Fig. 7 Inhomogeneity of products (see Annex A.3), given as relative standard deviation of test results

A = Flooring type product, B = Mineral wool type product, C = Liquid type product, D = Wooden flooring type product, E = Foam type product, F = • Solid product with high emissions from back, G = Wood-based panel type products .

Numbers after letter = individual VOCs, see results in table in Annex A.3.

0%

10%

20%

30%

40%

50%

A1 A2 A3 A4 A5 B1 C1 C2 C3 C4 C5 D1 E1 E1 E3 F1 G1

Product inhomogeneity

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3.3 Testing program and test results

The test program was designed in a manner that test chamber parameters were varied one by one for detecting their impact on VOC emission. In theory, the area specific emission rate (the emitted mass of substance per hour and per square me-ter) should remain constant during comparative testing. But it cannot be expected that this area specif-ic emission rate would be exactly the same in all individual tests due to influences such as ageing of samples, product inhomogeneity, and analytical differences between the involved laboratories.

3.3.1 Work package 1: Temperature and humidity

Goal: Study the impact on test result of changed temperature in test chamber in the range 19°C – 27°C with constant absolute humidity of

chamber supply air; changed RH of chamber supply air in the range 45% – 55% with constant temperature in test

chamber for three materials emitting formaldehyde based on different release mechanisms, and three materials emitting VOC with different emissions characteristics. Temperature range was larger than the range accepted in draft CEN/TC 351 standard for better being able to detect any correlations with test results larger than material inhomogeneity and analytical uncertainty.

Detailed findings

Temperature in test chamber:

The tested wooden flooring type product showed some increase of emissions with higher temperature but only for formaldehyde emissions (with a doubling of emission rate when in-creasing temperature from 19°C to 27°C). There was no clear trend for the other VOCs.

The tested wood-based panel type product showed no clear trend, even for formaldehyde. It should be noted that other but much older investigations [e.g. 43] – though under different testing setup – had shown a stronger impact on the area specific emission rate of formalde-hyde.

The tested mineral wool type product showed an increase only of formaldehyde emissions with higher temperature, but only after three days, not later on. The same product showed a slight decrease of ethylhexanol after three days. But these differences were not much larger than inhomogeneity of the material and analytical uncertainty. And it cannot be precluded that this VOC was emitted from the aluminium tape used for sealing back and edges, and not from the product itself.

The tested flooring type product showed some increase of emissions with higher temperature (with a doubling of emission rate when increasing temperature from 19°C to 27°C for some VOCs, especially for hexanal and for hexanoic acid, but not for acetic acid).

The tested liquid type product showed high variation of results. Experience from equivalent tests allows explaining this with very high initial concentrations of VOC and of water in test chamber. No observable trend could be detected that would have been stronger than this var-iation.

The tested foam type product showed large decrease of emissions of the VVOC n-pentane over storage time before start of test. No observable trend of emissions with increased tem-perature could be detected that would have been stronger than this decrease.

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Figure 8 Examples of change of specific emission rate with temperature (in °C); shown as % of test result obtained at 23°C after 4 weeks in test chamber (see Annex A.4.1).

- Formaldehyde, emitted from wooden flooring type products, wood-based panel type products, Mineral wool type product.

Figure 9 Examples of change of specific emission rate with temperature (in °C); shown as % of test result obtained at 23°C after 4 weeks in test chamber (see Annex A.4.1).

- Acetic acid, emitted from wooden flooring type products, wood-based panel type products, flooring type product. - Hexanal, emitted from flooring type product. - DEP, emitted from liquid type product.

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19 23 27 19 23 27 19 23 27

Emission rate and temperatureFormaldehyde

Wooden flooring, wood‐based panel, and mineral wool type product

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19 23 27 19 23 27 19 23 27 19 23 27 19 23 27

Emission rate and temperatureAcetic acid (3 x), hexanal, DEP

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Relative humidity of test chamber inlet air:

The tested wooden flooring type product showed a slight increase of formaldehyde emissions of some 20% (in some cases even some 50%) with higher relative humidity in the range 45% – 55%. This variation was slightly above analytical uncertainty and material inhomogeneity. There was no clear trend for other VOCs.

The tested wood-based panel type product showed an increase of emissions (+50% – 100%) of hexanal with higher relative humidity in the range 45% – 55%. There was no clear trend for other VOCs, even formaldehyde. It should be noted that other but much older investigations [e.g. 43] – though under different testing setup – had shown a stronger impact on area specific emission rate of formaldehyde.

The tested mineral wool type product showed an only slight increase of formaldehyde emis-sions (+20%) with higher relative humidity in the range 45% – 55%. This variation was close to analytical uncertainty and material inhomogeneity. There was no clear trend for the other VOCs.

The tested flooring type product showed no clear trend of VOC emissions with increased rela-tive humidity.

The tested liquid type product showed high variation of specific emission rates because of very high initial concentrations of VOC and of water in test chamber. No observable trend of emissions with increased relative humidity could be detected that would have been stronger than this variation.

The tested foam type product showed large decrease of emissions over time. No observable trend of emissions with increased relative humidity could be detected that would have been stronger than this decrease.

Figure 10 Examples of change of specific emission rate with relative humidity (in %); shown as % of result obtained at 50%RH after 4 weeks in test chamber (see Annex A.4.1).

- Formaldehyde, emitted from wooden flooring type products, wood-based panel type products, Mineral wool type product.

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45 50 55 45 50 55 45 50 55

Emission rate and relative humidityFormaldehyde

Wooden flooring, wood‐based panel, and mineral wool type product

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Figure 11 Examples of change of specific emission rate with relative humidity (in %); shown as % of result obtained at 50%RH after 4 weeks in test chamber (see Annex A.4.1).

- Acetic acid, emitted from wooden flooring type products, wood-based panel type products, flooring type product. - Hexanal, emitted from flooring type product. - DEP, emitted from liquid type product.

Wet applied products: The tested liquid type product that has been wet applied on an inert substrate showed large variation of test results. This can be explained by the very high concentrations in test chamber in the early phase of emissions testing:

High initial VOC concentrations can be partly adsorbed at, and later re-desorbed from test chamber walls, leading to contribution of "early" emissions to "later" emissions, even to those tested after e.g. 14 or 28 days. This is only partly predictable because these sink effects depend on test chamber geometry and air flow through test chamber, and this can easily differ between different types of test chambers. It should be noted that the tested product was especially prepared for showing high emissions.

High initial water concentrations can occur in case of water-based wet-applied products with high water content. This can lead to temporary condensation of water on test chamber walls. It cannot be excluded that some VOCs then can be dissolved temporarily in such condensed water, thus impairing the test result at certain points of time. During periods with high humidity in the test chamber even some condensation of water in air sampling tubes cannot be excluded. This water can contain dissolved VOCs and then induce high VOC test results if such condensation occurs.

Kramberger et al. [44] reported relative humidity around 100% in test chamber air when they placed 4 test specimens of plaster or putty products into different test chambers. Application amount was 4000-4800 g/m², and loading factor was 1,4 m²/m³ (scenario = walls + ceiling). It took between 5 and 8 days before humidity in test chamber air decreased down to 50%. This underlines the relevance of high ini-tial water concentrations in test chamber air.

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45 50 55 45 50 55 45 50 55 45 50 55 45 50 55

Emission rate and relative humidityAcetic acid (3 x), hexanal, DEP

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Summary of findings, conclusions

Some increase of emission rate with higher temperature was observed for some VOCs and some of the tested products, but in most cases to a low extent, and not for all VOCs and all products. Both some increase and some decrease of emission rate with higher relative humidity was observed for some VOCs and some of the products, but to a lower extent than for temperature, and not for all VOCs and all products. In some cases contradictory trends were observed for substances with differ-ent chemical and/or physical properties, within one set of comparative experiments. CEN/TC 351/WG 2 decided to maintain the acceptable range of temperature and relative humidity within ± 1°C and ± 5% RH, but with further specifications allowing short-term higher deviations, as long as the overall stability of temperature and relative humidity is given. A narrower interval cannot be justified by the obtained test data. A broader interval was rejected with the intention to avoid any im-pact of temperature and relative humidity on emissions, even for substances and products with high-est climate sensitivity of emission rates.

Wet-applied products High initial concentrations of water and of VOC in test chamber disturbed reliability of VOC determina-tion after 3 days, but also impacted testing after 14 days and 28 days. It is important to understand that this will not happen in reality because these initial concentrations will be adsorbed on walls made of wood, gypsum or concrete, and these adsorbed VOCs will not be desorbed from these surfaces as fast as from stainless steel test chamber walls. A possible solution is a separate pre-conditioning period outside the testing chamber before start of actual test that can avoid such effects. This would reflect the fact that rooms with freshly coated sur-faces normally will not be used immediately after coating, or at least with increased ventilation. Test specimens then are placed each in a separate environment (e.g. another chamber) during e.g. 3 days. Any water and VOCs initially adsorbed on walls then will stay in the pre-conditioning device and no longer impact emission testing. In that case only a dry or pre-dried product would be tested in actu-al test chamber – this would increase reliability of testing significantly. If a pre-conditioning period is applied for certain wet-applied products then it is essential to ensure that no cross-contamination between different test specimens can occur. Separate pre-conditioning cham-bers or similar solutions are specified in draft CEN/TS 16516, with ventilation and climate parameters being similar to actual test chamber, in any case within the range accepted by draft horizontal stand-ard. It is important that the time of transfer of test specimen into actual test chamber is regarded as starting time of test, and no emission test shall be performed at all immediately after that transfer. Sta-ble air concentrations in the test chamber require efficient mixing during several air changes before a reliable air measurement is possible. Formaldehyde Formaldehyde showed smaller influence of changes in temperature and humidity than expected. Ob-servable effects were seen mainly for mineral wool type products and for wooden flooring type prod-ucts, but not for wood-based panel type products. Therefore results obtained with the testing parame-ters specified in EN 717-1 ( (23 ± 0,5)°C and (45 ± 3)% RH) showed to be comparable with VOC test-ing if relative humidity remains within the overlapping interval of (45-48)% RH – and vice versa. It was demonstrated in chapter 3.3.3 that a recalculation between different loading factors and ventilation rates is possible within the relevant range. This is in contradiction with theoretical calculations of formaldehyde emissions that have been report-ed earlier [43] for a limited number of wood-based panels showing higher ranges of formaldehyde emissions than investigated in this study. A hypothesis is that the "Andersen formula" type theoretical calculations may not give precise predictions of experimentally determined formaldehyde emissions from low emitting wood-based type products as they are manufactured today, especially if the final product is coated.

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3.3.2 Work package 2.1: Chamber sizes

Goal: Study the impact on test result (in terms of area specific emission rate) when using 4 different test chamber sizes (20 l, 119 l, 1 m³, 3 m³) with constant loading factor and ventilation rate with products of different susceptibility to this parameter. According to theory, the area specific emission rate (µg/m²h) should remain constant in the selected range.

Detailed findings

The tested foam type product showed a slight tendency to higher specific emission rate in a smaller test chamber for some VOCs, namely styrene and ethyl benzene. This could be explained by the dif-ferent geometry of such samples in different chamber volumes. Even if all edges and the back have been covered by aluminium foil, it cannot be precluded that some small gaps between surface and foil lead to unexpected additional emissions. As height of test specimen had to be kept constant, the sur-face of edges and back relative to top surface is larger, and therefore the impact of these additional emissions on test result from edges is stronger in smaller test chambers than in larger ones. The VVOC n-pentane showed the opposite trend. This could be explained by the fact that n-pentane can be released already during the preparation of the test specimen. The smaller the test chamber, the larger is the total surface of the test specimen relative to its volume, and the larger is the potential loss of n-pentane before the test specimen is prepared and placed in the test chamber. Further to that, air sampling on Tenax TA is not a good method for VVOC monitoring due to low adsorption capacity of very volatile substances. This fact may impair the reliability of this finding. The tested liquid type product showed some differences between test results in test chambers of dif-ferent size, but these did not show a systematic trend. The reference material showed a satisfactory correlation between all test chambers except the 3 m³ test chamber which had the lowest loading factor. It could not be resolved whether the model for cal-culating expected emissions does not fit well under these conditions, or whether the 3 m³ test chamber (where also a lower loading factor had been applied) showed lower recovery (55% after 2 days and 62% after 3 days) than the involved smaller test chambers. Figure 12 Examples of specific emission rate in test chambers of different size; shown as % of result obtained in 1 m³ chamber after 4 weeks in test chamber (see Annex cl. A.4.2.1 and A.4.2.2).

- Styrene and n-pentane emitted from foam type product - DEP emitted from liquid type product

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L M S VS L M S VS L M S VS L M S VS L M S VS

Emission rate and test chamber sizeL=3,2 m³, M=1 m³, S=0,12 m³, VS=0,02 m³

Styrene (3d, 14d, 28d), DEP (28 d), n‐pentane (3d)

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Figure 13 Examples of specific emission rate in test chambers of different size; shown as recovery as % of predicted emission rate

- Toluene emitted from spiked films (reference material)(see Annex cl. A.4.2.3). Note: The test in large test chamber (3,2 m³) was performed at lower loading factor than in the other test chambers.


All in all, the involved test chambers with volumes between 20 liters and 3 m³ were comparable be-cause no general trend was observable. It could not be seen that larger or smaller chamber size al-ways and systematically would induce different area specific emission rate.

Any limitations of largest and smallest acceptable test chamber size only can be founded on inhomo-geneity of sampling material: Larger test specimens, as required for larger test chambers, will rule out inhomogeneity of tested products better than smaller test specimens for smaller test chambers.

The achieved data confirmed the present specifications in the draft horizontal testing standard.

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L M S VS L M S VS L M S VS

Emission rate and test chamber sizeL=3,2 m³, M=1 m³, S=0,12 m³, VS=0,02 m³Toluene, reference material (1d, 2d, 3d)

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3.3.3 Work package 2.2 – 2.4: Loading factor and ventilation

Goal: Study the impact on test result (in terms of area specific emission rate) of different air change rates with constant loading factor (0,4 m²/m³), different loading factors with constant air change rate, and with air change rate and loading factor changed simultaneously (with constant area specific air flow rate q at three levels). According to theory, the area specific emission rate (µg/m²h) should remain constant in the selected range.

Detailed findings

Flooring type product: A clear trend of VOC emissions when changing testing parameters could not be observed.

Figure 14 Examples of specific emission rate in test chambers at different loading factors and ventilation rates:

Left: 0,3 / 0,7 / 1,5 m²/m³ with ventilation 0,7 /h; shown as % of 0,7 m²/m³ Center: 0,3 / 0,7 / 1,5 /h with loading factor 0,7 m²/m³; shown as % of 0,7 /h Right: 0,3 / 0,7 / 1,5 m²/m³ with ventilation 0,3 / 0,7 / 1,5 /h; shown as % of 0,7 m²/m³ with 0,7 /h

Blue = 1 m³ test chamber, red = 0,125 m³ test chamber; all after 4 weeks in test chamber (see Annex cl. A.4.3.1).

Figure 15 Examples of specific emission rate in test chambers at different loading factors and ventilation rates: details as in figure 14 (see Annex cl. A.4.3.1).

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0,3 0,7 1,5 0,3 0,7 1,5 0,3 0,7 1,5

Emission rate, loading, ventilation Flooring type product ‐ Acetic acid (28 d)

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0,3 0,7 1,5 0,3 0,7 1,5 0,3 0,7 1,5

Emission rate, loading, ventilation Flooring type product ‐ Hexanal (28 d)

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Foam type product:

No clear trend of emissions of styrene and ethyl benzene when changing testing parameters could be observed.

Results for the VVOC n-pentane were strongly influenced by age of sample. This dominated any possible other effect. The tested foam type product showed large decrease of emissions of n-pentane over time. No observable trend could be detected that would have been stronger than this decrease.



Blue = 1 m³ test chamber, red = 0,255 m³ test chamber; all after 4 weeks in test chamber (see Annex cl. A.4.3.2).


- details as in figure 16 (see Annex cl. A.4.3.2).

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0,3 0,7 1,5 0,3 0,5 0,7 1,5 0,3 0,7 1,5

Emission rate, loading, ventilation Foam type product ‐ styrene (14 d)

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0,3 0,7 1,5 0,3 0,5 0,7 1,5 0,3 0,7 1,5

Emission rate, loading, ventilation Foam type product ‐ n‐pentane (14 d)

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Liquid type product:

There was a large variation of test results, probably due to very high concentration of both wa-ter and VOCs in test chamber in the early phase of emission testing, as outlined earlier in more detail (see discussion in chapter 3.3.1 on work package 1).

No clear trend for VOC emissions was observed when changing testing parameters. Air velocity over test specimen did not show any effect within the range 0,1 – 0,5 m/s.


Please note that the scale of the Y axis (% values) is different from the other tables in this chapter.


Blue = 1 m³ test chamber, red = 0,115 m³ test chamber, green = 0,024 m³ test chamber; all after 4 weeks in test chamber (see Annex cl. A.4.3.3).


- details as in figure 18 (see Annex cl. A.4.3.3).

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0,3 0,7 1,5 0,3 0,7 1,5 0,3 0,7 1,5

Emission rate, loading, ventilation Liquid type product ‐ diethylphthalate (28 d)

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Emission rate, loading, ventilation Liquid type product ‐ butyldiglycol (28 d)

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Figure 20 Examples of specific emission rate in test chambers with different air velocity above test specimen; shown as % of result with 0,3 m/s after 4 weeks in test chamber (see Annex cl. A.4.3.3.3).

- Butyldiglycol emitted from liquid type product - Diethylphthalate emitted from liquid type product


The solid products showed the expected constancy of area specific emission rates for the involved VOC. Only the VVOC n-pentane did not show the same trend in case of foam type product because any possible trend was overruled by a strong decrease of n-pentane emissions over storage time be-fore start of test.

The tested liquid type product showed:

High variation of area specific emission rate resulted in the fact that for some VOCs (e.g. butyldiglycol, TXIB) there was no clear trend observable that were larger than the variation of the analytical results.

For some other VOCs (e.g. diethylphthalate) there were indications that higher ventilation rate resulted in lower area specific emission rates, and higher loading factor gave higher area spe-cific emission rates.

Changing the air velocity over test specimen did not show any effect within the range 0,1 – 0,5 m/s.

Analysis of the achieved data confirmed the present specifications of accepted ranges of loading fac-tor and ventilation rate in the draft horizontal testing standard.

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Emission rate, air velocity Liquid type product ‐ 0,1 / 0,3 / 0,5 m/sButyldiglycol, diethylphthalate (28 d)

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3.3.4 Work package 2.1 – 2.4: Age of sample at start of test

The studies in work packages 2.1 – 2.4 revealed unintended but valuable information on the impact of sample age on test result.

Findings, conclusions

The freshly produced foam type product showed strong decrease of emissions of n-pentane between start of testing from August to December in both involved laboratories, giving lower test results the lat-er the test was started.

The linoleum flooring did not show that effect. This can be explained by the fact that linoleum has to cure a sufficient time before dispatch which will avoid elevated emissions initially after receipt at either customer or testing laboratory.

The liquid type product did not show that behavior because each test specimen is produced freshly from the original product which was stored in a well tightened container.

The other products did not show any observable ageing effects on emissions during the investigation period of 5 months as long as the sample was packaged properly and air tight.

The earlier specification ("start of test maximum 8 weeks after taking the sample") can be too long for products that are very sensitive to loss of emissions, but it can be too restrictive for products with more stable emissions. In future product specific standards, a specification on maximum age of sample at start of test could be differentiated per type of product when knowing the respective behavior of emissions over storage time. Figure 21 Examples of specific emission rate depending on age of a sample showing strong decrease of emissions; shown as % of result of the earliest test performed by the respective lab in September;

- n-pentane emitted from foam type product; 3 different labs; all results after 4 weeks in test chamber (see Annex cl. A.4.1.6, A.4.2.1, A 4.3.2). It is worth noting that other samples did not show the same decrease of specific emission rate, see text.

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Emission rate, age of sampleFoam type product ‐ n‐pentane (28 d), 3 labs

Lab 1 Lab 3Lab 2

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3.3.5 Work package 1, and 2.2 – 2.4: Determination of hexanal

The studies in work packages 1 and 2.2 – 2.4 revealed unintended but valuable information on the im-pact of selection of Tenax TA based (ISO 16000-6) or DNPH based (ISO 16000-3) air sampling and analysis on test result. Some analyses were conducted in parallel with both above mentioned methods. Earlier findings [42] led to the conclusion that DNPH method gives lower values for aldehydes with more than 4 carbon at-oms (e.g. butanal) than Tenax TA method.


Earlier findings on higher results obtained with Tenax TA method have not been confirmed. DNPH method gave higher results than Tenax TA results in all cases. Difference was small in many cases, but strong in several other cases. The horizontal testing standard (draft CEN/TS 16516) specifies only one testing method for hexanal and other carbonyl compounds for reducing systematic differences of test results between laborato-ries. Figure 22 Determination of n-hexanal with Tenax TA (ISO 16000-6) or DNPH (ISO 16000-3)

- Tenax TA result (ISO 16000-6) shown as % of DNPH result (ISO 16000-3), plotted against number of test (X axis)( see Annex cl. A.4.1.4, A.4.3.1.1, A.4.3.1.2, A.4.3.1.3).

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Determination of hexanalTenax TA result as % of DNPH result

Range: 10 ‐ 50 µg/m²hMedian 87%; 100% would mean identical results

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3.3.6 Work package 1, and 2.2 – 2.4: Determination of the VVOC n-pentane

The studies in work packages 1 and 2.2 revealed unintended but valuable information on challenges when determining high emissions of the very volatile organic compound (VVOC) n-pentane.


Parallel sampling of test chamber air with different air sampling volumes gave highly different results as long as the sample was not too old for determining any n-pentane emissions. But sampling on Tenax TA is not an appropriate method for determining n-pentane because the adsorption capacity of Tenax TA is too small for an appropriate air sampling of this very volatile compound. Use of another adsorbent will help solving this challenge. This finding is not applicable to all VVOC. ISO 16017-1 and Annex D of ISO 16000-6 (2011 version) give guidance on selection of an appropri-ate testing method. Figure 23 Air sampling volume and test result when tubes are overloaded with n-pentane:

Result obtained with 5,4 l air sampling volume, shown as % of the result obtained with 2,7 l air sampling volume; plotted against area specific emission rate (µg/m²h) obtained with 2,7 l air sampling volume (X axis) (see Annex cl. A.4.1.6).

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Determination of VVOCn‐pentane: 5,4 l air sample % of 2,7 l air sample

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3.3.7 Work package 3: Techniques for sealing back and edges

Goal: Study the impact on test result (in terms of area specific emission rate) of different techniques for seal-ing back and edges of a flat solid product if emissions from back or edges are much higher than emis-sions from top surface – and if only the top surface is in contact with indoor air under intended use conditions.


An investigation of the impact of techniques used for sealing back and edges on VOC area specific emission rate showed the effectiveness of different standard sealing techniques, but with minor rank-ing in effectiveness. The isolation of back and edges resulted in a complete or almost complete suppression of emissions from the back. Most efficient techniques were

back to back storage of plates, with edges covered with aluminium tape, tight coverage of edges and back with aluminium foil (almost identical result), seal box as specified in JIS A 1901.

Inclusion of a joint in wooden flooring type products test specimen did not cause any difference in area specific emission rate when compared with test specimens not including a joint. Less efficient sealing techniques were

pressing into a tray, fixing on a plate with tape (both specified in California CDPH Section 1350).

Any purchased aluminium tape should be checked for its emissions in á test chamber after being ap-plied on a glass or metal plate. Aluminium tapes are available that show only very low emissions of 2-3 glue specific VOCs, and only during the first 3 days. If a tape is covering rough surfaces (e.g. wood) then slightly higher emissions from the tape can be observed in the low µg/m³ range even later than after 3 days. The achieved data confirmed the present specifications in the draft horizontal testing standard (draft CEN/TS 16516). It is rated important to specify the appropriate sealing techniques for specific prod-ucts in product specific standards.

Figure 24 Efficiency of sealing technique for 3 different main VOCs emitted from back side after 4 weeks in test chamber (see Annex cl. A.4.4.1, A.4.4.2); red = complete retention. *: Almost identical result for tight coverage of back and edges with aluminium foil and aluminium tape, including a joint. WFTP: Wooden flooring type product; SPHEB: Solid product with high emissions from back

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Sealing techniquesfor sealing back and edges, after 3 days

fixed on glass,SPHEB

seal box,SPHEB

CDPH frame,SPHEB

back-to-back,WFTP *

back-to-back, SPHEB

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3.3.8 Work package 4: Reference material for method validation

Goal: Study the significance of a solid reference material for toluene for validation of the whole method, with participation of all involved laboratories. The reference material was a thin film spiked by Virginia Tech University with definite amounts of tolu-ene and placed into sample holders and then in the test chambers [45]. Previous investigations showed good stability of emission rates after 2 and after 3 days if stored cool all the time before test [46]. Transport of these reference samples occurred in containers with dry ice. Dry freezing was re-quired for storage in laboratory.


Most test results were between 80% and 120% recovery, especially after 2 days. This could serve as benchmark for both test chambers and for the prediction model. The use of such reference materials allows a quality check of the whole procedure including all steps from test chamber operation to VOC analysis. The draft standard recommends using this or equivalent reference material within quality assurance programs, especially for checking newly purchased test chambers. Figure 25 Recovery of toluene from spiked film after 48 hours, plotted against test chamber volume (as m³) (X axis) (see Annex cl. A.4.5). Red lines: Proposed benchmark for test chambers. It should be noted that loading factor in 3,2 m³ test chamber was much lower than in the other test chambers.

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3.3.9 Work package 5: Tenax TA tubes and benzene artefact generation

Goal: Investigation of the generation of benzene during air sampling and analysis in different labs with dif-ferent experimental settings, for identifying options to control and minimize benzene artefact formation.


The investigation showed that some laboratories reported unexpected increase of benzene levels on Tenax TA tubes after sampling from an atmosphere known to be free of benzene. In these cases, this benzene level was higher than blank level determined from the same Tenax TA tube before air sam-pling. In most (but not all) of the cases benzene increased during air sampling in the low nanogram range (on the sampling tube), resulting in false chamber air concentrations most times below 0,2 µg/m³, but up to 2 µg/m³ in other cases. This can impair accuracy of benzene determination in low levels in the µg/m³ range.

Lab Sample volume

Increase benzene

Thermal desorp-tion

Main VOCs in sampled atmosphere

no. Liters ng °C Minutes

1 1 0 – 0,2 290 5 DEP, texanol

2 2,8 – 5,4 0 290 8 n-butanol, n-hexanal, butylglycol

3 5 0 – 0,7 290 15 D3-carene, α-/β-pinene, aldehydes, n-butanol, …

4 9,6 0,5 – 1,2 300 7 2,2,4,6,6-pentamethylheptane

5 0,9 – 2,5 0 – 1,3 260 10 cyclohexane, octane, decane, hexadecane

6 4 3 – 13 300 10 decane, dodecane, and traces of more VOCs

7 5,4 0 – 1,0 275 15 propylene glycol, C10-C16 alkanes

8 4,3 – 4,7 1,6 – 2,9 260 6 organic acids and aldehydes

9 6 0,4 – 1,4 290 8 α-pinene, acetone Table 2 Formation of benzene artefacts during air sampling of atmosphere free of benzene (see Annex cl. A.4.6). If the column "increase benzene - ng" contains a 0 value then the benzene level detected in a sampling tube after sampling air from an atmosphere free of benzene was not higher than the blank value of the same sampling tube before sampling.

One possible assumption is that benzene is generated on Tenax TA tubes during air sampling under certain conditions. The mechanism has not been identified. It cannot be excluded that certain VOC mixtures after adsorption undergo chemical reaction while sampling air continues to pass over the sur-face of Tenax TA. As benzene test results in the low µg/m³ range can be falsified by artefact generation to a significant extent, the draft standard recommends to verify low-level test results with an independent second test-ing method before assessing a test result showing small benzene levels against any low limit value of e.g. 1 µg/m³.

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4. Repeatability of testing within one laboratory

4.1 Study design

The studies within work packages 1 and 2 delivered unintended but valuable information on the re-peatability of VOC emissions testing within one laboratory. All test results analyzed for repeatability were obtained by testing two or three test specimens from the same sample under identical conditions (in terms of temperature, relative humidity, loading factor, and ventilation rate) in the same laboratory during this study. All of the testing conditions were within the accepted ranges as specified in the draft TS 16516. Each result was analyzed for each main VOC. The following tables in the Annex of this document have been analyzed for repeatability of tests that have been conducted under identical conditions (in terms of temperature, relative humidity, loading factor, and ventilation rate):

Ch. A.4.1: Tests at 23°C and 50% RH (2 tables per product, 12 tables in total) Ch. A.4.3.1.1, A.4.3.1.2, A.4.3.1.3: Tests with 0,7 m²/m³ and 0,7 /h

(3 tables per product and test chamber size, 6 tables in total) Ch. A.4.3.2.1, A.4.3.2.2, A.4.3.2.3: Tests with 0,7 m²/m³ and 0,7 /h

(3 tables per product and test chamber size, 6 tables in total) Ch. A.4.3.3.1, A.4.3.3.1, A.4.3.3.3: Tests with 0,7 m²/m³ and 0,7 /h

(3 tables per product and test chamber size, 9 tables in total) Ch. A.4.3.3.4: Tests with 0,7 m²/m³ and 0,7 /h (3 tables)

This resulted in:

Number of chamber tests: 36. Number of involved products: 6. Number of involved testing laboratories: 9. Number of repeatability data (= number of individual VOCs analyses in these tests): 178.

o 57 data for individual VOCs from duplicate determination o 121 data for individual VOCs from tests with triplicate determination.

4.2 Findings

The deviation of individual emission chamber test results from their mean value was calculated as % of their mean value. Repeatability resulted as follows:

50% of all test data showed a deviation of individual test results from their mean value below 14% (the median of all findings).

75% of all test data showed a deviation of individual test results from their mean value below 27% (75 percentile of all findings).

95% of all test data showed a deviation of individual test results from their mean value below 54% (95 percentile of all findings).

Standard deviation (1 ) of all test results was 17%. The expanded uncertainty (2 ) of all test results, representing the 95% confidence interval,

was 35%.

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Repeatability of VOC emissions testing depended strongly on:

Inhomogeneity of the tested product. Chemical characteristics of the identified VOCs. Height of emissions when testing; small traces of VOC emissions and very high emissions are

difficult to analyze. Emissions mechanisms, and emissions decay over time of the tested product. Storage duration of test sample before testing, especially in the case of the foam type product.

The selected VOCs for analysis; in the case of the liquid type product not all laboratories se-lected the same list of VOCs for testing. This gives less data for the evaluation and statistics.

4.3 Conclusions on repeatability within one laboratory

The repeatability of VOC emissions testing within one laboratory needs to be specified per product group when establishing product specific standards because it can be influenced by the above men-tioned factors, and some of these are specific to certain types of products. In general, it has been found that repeatability can vary between very low (= below ± 10%) and high or even very high (± 50%, or even more in the case of the VVOC n-pentane). It has to be considered that material inhomogeneity between test specimens taken from the same received test sample contrib-utes to this variation.

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4.4 Detailed findings per tested product

Figure 26 Repeatability within one laboratory – Wood flooring type product Figure 27 Repeatability within one laboratory – Wood-based panel type product

0%0%

5%

10%

15%

20%

25%

30%

3d 10d 28d

Repeatability within one labDeviation from mean value:

Wood‐based panel type product

Formaldehyde

Acetaldehyde

Hexanal

0%0%

5%

10%

15%

20%

25%

3d 10d 28d


Wooden flooring type product

Formaldehyde

Acetaldehyde

Acetic acid

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Figure 28 Repeatability within one laboratory – Flooring type product, 3 days Figure 29 Repeatability within one laboratory – Flooring type product, 10 days Figure 30 Repeatability within one laboratory – Flooring type product, 28 days

0%10%20%30%40%50%60%

Repeatability within one labDeviation from mean value: Flooring type product, 3 days

Lab A

Lab B

0%10%20%30%40%50%60%


Flooring type product, 10 days

Lab A

Lab B

0%10%20%30%40%50%60%


Flooring type product, 28 days

Lab A

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Figure 31 Repeatability within one laboratory – Foam type product, 3 days Figure 32 Repeatability within one laboratory – Foam type product, 10 days Figure 33 Repeatability within one laboratory – Foam type product, 28 days

0%

20%

40%

60%

80%

100%

n‐Pentane Styrene Ethylbenzene

Repeatability within one labDeviation from mean value: Foam type product, 3 days

Lab A

Lab B

Lab C

0%

20%

40%

60%

80%

100%



Lab A

Lab B

Lab C

0%

20%

40%

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80%

100%



Lab A

Lab B

Lab C

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Figure 34 Repeatability within one laboratory – Liquid type product, 3 days Figure 35 Repeatability within one laboratory – Liquid type product, 10 days Figure 36 Repeatability within one laboratory – Liquid type product, 28 days

0%10%20%30%40%50%60%70%

Repeatability within one labDeviation from mean value: Liquid type product, 10 days

Lab A

Lab B,1 m³

Lab B,24 l

0%10%20%30%40%50%60%70%


Lab A

Lab B,1 m³

Lab B,24 l

0%10%20%30%40%50%60%70%


Lab A

Lab B,1 m³

Lab B,24 l

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5. Project results – summary and interpretation

This project had the goal to deliver scientific data and information for robustness validation of VOC emission chamber testing as specified in the draft horizontal testing standard CEN/TS 16516. The work was performed on basis of the earlier draft version as in the document CEN/TC 351/WG 2/N129. The experimental part of the project concentrated on delivering data for filling those information gaps that had been identified in chapter 2. 5.1 Conclusions on robustness validation of draft CEN/TS 16516

The validity of most parts of the draft testing standard could be confirmed. Only minor changes had been recommended to CEN/TC 351/WG 2, many of these of editorial nature – and most of these had been confirmed by CEN/TC 351/WG 2. There are no criteria available for assigning "robustness" to a testing standard. It is only possible to show the degree of robustness of the test method against modifications of testing parameters with po-tential impact on the test result. It could be shown that the specifications of draft CEN/TS 16516 allow determination of emissions of volatile organic compounds with a degree of reliability that is not impaired by systematic errors from any specifications of testing parameters. Remaining uncertainty of test results is caused partly by in-homogeneity of the tested products, and partly by differences in the analytical practice in the involved testing laboratories that cannot be improved without unacceptable impact on testing costs. 5.2 Conclusions on comparability with other testing standards

It has been demonstrated in above documentation that a test under slightly different testing parame-ters (temperature, RH, ventilation, loading) gave comparable test results as when using the testing pa-rameters of draft CEN/TS 16516, as long as the test results either are expressed as specific emission rate, or are recalculated to the specifications of the European Reference Room (see cl. 4 of draft CEN/TS 16516). This allows some flexibility (even though within narrow limitations) of the testing laboratories. It also al-lows performing a test under the specifications of other testing standards (e.g. US American stand-ards, or EN 717-1, applying other ventilation rate and different loading factors), and then obtaining the test results for CEN/TS 16516 just by recalculation, without the need of another test, see the specifica-tions in clause 7 and the calculation formulas in clause 9 of draft CEN/TS 16516. This applies to all products except wood-based panels with formaldehyde-urea binder. There still is an on-going dispute whether determination of formaldehyde generation from those specific products re-quires use of the testing parameters as specified in EN 717-1 without any deviations. 5.3 Further improvements

Some further improvement of reliability of VOC emission testing is possible if the involved testing la-boratories compare their performance in round robin tests and by testing of reference material, as specified in cl. 8.4 of draft CEN/TS 16516. This allows early determination and remediation of any non-appropriate working routines in case of bad performance. The project consortium would welcome if standardization committees inside and outside CEN would use the findings of this study, together with final text of CEN/TS 16516, for further optimization and for global harmonization of VOC emission testing standards.

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6. Bibliography

1. International Organization for Standardization (ISO), Indoor Air - Part 9: Determination of the emission of volatile organic compounds from building products and furnishing - Emission test chamber method (ISO 16000-9:2006), 2006. Beuth, Berlin 2. International Organization for Standardization (ISO), Indoor Air - Part 3: Determination of formaldehyde and other carbonyl compounds - Active sampling method (ISO 16000-3:2001), 2002. Beuth, Berlin 3. International Organization for Standardization (ISO), Indoor air - Part 6: Determination of volatile organic compounds in indoor and test chamber air by active sampling on Tenax TA® sorbent, thermal desorption and gas chromatography using MS/FID (ISO 16000-6:2004), 2004. Beuth, Berlin 4. International Organization for Standardization (ISO), Indoor air - Part 11: Determination of the emission of volatile organic compounds from building products and furnishing - Sampling, storage of samples and preparation of test specimens, 2006. Beuth, Berlin 5. International Organization for Standardization (ISO), Indoor, ambient and workplace air - Sampling and analysis of volatile organic compounds by sorbent tube/thermal desorption/capillary gas chromatography - Part 1: Pumped sampling (ISO 16017-1:2000), 2000. Beuth, Berlin 6. CEN/TR 16220 Construction products - Assessment of release of dangerous substances - Complement to sampling, 2011 7. California Department of Public Health and California Health and Human Services Agency, Standard method for the testing and evaluation of volatile organic chemical emissions from indoor sources using environmental chambers - Version 1.1, 2010. 8. Gemeinschaft Emissionskontrollierte Verlegewerkstoffe, Klebstoffe und Bauprodukte e.V. (GEV), Bestimmung flüchtiger organischer Verbindungen zur Charakterisierung emissionskontrollierter Verlegewerkstoffe, Klebstoffe, Bauprodukte und Parkettlacke (in German; Determination of volatile organic compounds for the characterization of emission controlled flooring materials, adhesives, building materials and parquet lacqeurs), 2011. 9. Deutsches Institut für Bautechnik (DIBt), Grundsätze zur gesundheitlichen Bewertung von Bauprodukten in Innenräumen (in German; Principles of health evaluation of building products), in: DIBt-Mitteilungen 5/2010, 2010: p. 209-247. 10. Confidential data in unpublished work that was allowed to be used in this study 11. European Commission - Joint Research Centre - Environment Institute, ECA Report No 21 - European Inter-laboratory Comparison on VOC emitted from building materials and products, 1999. Office for Official Publications of the European Communities, Luxembourg 12. Kim, S., Kim, J.-A., Kim, H.-J., Hyoung Lee, H. and Yoon, D.-W., The effects of edge sealing treatment applied to wood-based composites on formaldehyde emission by desiccator test method. Polymer Testing, 2006. 25 (7): p. 904-911. 13. Windhövel, U. and Oppl, R., Praktische Überprüfung des Konzepts zur gesundheitlichen Bewertung von Bauprodukten (in German; Practicable evaluation of the approach for health evaluation of building products). Gefahrstoffe - Reinhaltung der Luft, 2005. 65 (3): p. 81-89. 14. Kirchner, D., Emissionsmessungen auf dem Prüfstand (in German; Emissions tests put to test). DIBt Mitteilungen, 2007: p. 77-85.

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15. Horn, W. Wiegner, K., Wilke, O., Jann, O., Richter, M., Kalus, S., Brödner, D., Juritsch, E., Till, C., Entwicklung eines allgemeinen, externen Qualitätsmanagementsystems für den Nachweis von relevanten chemischen Schadstoffen der produktemission und in Innenräumen (in German; General, external quality management system for the determination of relevant chemical compounds from the emission of products or in indoor air), BAM Bundesanstalt für Materialforschung und -prüfung, Final Report, 2010. Berlin 16. Wilke, O., Horn, W., Wiegner, K., Jann, O., Bremser, W., Brödner, D., Kalus, S., Juritsch, E., Till, C., Investigations for the improvement of the measurement of volatile organic compounds from floor coverings within the health-related evaluation of building products, BAM Bundesanstalt für Materialforschung und -prüfung, Final Report, 2009. Berlin www.bam.de/en/service/publikationen/publikationen_medien/abschlussbericht_engl_ils_dibt_2009.pdf 17. Hansen, V., Larsen, A. and Wolkoff, P. Nordic round-robin emission testing of a lacquer: Consequences of product in-homogeneity. in Proceedings of Healthy Buildings 2000. 2000. Espoo, Finland. 18. European Commission - Joint Research Centre - Environment Institute, ECA Report No 13 - Determination of VOCs emitted from indoor materials and products - Inter-laboratory Comparison of small chamber measurement, 1993. Office for Official Publications of the European Communities, Luxembourg 19. Yrieix, C., Dulaurent, A., Laffargue, C., Maupetit, F., Pacary, T. and Uhde, E., Characterization of VOC and formaldehyde emissions from a wood based panel: Results from an inter-laboratory comparison. Chemosphere, 2010. 79 (4): p. 414-419. 20. GUT-Ringversuch 2005. Bestimmung flüchtiger organischer Komponenten aus einer Teppichfliese nach dem Prüfkammerverfahren (in German; Determination of volatile organic compounds of a carpet tile with test chamber methodology), 2005. Internal working document of GUT 21. Wilke, O., Jann, O., Brödner, D. and Rother, I. Comparison of different types of emission test chambers and cells regarding VOC- and SVOC-emission. in Proceedings of Indoor Air Conference 2005. 2005. Beijing, China. 22. Jann, O., Wilke, O., Brödner, D., Entwicklung eines Prüfverfahrens zur Ermittlung der Emission flüchtiger organischer Verbindungen aus beschichteten Holzwerkstoffen und Möbeln (in German; Development of a test method for the determination of volatile organic compounds from coated wood based materials and furniture), BAM Bundesanstalt für Materialforschung und -prüfung, Final Report, UBA-Texte 74/99, 1999. Berlin 23. Sollinger, S., Levsen, K. and Wünsch, G., Indoor air pollution by organic emissions from textile floor coverings. Climate chamber studies under dynamic conditions. Atmospheric Environment. Part B. Urban Atmosphere, 1993. 27 (2): p. 183-192. 24. Katsoyiannis, A., Leva, P. and Kotzias, D., VOC and carbonyl emissions from carpets: A comparative study using four types of environmental chambers. Journal of Hazardous Materials, 2008. 152 (2): p. 669-676. 25. De Bortoli, M., Kephalopoulos, S., Kirchner, S., Schauenburg, H. and Vissers, H., State-of-the-Art in the Measurement of Volatile Organic Compounds Emitted from Building Products: Results of European Inter laboratory Comparison. Indoor Air, 1999. 9 (2): p. 103-116. 26. Oppl, R. and Winkels, K. Uncertainty of VOC and SVOC measurement - how reliable are results of chamber emission testing? in Proceedings of Indoor Air 2002. 2002. Monterey, USA. 27. Oppl, R., Reliability of VOC emission chamber testing - progress and remaining challenges. Gefahrstoffe - Reinhaltung der Luft, 2008. 68 (3): p. 83-86.

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28. Deutsches Institut für Normung (DIN), Wood based panels - Determination of formaldehyde release - Part 1: Formaldehyde emission by the chamber method; German version EN 717-1:2004, 2004. Beuth, Berlin 29. Wilke, O., Jann, O. and Brödner, D. Effects of temperature, humidity, air exchange rate, loading factor and storage-conditions on VOC-emissions. in Proceedings of Indoor Air Conference 1999. 1999. Edinburgh, Scotland. 30. Sollinger, S., Levsen, K. and Wünsch, G., Indoor pollution by organic emissions from textile floor coverings: Climate test chamber studies under static conditions. Atmospheric Environment, 1994. 28 (14): p. 2369-2378. 31. Gene Tucker, W., Emission of organic substances from indoor surface materials. Environment International, 1991. 17 (4): p. 357-363. 32. Wolkoff, P., Impact of air velocity, temperature, humidity, and air on long-term voc emissions from building products. Atmospheric Environment, 1998. 32 (14-15): p. 2659-2668. 33. Jann, O., Wilke, O. and Brödner, D. VOC-emissions from furnitures and coated wood based products. in Proceedings of Healthy Buildings Conference 1997. 1997. Washington DC, USA. 34. European Commission - Joint Research Centre - Environment Institute, ECA Report No 16 - Determination of VOCs emitted from indoor materials and products - Second Inter-laboratory Comparison of small chamber measurement, 1995. Office for Official Publications of the European Communities, Luxembourg 35. Wilke, O., Jann, O., Brödner, D., Untersuchung und Ermittlung emissionsarmer Klebstoffe und Bodenbeläge (in German; Investigations on and Determination of low-emitting adhesives and flooring materials), BAM Bundesanstalt für Materialforschung und -prüfung, Final Report, UBA-Texte 27/03, 2003. Berlin 36. European Commission - Joint Research Centre - Environment Institute, ECA Report No 8 - Guideline for the Characterization of Volatile Organic Compounds emitted from Indoor Materials and Products using Small Test Chambers, 1991. Office for Official Publications of the European Communities, Luxembourg 37. Horn, W., Jann, O., Kasche, J., Bitter, F., Müller, D., Müller, B., Environmental and health provisions for building products - Identification and evaluation of VOC emissions and odour exposure, BAM Bundesanstalt für Materialforschung und -prüfung, Final Report, UBA-Texte 21/07, 2007. Berlin 38. Richter, M., Jann, O., Horn, W. and Pyza, L. Development and validation of a new gas mixing device for low concentrations. in Proceedings of Healthy Buildings Conference 2009. 2009. Syracuse, USA. 39. Richter, M., Horn, W., Jann, O., Brödner, D. and Till, C. Application of a new gas mixing device to test adsorptive wall materials. in Proceedings of Healthy Buildings Conference 2005. 2009. Syracuse, USA. 40. Levin, J.-O., Lindahl, R., Heeremans, C.E.M. and van Oosten, K., Certification of reference materials related to the monitoring of aldehydes in air by derivatization with 2,4-dinitrophenylhydrazine. ANALYST, 1996. 121 (9): p. 1273-1278. 41 WASP: www.hsl.gov.uk/centres-of-excellence/proficiency-testing-schemes/wasp.aspx. 42. Salthammer, T. and Mentese, S., Comparison of analytical techniques for the determination of aldehydes in test chambers. Chemosphere, 2008. 73 (8): p. 1351-1356. 43 Edmone Roffael: Die Formaldehyd-Abgabe von Spanplatten und anderen Werkstoffen. DRW-Verlag, Stuttgart, 1982, pp 68-73

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44 Personal correspondence by H. Kramberger, J. Beilstein, Dr. Robert-Murjahn-Institute, 2011 45 Cox, S. S., Liu, Z., Little, J. C., Howard-Reed, C., Nabinger, S., and Persily, A. “Diffusion-Controlled Reference Material for VOC Emissions Testing: Proof of Concept,” Indoor Air, Vol. 20, No. 5, 2010, pp. 424-433. 46 Howard-Reed, C., Liu, Z., Benning, J., Cox, S. S., Samarov, D., Leber, D., Hodgson, A., Mason, S., Won, D. and Little, J. C. “Diffusion-Controlled Reference Material for Volatile Organic Compound Emissions Testing: Pilot Inter-laboratory Study,” Building and Environment, Vol. 46, 2011, pp. 1504-1511.41.

Literature that was taken into consideration but not included in this study

Brown, V and Crump, D (2011). Optimization of analytical parameters for the determination of VOCs emitted by construction and consumer products. Proceedings of the 2011 Annual UK Review meeting on outdoor and indoor air pollution research, Cranfield University, 10 – 11 May 2011 IEH web report (in press). ECA Report No. 2, 1989: Formaldehyde Emission from Wood-based Materials. Guideline for the Determination of Steady State Concentrations in Test Chambers. Lor, M., et. al. Horizontal Evaluation Method for the Implementation of the Construction Products Directive (HEMICPD), Final report, published in 2010 by the Belgian Science Policy, www.belspo.be Marutzky, R., Schripp, T. Erarbeitung der Grundlagen zur Evaluierung und Aktualisierung der bauaufsichtlichen Bestimmungen für die Formaldehydabgabe aus Baustoffen: Holzwerkstoffe, Abschlussbericht zum Forschungsvorhaben für das DIBt, 2010. Yu,C. W. F. and Crump, D. R. Small Chamber Tests for Measurement of VOC Emissions from Flooring Adhesives. Indoor and Built Environment 2003; Vol. 12 (issue 5), pp. 299-310. Yu, C. and Crump, D. Methods for measuring VOC emission from interior paints. Surface Coating International, Vol. 83, No. 11, p. 548-556, November 2000. Yu, C., Crump, D. R. Testing for Formaldehyde Emissions from Wood-based Products – A Review. Indoor and Built Environment, Vol. 8, 1999, p. 280-286.

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ANNEX: Data obtained by laboratory testing

A.1 Introduction

A.2 Testing Samples

Testing samples were acquired from leading manufacturers. The project team expresses its gratitude to the suppliers of the test samples. The samples were selected in such a manner that they were expected to show measurable emissions even after 28 days, higher than normal products. One sample was even spiked with some VOCs for better use within this project. For these reasons, the test results cannot be linked to any typical emissions of the selected product groups; there are good reasons to assume that the measured emissions were rather higher than the emissions from normal products available in the market. Some of the suppliers asked the project team not to disclose more details because their samples were not regarded representative for any product group, or for an application area of any certain CEN TC dealing with specific product groups. The testing samples were selected for representing different types of products with respect to VOC emissions mechanisms:

Flooring type product Mineral wool type product Liquid type product Wooden flooring type product Foam type product Solid product with high emissions from back Wood-based panel type product

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A.3 Homogeneity testing

A.3.1 Testing plan

A.3.1.1 Flooring type product

30 m² (2 m x 15 m) of the test material was delivered as a roll. Test specimens for homogeneity testing and for robustness validation exercise were cut out as shown in figure 37.

Figure 07: Sampling scheme for flooring type product The test specimens for homogeneity testing were cut into pieces of 20 cm x 20 cm in size. Four pieces (marked with X) were selected as depicted in Figure 37for testing with test cells of 1 l volume. The compounds with highest concentrations were monitored for the estimation of homogeneity.

A.3.1.2 Mineral wool type product

The test sample was delivered as a roll with dimensions 1,2 m x 7,5 m. Test specimens for homogeneity testing and for robustness validation exercise were cut out as shown in figure 38. The six samples marked ‘BAM’ (10 cm x 10 cm) were selected for homogeneity testing and sealed individually in hermetic bags. Homogeneity testing took place in 24 l test chambers. Only formaldehyde was monitored for the estimation of homogeneity. Figure 38: Sampling scheme for mineral wool type product

discarded

sample for validation testing

sample for homogeneity testing

sample for validation testing


discarded


X

X

X X

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A.3.1.3 Liquid type product

A liquid type product spiked with six VOC was delivered in a can of 20 liters. After its homogenization with a mixer the product was divided into 16 portions and filled into plastic bottles with a volume of 500 ml each. 6 out of these bottles were selected randomly for homogeneity testing in µ-chambers. Only the spiked target compounds were monitored for the estimation of homogeneity.

A.3.1.4 Wooden flooring type product

Samples were taken out of two packages of wooden flooring. In each case three boards from the middle of the staple (boards 1 to 3 from package 1 and boards 4 to 6 from package 2) were cut as depicted in figure 39.

A 1 B 1 C 1 BAM 1 D 1 E 1 F 1 A: Sample 19°C

C 2 A 2 B 2 BAM 2 F 2 D 2 E 2 B: Sample 23°C

B 3 C 3 A 3 BAM 3 E 3 F 3 D 3 C: Sample 27°C

D 4 E 4 F 4 BAM 4 A 4 B 4 C 4 D: Sample 45% r.H.

F 5 D 5 E 5 BAM 5 C 5 A 5 B 5 E: Sample 50% r.H.

E 6 F 6 D 6 BAM 6 B 6 C 6 A 6 F: Sample 55% r.H.6

5

4

3

2

1

Figure 39: Sampling scheme for wooden flooring type product The six ‘BAM’ marked samples were selected for homogeneity testing and the other ones were shipped to the involved partner institutes for robustness validation testing. Homogeneity testing took place in 24 l test chambers. Edges were sealed with aluminum tape. Only formaldehyde was monitored for the estimation of homogeneity.

A.3.1.5 Foam type product

Six randomly chosen test specimens of a foam type product with 17 cm x 17 cm x 10 cm in size were delivered by Eurofins. Homogeneity testing took place in 24 l test chambers. The edges were sealed with aluminum tape. The compounds with highest concentrations were monitored for the estimation of homogeneity.

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A.3.1.6 Solid product with high emissions from back

Six randomly chosen test specimens of a solid product with 20 cm x 20 cm in size were cut out of the delivered roll by Eurofins as shown in figure 40.

Figure 40: Sampling scheme for solid product Four of these test specimens were randomly chosen and tested top-side with test cells of 1 l. Phenol was the only compound detected and, thus, monitored for the estimation of homogeneity.

A.3.1.7 Wood-based panel type product

12 samples of a wood-based panel type product with 19 cm x 19 cm in size were delivered as a staple by WKI. Six test specimens were randomly chosen from the middle of the staple and tested in test chambers of 24 l. The edges were sealed with aluminum tape. Only formaldehyde was monitored for the estimation of homogeneity.

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A.3.2 Results

Any effect of testing parameters observed in this report needs to show larger differences than the reported inhomogeneity.

CAS No.

Air concentration under test conditions on day 7 [µg/m³]

Average

Std. dev.

Rel. std. dev.

Sample # [µg/m³] [µg/m³] [%] 1 2 3 4 5 6

1) Flooring type product **, used in WP 1 and 2.2 – 2.4 (1 liter test cell)

Hexanal 108-95-2 3,9 3,4 3,3 3,0 - - 3 0,4 11%

Hexanoic acid 142-62-1 90 92 82 84 - - 87 4,7 5%

Octanal 124-13-0 2,1 1,9 1,8 1,8 - - 2 0,1 7%

Nonanal 124-19-6 3,0 3,0 2,6 2,4 - - 3 0,3 10%

Octanoic acid 124-07-2 43 43 38 41 - - 41 2,1 5%

2) Mineral wool type product *, used in WP 1 (24 liter test chamber)

Formaldehyde 50-00-0 6,0 7,5 6,6 6,5 8,4 4,7 7 1,3 19%

3) Liquid type product ***, used in WP 1 and 2.1 – 2.4 (Microchamber)

Acetic acid 64-19-7 < 10 < 10 < 10 < 10 < 10 < 10 < 10

Propylene glycol 57-55-6 59 68 65 66 60 55 62 4,8 8%

Butyldiglycol 112-34-5 108 118 117 122 111 102 113 7,3 6%

Texanol 25265-77-4 132 148 145 151 137 125 140 10,1 7%

Diethyl phthalate 84-66-2 181 201 177 172 168 163 177 13,6 8%

n-Hexadecane 544-76-3 1,4 1,4 1,1 1,0 1,2 1,0 1 0,2 15%

4) Wooden flooring type product *, used in WP 1 and 3 (24 liter test chamber)

Formaldehyde 50-00-0 3,8 4,2 4,8 4,0 5,4 10,0 5 2,3 44%

5) Foam type product *, used in WP 1 and 2.1 – 2.4 (24 liter test chamber)

Ethylbenzene 100-41-4 33 26 35 43 30 42 35 6 18%

Styrene 100-42-5 233 241 215 355 278 238 277 53 19%

Acetophenone 98-86-2 27 22 23 28 26 28 26 2 10%

6) Solid product with high emitting back **, used in WP 3 (1 liter test cell)

Phenol 108-95-2 6,2 7,4 8,3 8,3 - - 8 1 13%

No other VOC were detected

7) Wood-based panel type product *, used in WP 1 (24 liter test chamber)

Formaldehyde 50-00-0 56 55 67 63 59 59 59,8 4,5 8%

All VOCs were below 2 µg/m³

* Tested in test chambers of 24 liters volume ** Tested with test cells of 1 liter volume. *** Tested in µ-chamber. NOTE: These test results are not at all representative for the respective product groups.

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A.4 Testing program and data

Each figure in the following tables is from one test with one sample tested, based on evaluation of duplicate air sampling from test chamber. The participating laboratories were required to deliver one final test result per test sample. If unexpected values were delivered then the laboratory was asked to check the result, and then to correct or to confirm the result.

A.4.1 Work package 1: Temperature and humidity

Goal: Study the impact of

changed temperature in test chamber in the range 19°C – 27°C with constant absolute humidity of chamber supply air;

changed RH of chamber supply air in the range 45% – 55% with constant temperature in test chamber

on test result for three materials emitting formaldehyde based on different release mechanisms, and three materials emitting VOC with different emissions characteristics. According to theory, the area specific emission rate (µg/m²h) should remain constant in the selected range. Testing plan: Testing was performed at 19°C, 23°C, 27°C temperature in test chamber with constant absolute humidity of chamber supply air, meaning 8,7 g/kg corresponding to: 50% RH at 23 °C, 39% RH at 27°C and 64% RH at 19 °C, or equivalent. This range was selected for testing because the project needed a sufficiently high variation of temperature for being able to detect any impact of temperature on test result higher than material inhomogeneity and analytical uncertainty. Absolute humidity was kept constant for separating any effect of changed temperature from any effect of changed humidity. Other testing was performed at 45%, 50%, 55% RH of chamber supply air with constant temperature in test chamber. Loading factor and ventilation rate have been selected by the laboratories and were kept constant during the experiments. Both test series were performed for …

Products with release of formaldehyde from binder by hydrolysis o Wooden flooring type product by eco o Mineral wool type product by Saint-Gobain o Wood-based panel type product by WKI

Products with emission by other mechanisms o Flooring type product by eco o Liquid type product by WKI o Foam type product by DTI

Testing: After 3, 14 and 28 days storage in the test chamber, no storage outside test chamber during the test. Compounds to be measured: Selected dominating VOC, formaldehyde. If measurement at the first point of time (after 3 days) showed that there is no formaldehyde, then it was not necessary to continue with the DNPH measurements at later points of time.

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A.4.1.1 WP 1 – Results: Wooden flooring type product

Product: Wooden flooring, selected for expected relatively high emissions Loading factor 0,4 m²/m³ Air change rate 0,5 / h Edges, back Covered with aluminum foil Test chamber 250 l

Month: September / October 2011 Lab: eco

Temperature 19°C Supply air relative humidity

64%

Substance µg/m²h after 3 days µg/m²h after 14 days µg/m²h after 28 days

Formaldehyde 41 29 28

Acetaldehyde 15 6 4

Acetic acid 150 150 86



50%



Acetaldehyde 15 6 4


Month: October / November 2011 Lab: eco


39%



Acetaldehyde 18 5 <3

Acetic acid 290 200 140 NOTE: These test results are not at all representative for the respective product group.

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A.4.1.1 WP 1 – Results: Wooden flooring type product (continued)



45%



Acetaldehyde 16 5 4




50%



Acetaldehyde 13 6 4




55%



Acetaldehyde 19 6 6

Acetic acid 240 180 140 NOTE: These test results are not at all representative for the respective product group.

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A.4.1.2 WP 1 – Results: Wood-based panel type product

Product: Wood-based panel, selected for expected relatively high emissions Loading factor 1,0 m²/m³ Air change rate 1,0 / h Edges Covered with aluminum foil Back Not covered Test chamber 1 m³

Month: October / November 2011 Lab: WKI

Temperature 19,1°C Supply air relative humidity

66,1%




Hexanal 19 11 11

Month: September / October 2011 Lab: WKI


52%




Hexanal 32 21 17



42%




Hexanal 22 18 14 NOTE: These test results are not at all representative for the respective product group.

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A.4.1.2 WP 1 – Results: Wood-based panel type product (continued)



44,9%




Hexanal 26 13 9



50,1%




Hexanal 34 19 10



55,6%





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A.4.1.3 WP 1 – Results: Mineral wool type product

Product: Mineral wool type product, selected for expected relatively high emissions Loading factor 1,0 m²/m³ Air change rate 0,5/h Edges Not covered Back Covered with aluminum foil Test chamber 190 l

Month: September 2011 Lab: Saint-Gobain

Temperature 19°C (18,8°C – 19,0 °C)

Supply air relative humidity

64% (63,3% - 64,3%)



Ethylhexanol 41 <4 <4

Month: July/August 2011 Lab: Saint-Gobain

Temperature 23°C (22,8°C – 23,2°C)


50% (49,0% - 50,2%)



Ethylhexanol 27 6 <4

Month: September 2011 Lab: Saint-Gobain



39% (38,6% - 39,2%)




Month: July/August 2011 Lab: Saint-Gobain



45% (44,7% - 45,7%)




Month: October / November 2011 Lab: Saint-Gobain



50% (49,0% - 49,6%)




Month: October / November 2011 Lab: Saint-Gobain



55% (54,4% - 54,8%)



Ethylhexanol 16 <4 <4 NOTE: These test results are not at all representative for the respective product group.

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A.4.1.4 WP 1 – Results: Flooring type product

Product: Flooring type product, selected for expected relatively high emissions Loading factor 0,4 m²/m³ Air change rate 0,5/h Edges, back Covered with aluminum foil Test chamber 250 l

Month: September/October 2011 Lab: eco


64%



Hexanoic acid 36 30 16

Heptanoic acid 8 9 5

Octanoic acid 6 8 5

Hexanal (Tenax TA) 20 14 14

Hexanal (DNPH) 28 18 16



50%





Octanoic acid 10 9 6



Month: October/November 2011 Lab: eco


39%







Hexanal (DNPH) 49 45 49 NOTE: These test results are not at all representative for the respective product group.

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A.4.1.4 WP 1 – Results: Flooring type product (continued)



45%










50%










55%







Hexanal (DNPH) 34 25 25 NOTE: These test results are not at all representative for the respective product group. CEN/TC 35

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ort


A.4.1.5 WP 1 – Results: Liquid type product

Product: Liquid type product, spiked with a number of VOC. Application on mineral with a brush. Loading factor 1,0 m²/m³ Air change rate 1,0 / h Test chamber 1 m³


Application: 176 g/m²


68,1%


Acetic acid 220 16 < 1

Propyleneglycol 26000 < 1 < 1 Butyldiglycol 7400 < 1 < 1 Texanol 3300 11 < 1 Diethylphthalat 240 330 160 2-Methyl-4-isothia-zolin-3-one (MIT)

170 10 < 1




52,6%


Acetic acid 250 < 1 < 1

Propyleneglycol 610 < 1 < 1 Butyldiglycol 5400 2 < 1 Texanol 4500 < 1 < 1 Diethylphthalat 980 230 140 2-Methyl-4-isothia-zolin-3-one (MIT)

490 2 < 1




42,6%



Propyleneglycol 210 6 < 1 Butyldiglycol 2800 3 < 1 Texanol 3100 2 < 1 Diethylphthalat 610 330 170 2-Methyl-4-isothia-zolin-3-one (MIT)

160 3 < 1

Formaldehyde was detected in no single case in all 3 above tables. Results after 3 days are imprecise due to high loading of tubes in all 3 above tables. NOTE: These test results are not at all representative for the respective product group.

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A.4.1.5 WP 1 – Results: Liquid type product (continued)




45,5%



Propyleneglycol 2200 24 < 1 Butyldiglycol 5300 140 22 Texanol 2900 190 23 Diethylphthalat 290 180 140 2-Methyl-4-isothia-zolin-3-one (MIT)

160 12 4

Formaldehyde was detected in no single case. Results after 3 days are imprecise due to high loading of tubes.




50,8%




78 8 2





55,1%




190 20 6

Formaldehyde was detected in no single case. Results after 3 days are imprecise due to high loading of tubes. NOTE: These test results are not at all representative for the respective product group.

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A.4.1.6 WP 1 – Results: Foam type product

Product: Foam type product, selected for expected relatively high emissions Loading factor 1,0 m²/m³ Air change rate 1,0 / h Back Covered by placing test specimen on chamber bottom Test chamber 225 l Analyses of VOC air samples Subcontracted due to disturbance of analytical devices

Please note that the emissions of the product decreased during project time. This may explain some of the observed differences. Formaldehyde was either not found, or only in traces (1 or 2 µg/m³).

Month: October 2011 Lab: DTI


64%


n-Pentane, mean 220 220 71

2,7 l air volume 240 160 88

5,4 l air volume 200 104 55

Ethylbenzene 13 9 6

Styrene 120 68 46 Note: 2nd air sampling was performed after 10 days, not after 14 days.

Month: August 2011 Lab: DTI


45%



2,7 l air volume 2100 830

5,4 l air volume 850 530

Ethylbenzene 20 11 9

Styrene 380 110 74

Month: August 2011 Lab: DTI


39%



2,7 l air volume 2400 970 330

5,4 l air volume 790 520 180


Styrene 310 110 84 NOTE: These test results are not at all representative for the respective product group.

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A.4.1.6 WP 1 – Results: Foam type product (continued)

Month: November 2011 Lab: DTI


45%



2,7 l air volume 12

5,4 l air volume 10


Styrene 140 83 52

Month: September 2011 Lab: DTI


50%



2,7 l air volume 560 350 160

5,4 l air volume 340 180 86

Ethylbenzene 16 9 7

Styrene 180 86 65

Month: November 2011 Lab: DTI


55%



2,7 l air volume 25

5,4 l air volume 13

Ethylbenzene 15 7 5


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A.4.2 Work package 2.1: Chamber sizes

Goal: Study the impact of using 4 different test chamber sizes (20 l, 119 l, 1 m³, 3 m³) with constant loading factor and ventilation rate on test result (in terms of emission rate) with products of different susceptibility to this parameter. According to theory, the area specific emission rate (µg/m²h) should remain constant in the selected range. Testing plan: Testing was performed in test chambers of 20 l, 119 l, 1 m³, 3 m³ with constant air velocity with: Foam type product Liquid type product Testing: After 3, 14 and 28 days storage in the test chamber, no storage outside test chamber during the test. All tests were performed under uniform conditions, as regards loading, ventilation, temperature, and humidity of supply air. Compounds to be measured: Selected dominating VOC, formaldehyde. Another test was performed with: Solid reference material Testing: After 2 and 3 days storage in the test chamber, no storage outside test chamber during the test. All tests were performed under standard conditions, as regards ventilation, temperature, and humidity of supply air. This work package was performed by Eurofins.

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A.4.2.1 WP 2.1 – Results: Foam type product

Product: Foam type product, selected for expected relatively high emissions Loading factor 0,4 m²/m³ Air change rate 0,5 / h Temperature 23 °C Humidity of supply air 50% RH Edges, back Covered with aluminum foil

Month: September 2011

Test chamber: 3,2 m³ Lab: Eurofins


Pentane 1200 740 250

Ethylbenzene 28 9,1 10

Styrene 210 59 69


Test chamber: 1 m³ Lab: Eurofins


Pentane 1100 * *

Ethylbenzene 20 13 8,8

Styrene 150 83 54 * no data due to error in GC instrument programming


Test chamber: 119 l Lab: Eurofins


Pentane 1000 * *


Styrene 120 80 63 * no data due to error in GC instrument programming




Pentane 880 800 240


Styrene 250 140 95 NOTE: These test results are not at all representative for the respective product group. CEN/TC 35

1 rep

ort


A.4.2.2 WP 2.1 – Results: Liquid type product

Product: Liquid type product, spiked with a number of VOC. Application: Exactly 200 g/m² on mineral with a brush. All these tests were all performed in August 2011. Loading factor 0,4 m²/m³ Air change rate 0,5 / h Temperature 23 °C Humidity of supply air 50% RH

Test chamber: 3,2 m³ Lab: Eurofins


Propyleneglycol > 11000 15 11 Butyldiglycol > 5300 110 34 Texanol > 3800 330 61 Diethylphthalate > 280 310 160 TXIB > 41 8,6 < 7

Hexadecane > 910 84 110

Test chamber: 1 m³ Lab: Eurofins


Propyleneglycol 410 < 7 < 7

Butyldiglycol 4100 9,3 < 7

Texanol 3800 96 < 7

Diethylphthalate 560 400 250

TXIB 53 < 5 < 7

Hexadecane 460 51 11



Propyleneglycol 1300 < 7 < 7

Butyldiglycol 4900 < 7 < 7

Texanol 3400 99 < 7

Diethylphthalate 350 240 230

TXIB 38 < 7 < 7

Hexadecane 850 8,5 < 7



Propyleneglycol 550 12 < 7 Butyldiglycol 2800 310 51 Texanol 2400 280 100 Diethylphthalate 300 250 160 TXIB 36 < 7 < 7 Hexadecane 510 98 56

Results after 3 days are imprecise due to high loading of tubes in all above 4 tables. NOTE: These test results are not at all representative for the respective product group.

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A.4.2.3 WP 2.1 – Results: Solid reference material

Product: Plastic film spiked with toluene by Virginia Tech, USA, in cooperation with NIST (National Institute of Standards and Technology, Gaithersburg, MD, USA). Air change rate 0,5 / h Temperature 23 °C Humidity of supply air 50% RH Predicted concentration Calculated by NIST using a model developed by John Little, Virginia

Tech, USA.

Test chamber: 3,2 m³ Loading factor 0,05 m²/m³

Toluene µg/m³ after 1 day µg/m³ after 2 days µg/m³ after 3 days

Measured 81 37 26

Predicted 110 67 42 Measured, % of predicted 74% 55% 62%

Test chamber: 1 m³ Loading factor 0,08 m²/m³


Measured 150 88 79


Test chamber: 119 l Loading factor 0,17 m²/m³


Measured 380 250 170






NOTE: These test results are not at all representative for the respective product group. CEN/TC 35

1 rep

ort


A.4.3 Work package 2.2 – 2.4: Loading factor and ventilation

Goal: Study the impact of different air change rate with constant loading factor (0,4 m²/m³), of different loading factor with constant air change rate, and of simultaneous change of air change rate and loading factor (with constant area specific air flow rate q), on test result (in terms of emission rate). According to theory, the area specific emission rate (µg/m²h) should remain constant in the selected range. Testing plan: Testing was to be performed with different ventilation, with air change rate

o 0,3 per hour o 0,7 per hour o 1,5 per hour o with constant loading factor (0,7 m²/m³)

loading factor

o 0,3 m²/m³ o 0,7 m²/m³ o 1,5 m²/m³ o with constant air change rate (0,7 per hour)

air change rate changed simultaneously with loading factor, with keeping constant q

(recommended q = 1.0 m³/m²h) o 0,3 m²/m³ o 0,7 m²/m³ o 1,5 m²/m³

All tests were performed in test chambers of different sizes and with products of different

susceptibility to these parameters: o Flooring type product o Foam type product o Liquid type product

Testing: After 3, 14 and 28 days storage in test chamber, no storage outside chamber during the test. Compounds to be measured: Selected dominating VOC, formaldehyde. All tests were performed under standard conditions, as regards temperature, and humidity of supply air. If measurement at the first point of time (after 3 days) showed that there was no formaldehyde detectable, then it was considered not necessary to continue with the DNPH measurements at later points of time. Additionally, a liquid type product sample was tested by eco at loading factor 0.4 m²/m³ at three different air velocities above surface of test specimen for showing how increase of air velocity will impact test result with all other testing parameters being unchanged.

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Testing was performed by:

1 m³ test chamber 100 – 250 l test chamber 20 – 25 l test chamber

3 loading factors

Flooring type product VTT eco –

Foam type product eurofins IDMEC –

Liquid type product BAM Mapei BAM

3 air change rates




3 loading factors with simultaneous change of air change rate




3 different air velocities

Liquid type product eco

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A.4.3.1 WP 2.2 – 2.4 – Results: Flooring type product

Product: Flooring type product, selected for expected relatively high emissions Temperature 23 °C Humidity of supply air 50% RH Back Covered with aluminum foil

Please note that the emissions of the product decreased during project time. This may explain some of the observed differences.

A.4.3.1.1 WP 2.2 – Results: Flooring type product, 3 loading factors

Month: December 2011 Lab: VTT

Test chamber: 1 m³

Loading factor 0,3 m²/m³ Air change rate 0,7/h






Hexanal 35 25 26


Test chamber: 1 m³







Hexanal 51 40 41


Test chamber: 1 m³







Hexanal 64 42 53 NOTE: These test results are not at all representative for the respective product group. CEN/TC 35

1 rep

ort


A.4.3.1.1 WP 2.2 – Results: Flooring type product, 3 loading factors (continued)


Test chamber: 125 l










Test chamber: 125 l






Octanoic acid 7 7 7




Test chamber: 125 l






Octanoic acid 5 4 4



1 rep

ort


A.4.3.1.2 WP 2.3 – Results: Flooring type product, 3 air change rates

Month: October 2011 Lab: VTT

Test chamber: 1 m³







Hexanal 6 8 7


Test chamber: 1 m³







Hexanal 16 17 14


Test chamber: 1 m³








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A.4.3.1.2 WP 2.3 – Results: Flooring type product, 3 air change rates (continued)


Test chamber: 125 l






Octanoic acid 4 5 5




Test chamber: 125 l










Test chamber: 125 l








Hexanal (DNPH) 28 19 19 NOTE: These test results are not at all representative for the respective product group.

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A.4.3.1.3 WP 2.4 – Results: Flooring type product, 3 loading factors with simultaneous change of air change rate

Month: November 2011 Lab: VTT

Test chamber: 1 m³







Hexanal 19 13 14


Test chamber: 1 m³







Hexanal 44 31 36


Test chamber: 1 m³








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A.4.3.1.3 WP 2.4 – Results: Flooring type product, 3 loading factors with simultaneous change of air change rate (continued)


Test chamber: 125 l










Test chamber: 125 l






Octanoic acid 7 8 6




Test chamber: 125 l









1 rep

ort


A.4.3.2 WP 2.2 – 2.4 – Results: Foam type product

Product: Foam type product, selected for expected relatively high emissions Temperature 23 °C Humidity of supply air 50% RH Edges, back Covered with aluminum foil

Please note that the emissions of the product decreased during project time. This may explain some of the observed differences.

A.4.3.2.1 WP 2.2 – Results: Foam type product, 3 loading factors

Month: October / November 2011 Lab: eurofins

Test chamber: 1 m³



n-Pentane 470 350 83


Styrene 280 180 56


Test chamber: 1 m³



n-Pentane 440 230 280


Styrene 230 86 57


Test chamber: 1 m³



n-Pentane 510 430 330



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A.4.3.2.1 WP 2.2 – Results: Foam type product, 3 loading factors (continued)

Month: August 2011 Lab: IDMEC

Test chamber: 255 l



n-Pentane * 790 390 250


Styrene 220 160 97 * calculated as toluene equivalent.


Test chamber: 255 l



n-Pentane * 1200 310 140




Test chamber: 255 l



n-Pentane * 850 390 150


Styrene 290 170 110 * calculated as toluene equivalent. NOTE: These test results are not at all representative for the respective product group.

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A.4.3.2.2 WP 2.3 – Results: Foam type product, 3 air change rates

Please note that the emissions of the product decreased during project time. This concerned the emissions tests in the 255 l test chambers. Direct comparison of test results between test chambers of different volume is not possible for that reason.

Month: November/December 2011 Lab: eurofins

Test chamber: 1 m³



n-Pentane 200 99 73

Ethylbenzene 22 19 < 7

Styrene 150 120 17


Test chamber: 1 m³



n-Pentane 210 180 180


Styrene 180 140 190 This test could not be performed at higher air change rate for temporary technical reasons. Therefore a medium air change rate was selected as third level.


Test chamber: 1 m³



n-Pentane 240 160 140



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A.4.3.2.2 WP 2.3 – Results: Foam type product, 3 air change rates (continued)

Month: September 2011 Lab: IDMEC

Test chamber: 255 l



n-Pentane * 160 67 37




Test chamber: 255 l



n-Pentane * 170 48 25




Test chamber: 255 l



n-Pentane * 104 37 20



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A.4.3.2.3 WP 2.4 – Results: Foam type product, 3 loading factors with simultaneous change of air change rate

Please note that the emissions of the product decreased during project time. This concerned the emissions tests in the 255 l test chambers. Direct comparison of test results between test chambers of different volume is not possible for that reason.


Test chamber: 1 m³



n-Pentane 380 250 230


Styrene 230 120 90


Test chamber: 1 m³



n-Pentane 460 310 270


Styrene 210 97 81


Test chamber: 1 m³



n-Pentane 130 150 100

Ethylbenzene 13 9,5 7,4


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A.4.3.2.3 WP 2.4 – Results: Foam type product, 3 loading factors with simultaneous change of air change rate (continued)

Month: October 2011 Lab: IDMEC

Test chamber: 255 l



n-Pentane * 58 40 29




Test chamber: 255 l




Ethylbenzene 15 8,7 7,4



Test chamber: 255 l






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A.4.3.3 WP 2.2 – 2.4 – Results: Liquid type product

Product: Liquid type product, spiked with a number of VOCs for achieving relatively high emissions. Temperature 23 °C Humidity of supply air 50% RH Application Target application – 200 g/m² with a brush;

some tests were performed with application by a trowel

A.4.3.3.1 WP 2.2 – Results: Liquid type product, 3 loading factors

Month: September 2011 Lab: BAM

Test chamber: 1 m³ Application: 138 g/m²



Acetic acid < 5 18 6,3

Propyleneglycol < 5 9,3 9,0 Butyldiglycol 28 10 7,3 Texanol 12 2,8 1,0 Diethylphthalate ---* ---* 190 Hexadecane 4,7 8,3 0,5

Measurement after 3 days failed and was substituted by measurement after 7 days. * No data due to non-optimized GC instrument.






Propyleneglycol 44 14 6,3 Butyldiglycol 170 18 5,4 Texanol 500 6,4 1,3 Diethylphthalate ---* ---* 240 Hexadecane 5,8 1,3 0,3

Measurement after 3 days failed and was substituted by measurement after 6 days. * No data due to non-optimized GC instrument.






Propyleneglycol 35 12 < 5

Butyldiglycol 430 32 8,3 Texanol 680 99 3,5 Diethylphthalate ---* ---* 200 Hexadecane 25 4,0 1,0

Formaldehyde was detected in no single case in all above 3 tables. Measurement after 3 days failed and was substituted by measurement after 7 days. * No data due to non-optimized GC instrument. NOTE: These test results are not at all representative for the respective product group.

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A.4.3.3.1 WP 2.2 – Results: Liquid type product, 3 loading factors (continued)

Month: September 2011 Lab: MAPEI

Test chamber: 110 l Application: 203 g/m²



Acetic acid* 35 <1 <1

Propyleneglycol 2200 84 <1 Butyldiglycol 4500 91 67 Texanol 4200 42 27 Diethylphthalate 1300 560 740 TXIB * 101 18 11 Hexadecane 9200 1100 320

* calculated as toluene equivalent.





Acetic acid * 20 <1 <1

Propyleneglycol 6100 59 34 Butyldiglycol 4300 103 31 Texanol 2600 240 39 Diethylphthalate 610 400 410 TXIB * 75 18 13 Hexadecane 2800 370 75








* calculated as toluene equivalent. Formaldehyde was detected in no single case in all above 3 tables. Results after 3 days are imprecise due to high loading of tubes in all above 3 tables. NOTE: These test results are not at all representative for the respective product group.

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A.4.3.3.1 WP 2.2 – Results: Liquid type product, 3 loading factors (continued)





Acetic acid < 5 14 7,0

Propyleneglycol < 5 10 6,5 Butyldiglycol 23 7,9 7,0 Texanol 17 3,1 1,0 Diethylphthalate ---* ---* 150 Hexadecane 20 6,8 2,2

Formaldehyde was detected in no single case. Measurement after 3 days failed and was substituted by measurement after 7 days. * No data due to non-optimized GC instrument.






Propyleneglycol 35 10 6,1 Butyldiglycol 66 15 5,0 Texanol 210 3,0 0,9 Diethylphthalate ---* ---* 170 Hexadecane 10 1,8 0,9

Formaldehyde was detected in no single case. Measurement after 3 days failed and was substituted by measurement after 6 days. * No data due to non-optimized GC instrument.






Propyleneglycol 72 24 8,8 Butyldiglycol 1600 120 9,2 Texanol 430 320 12 Diethylphthalate ---* ---* 190 Hexadecane 1400 6,7 1,0

Formaldehyde was detected in no single case. Measurement after 3 days failed and was substituted by measurement after 7 days. * No data due to non-optimized GC instrument. NOTE: These test results are not at all representative for the respective product group.

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A.4.3.3.2 WP 2.3 – Results: Liquid type product, 3 air change rates

Month: October 2011 Lab: BAM




Acetic acid 150 13 9,2

Propyleneglycol 2800 47 11 Butyldiglycol 9000 340 27 Texanol 2700 550 62 Diethylphthalate 120 220 220 Hexadecane 740 28 5,8

Formaldehyde was detected in no single case. Measurement after 3 days failed and was substituted by measurement after 5 days.





Acetic acid 330 9,2 4,0

Propyleneglycol 1300 16 5,0 Butyldiglycol 13000 18 5,4 Texanol 6200 38 2,3 Diethylphthalate 350 520 380 Hexadecane 590 2,0 1,2






Acetic acid 310 5,6 < 5

Propyleneglycol 140 5,8 < 5

Butyldiglycol 2600 9,4 4,4 Texanol 3600 4,1 2,1 Diethylphthalate 660 710 370 Hexadecane 28 2,1 1,4

Formaldehyde was detected in no single case. Results after 3 days are imprecise due to high loading of tubes. NOTE: These test results are not at all representative for the respective product group. CEN/TC 35

1 rep

ort


A.4.3.3.2 WP 2.3 – Results: Liquid type product, 3 air change rates (continued)

Month: October / November 2011 Lab: MAPEI






Formaldehyde was detected in no single case. Results after 3 days are imprecise due to high loading of tubes. * calculated as toluene equivalent.






Propyleneglycol 5900 126 34 Butyldiglycol 4000 90 <1 Texanol 2200 340 6 Diethylphthalate 400 450 290 TXIB * 49 13 3 Hexadecane 3200 290 24

Formaldehyde was detected in no single case. Results after 3 days are imprecise due to high loading of tubes. * calculated as toluene equivalent.






Propyleneglycol 1400 <1 <1 Butyldiglycol 5300 9 <1 Texanol 3500 93 <1 Diethylphthalate 560 480 320 TXIB * 66 12 <1 Hexadecane 9200 540 <1

Formaldehyde was detected in no single case. Results after 3 days are imprecise due to high loading of tubes. * calculated as toluene equivalent. NOTE: These test results are not at all representative for the respective product group.

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A.4.3.3.2 WP 2.3 – Results: Liquid type product, 3 air change rates (continued)






Propyleneglycol 2900 62 12 Butyldiglycol 8800 370 12 Texanol 2600 630 38 Diethylphthalate 100 230 200 Hexadecane 830 23 3,1

Formaldehyde was detected in no single case. Measurement after 3 days failed and was substituted by measurement after 5 days.






Propyleneglycol 1200 17 < 5 Butyldiglycol 11000 20 4,1 Texanol 5900 58 2,4 Diethylphthalate 310 460 340 Hexadecane 1000 4,8 2,0







Propyleneglycol 300 21 8,5 Butyldiglycol 7000 18 6,8 Texanol 6000 18 4,3 Diethylphthalate 580 780 460 Hexadecane 2200 11 4,6


CEN/TC 351 r

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A.4.3.3.3. WP 2.4 – Results: Liquid type product, 3 loading factors with simultaneous change of air change rate

Month: November 2011 Lab: BAM





Propyleneglycol 3400 29 9,5 Butyldiglycol 13000 77 17 Texanol 5900 105 10 Diethylphthalate 310 240 300 Hexadecane 1000 44 6,3
















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A.4.3.3.3. WP 2.4 – Results: Liquid type product, 3 loading factors with simultaneous change of air change rate (continued)









Month: November 2011












Propyleneglycol 8100 57 <1 Butyldiglycol 4300 195 <1 Texanol 2300 520 17 Diethylphthalate 420 430 280 TXIB * 52 21 1 Hexadecane 3400 330 58

* calculated as toluene equivalent. Formaldehyde was detected in no single case n all above 3 tables. Results after 3 days are imprecise due to high loading of tubes n all above 3 tables. NOTE: These test results are not at all representative for the respective product group.

CEN/TC 351 r

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A.4.3.3.3. WP 2.4 – Results: Liquid type product, 3 loading factors with simultaneous change of air change rate (continued)













Propyleneglycol 1200 15 5,7 Butyldiglycol 13000 11 5,2 Texanol 6800 7,7 2,5 Diethylphthalate 330 360 300

Hexadecane 870 7,7 3,2 Formaldehyde was detected in no single case. Results after 3 days are imprecise due to high loading of tubes.








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A.4.3.3.3. WP 2.4 – Results: Liquid type product, 3 different air velocities




Air velocity above test specimen: 0,1 m/s


Acetic acid 140 25 <1

Propyleneglycol 1300 10 <1 Butyldiglycol 12000 280 73 Texanol 1900 140 40 Diethylphthalat 350 260 110 TXIB 11 20 10 Hexadecane 190 55 33







Propyleneglycol 1400 3 1 Butyldiglycol 11000 290 84 Texanol 1900 140 44 Diethylphthalat 380 250 110 TXIB 10 20 13 Hexadecane 380 54 39







Propyleneglycol 1000 6 <1 Butyldiglycol 9400 260 66 Texanol 1800 140 36 Diethylphthalat 380 230 99 TXIB 10 24 13 Hexadecane 360 66 40

Formaldehyde was detected in no single case in all above 3 tables. Results after 3 days are imprecise due to high loading of tubes n all above 3 tables. NOTE: These test results are not at all representative for the respective product group.

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A.4.4 Work package 3: Sealing technique for back and edges

Goal: Study the impact on test result (in terms of area specific emission rate) of different air sealing techniques of back and edges with flat solid products with different level of emissions from edges resp. from back than from top surface. Testing plan: Testing was performed with: Wooden flooring type product: No sealing Partial sealing (as DIBt for wooden flooring type products) Back-to-back and complete sealing of edges with tape Tape emissions (as blank) Solid product with higher emissions from back than from top surface: FLEC test on top of product (as reference) FLEC test on back of product (as reference) Back-to-back and sealing of edges with tape Placement on mineral plate and sealing of edges with tape Seal box (JIS A1901) Tray (California CDPH Section 1350, CRI) Testing: After 3, 14 and 28 days storage in the test chamber, no storage outside test chamber during the test. Compounds to be measured: Selected dominating VOC, formaldehyde. This work package was performed by Eurofins. An inquiry among test laboratories on the brands of aluminum tape in use gave feedback from 6 laboratories with this result: Lab # Aluminum tape in use 1 TESA #60576 2 Rubans de Normandie 3 3M - HD 425 4 3M 5 TESA #50565 with liner 6 Neolab

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A.4.4.1 Results – Wooden flooring type product

Product: Commercial wooden flooring type product, selected for expected relatively high emissions Loading factor 0,8 m²/m³ Air change rate 0,5 / h Temperature 23 °C Humidity of supply air 50% RH

Test chamber: 119 l

no coverage, all sides exposed, as reference


Formaldehyde 350 190 170 Acetic acid 190 81 81 Hexanal 47 21 13 2-Ethyl-1-hexanol < 1 < 1 < 1

Ethyl hexyl acetate < 1 < 1 < 1 2-Ethylhexylacrylate < 1 < 1 < 1

Test chamber: 119 l

Coverage of edges and back, including joint as specified by DIBt


Formaldehyde 16 11 13 Acetic acid < 3 < 3 < 3 Hexanal 13 8,8 11 2-Ethyl-1-hexanol 6,9 2,8 3,5

Ethyl hexyl acetate 2,4 1,3 1,3 2-Ethylhexylacrylate 5,8 2,8 3,1

Test chamber: 119 l

back to back, sealed with tape, no joint included


Formaldehyde 18 14 19 Acetic acid < 3 < 3 < 3 Hexanal 14 8,8 13 2-Ethyl-1-hexanol 7,5 1,1 1,6

Ethyl hexyl acetate 3,4 1,3 1,0 2-Ethyl hexyl acrylate 7,5 2,1 2,3

Test chamber: 119 l

Sealing tape test of the tape, applied on a mineral plate, as reference


Formaldehyde < 2 < 2 < 2 2-Ethyl-1-hexanol 2,2 < 1 < 1

Ethyl hexyl acetate < 1 < 1 < 1 2-Ethylhexylacrylate 1,3 < 1 < 1

NOTE: These test results are not at all representative for the respective product group.

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A.4.4.2 Results – Solid product with high emissions from back

Product: Trial solid product with high emissions from back, selected for expected relatively high difference of emissions from back and from top surface. Area specific air flow rate 1,25 m³/m²h Loading factor (chambers only) 0,4 m²/m³ Air change rate (chambers only) 0,5 / h Temperature 23 °C Humidity of supply air 50% RH

Test chamber: FLEC cell

Top surface as reference


Formaldehyde < 4 < 4 < 4 Phenol 8,4 < 7 < 7

Butyldiglycol < 7 < 7 < 7

2-Ethylhexanoic acid < 7 < 7 < 7

2-Ethyl-1-hexanol < 7 < 7 < 7

2-Ethylhexylacrylat < 7 < 7 < 7

Test chamber: FLEC cell

Back surface as reference


Formaldehyde < 4 < 4 < 4 Phenol 73 68 89

Butyldiglycol 690 200 310

2-Ethylhexanoic acid 43 58 36



Test chamber: 119 l

Back to back, sealed with tape


Formaldehyde < 4 < 4 < 4

Phenol 12 9,4 6,8



2-Ethyl-1-hexanol 7 < 7 < 7

2-Ethylhexylacrylat 9,1 < 7 < 7 NOTE: These test results are not at all representative for the respective product group. CEN/TC 35

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A.4.4.2 Results – Solid product with high emissions from back (continued)

Test chamber: 119 l

Fixed on mineral plate, edges sealed with tape


Formaldehyde < 4 < 4 < 4 Phenol 31 15 12

Butyldiglycol 34 18 < 7




Test chamber: 119 l

Seal box as specified in JIS A1901


Formaldehyde < 4 < 4 < 4 Phenol 17 15 9,3





Test chamber: 119 l

Steel frame as specified by US Carpet & Rug Institute and by California CDPH method "Section 01350"


Formaldehyde < 4 < 4 < 4 Phenol 18 12 12 Butyldiglycol 15 7,4 < 7



2-Ethylhexylacrylat < 7 < 7 < 7 NOTE: These test results are not at all representative for the respective product group.

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A.4.5 Work package 4: Evaluate reference material for method validation

Goal: Study the significance of a solid reference material for toluene for validation of whole method with participation of all involved laboratories. Testing plan: Testing was performed with toluene spiked films, produced by Virginia Tech in cooperation with NIST, dispatched in dry ice cooled containers. Testing included a test for toluene emissions in test chamber at least after 2 and 3 days, with operation parameters as they are used normally to the most possible extent. This work package was performed by all participating laboratories.

A.4.5.1 Results

Lab: Lab 1

Status of material when arriving: Cool but not cold



Measured 212 130 92


Lab: Lab 2

Status of material when arriving: Room temperature



Measured - 216 154

Predicted - 254 161 Measured, % of predicted - 85% 96%

Lab: Lab 3




Measured - 180 130

Predicted - 216 134 Measured, % of predicted - 83% 97%

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A.4.5.1 Results – reference material (continued)

Lab: Lab 4a

Status of material when arriving: Cold

Test chamber: 3,2 m³ Loading factor 0,05 m²/m³

Toluene µg/m²h after 1 day µg/m²h after 2 days µg/m²h after 3 days

Measured 81 37 26


Lab: Lab 4b




Measured 150 88 79


Lab: Lab 4c






Lab: Lab 4d






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A.4.5.1 Results – reference material (continued)

Lab: Lab 5






Lab: Lab 6



Substance µg/m³ after 1 day µg/m³ after 2 days µg/m³ after 3 days


NIST model 406 244 152 Measured, % of model 71% 86% 103%

Lab: Lab 7






Lab: Lab 8




Measured 98,3 61,2 52,5


Lab: Lab 9




Measured 158 118 84


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A.4.6 Work package 5: Tenax TA tubes and benzene artifact generation

Goal: Investigate the generation of benzene during air sampling and analysis in different labs with different experimental settings for identifying options to control and minimize benzene artifact formation and to adapt the standard text accordingly. Testing plan: Procedure: Preparation / cleaning of 10 Tenax TA tubes; in best case 5 new tubes and 5 old (re-used) tubes. Analysis of blank value of BTX (benzene, toluene, xylene); for benzene please a detection limit of

0,1 µg/m³ should be targeted (if calculated with the typical sampling volume in the respective lab). Air sampling from any atmosphere known to be free of BTX, containing some tens or even

hundreds µg/m³ of other VOCs. Analysis of these tubes for BTX, including reporting of the main other VOCs on the tube. This work package was performed by all participating laboratories.

A.4.6.1 Results

BTX results before (blank) and after (exposed) exposure to BTX free air sample.

A.4.6.1.1Summary

Lab Sample volume

Increase benzene

Thermal desorption Other VOCs in sampled atmosphere

no. liters ng °C minutes

1 1 0 – 0,2 290 5 DEP, texanol

2 2,8 – 5,4 0 290 8 n-butanol, n-hexanal, butylglycol

3 5 0 – 0,7 290 15 D3-carene, α-/β-pinene, aldehydes, n-butanol, …

4 9,6 0,5 – 1,2 300 7 2,2,4,6,6-pentamethylheptane

5 0,9 – 2,5 0 – 1,3 260 10 Cyclohexane, octane, decane, hexadecane

6 4 3 – 13 300 10 decane, dodecane, and traces of more VOCs

7 5,4 0 – 1,0 275 15 propylene glycol, C10-C16 alkanes

8 4,3 – 4,7 1,6 – 2,9 260 6 organic acids and aldehydes

9 6 0,4 – 1,4 290 8 α-pinene, acetone

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A.4.6.1.2 Details – benzene artifact test

Lab: Lab 1 Main VOC: DEP, texanol Sample volume: 1,0 l air

Tube # Benzene ng Benzene µg/m³

Toluene µg/m³ Xylenes µg/m³

Blank Exposed Increase Increase Blank Exposed Blank Exposed ng ng ng µg/m³ µg/m³ µg/m³ µg/m³ µg/m³ New tubes 1 0,6 0,6 0 0 < 0,1 < 0,1 < 0,1 < 0,1 2 0,7 0,8 0,1 0,1 < 0,1 < 0,1 < 0,1 < 0,1 3 0,8 1,0 0,2 0,2 < 0,1 < 0,1 < 0,1 < 0,1 4 0,8 1,0 0,2 0,2 < 0,1 < 0,1 < 0,1 < 0,1 5 0,8 0,9 0,1 0,1 < 0,1 < 0,1 < 0,1 < 0,1 Re-used tubes 6 0,8 0,8 0 0 < 0,1 < 0,1 < 0,1 < 0,1 7 0,8 0,9 0,1 0,1 < 0,1 < 0,1 < 0,1 < 0,1 8 0,8 0,9 0,1 0,1 < 0,1 < 0,1 < 0,1 < 0,1 9 0,7 0,8 0,1 0,1 < 0,1 < 0,1 < 0,1 < 0,1 10 0,8 0,8 0 0 < 0,1 < 0,1 < 0,1 < 0,1

Lab: Lab 2 (tubes exposed in lab 2 and analyzed in lab 9) Main VOC: n-Butanol, n-Hexanal, Butylglycol Sample volume: 2,8 – 5,4 l air (tube #1: 5,1 l; #2: 2,8 l; #3: 5,4 l; #4: 2,8 l)



Blank Exposed Increase Increase Blank Exposed Blank Exposed ng ng ng µg/m³ µg/m³ µg/m³ µg/m³ µg/m³ New tubes 1 < 2 < 2 0 0 < 0,4 < 0,4 < 0,4 < 0,4 2 < 2 < 2 0 0 < 0,9 < 0,9 < 0,9 < 0,9 Re-used tubes 3 < 2 < 2 0 0 < 0,5 < 0,5 < 0,5 < 0,5 4 < 2 < 2 0 0 < 0,9 < 0,9 < 0,9 < 0,9

Lab: Lab 3 Main VOC: D3-carene, α-/β-pinene, aldehydes, n-butanol, n-butyl acetate, … Sample volume: 5 l air



Blank Exposed Increase Increase Blank Exposed Blank Exposed ng ng ng µg/m³ µg/m³ µg/m³ µg/m³ µg/m³ New tubes 1 1,4 1,3 -0,1 0,0 <1 <1 <1 <1 2 1,5 1,4 -0,1 0,0 <1 <1 <1 <1 3 1,3 1,5 0,2 0,0 <1 <1 <1 <1 4 1,7 1,7 0,0 0,0 <1 <1 <1 <1 5 1,7 1,8 0,1 0,0 <1 <1 <1 <1 Re-used tubes 6 3,2 3,2 0,0 0,0 <1 <1 <1 <1 7 2,7 2,5 -0,2 0,0 <1 <1 <1 <1 8 2,6 2,6 0,0 0,0 <1 <1 <1 <1 9 2,4 3,2 0,7 0,1 <1 <1 <1 <1 10 3,2 3,4 0,2 0,0 <1 <1 <1 <1

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A.4.6.1.2 Details – benzene artifact test (continued) Lab: Lab 4 Main VOC: 2,2,4,6,6-Pentamethylheptane, TVOC 50-60 µg/m³ Sample volume: 9,6 l air



Blank Exposed Increase Increase Blank Exposed Blank Exposed ng ng ng µg/m³ µg/m³ µg/m³ µg/m³ µg/m³ New tubes 1 < 1 2,2 1,2 0,12 < 0,1 0,5 < 0,1 0,19 2 < 1 2,1 1,1 0,11 < 0,1 0,29 < 0,1 0,19 3 < 1 1,6 0,6 0,06 < 0,1 0,21 < 0,1 0,17 4 < 1 1,6 0,6 0,06 < 0,1 0,34 < 0,1 0,19 5 < 1 1,7 0,7 0,07 < 0,1 0,59 < 0,1 0,17 Re-used tubes 6 < 1 1,7 0,7 0,07 < 0,1 0,18 < 0,1 0,16 7 < 1 1,8 0,8 0,08 < 0,1 0,2 < 0,1 0,16 8 < 1 1,6 0,6 0,06 < 0,1 0,47 < 0,1 0,17 9 < 1 1,5 0,5 0,05 < 0,1 0,29 < 0,1 0,16 10 < 1 2,1 1,1 0,11 < 0,1 0,2 < 0,1 0,15

Lab: Lab 5 Main VOC: Cyclohexane, octane, decane, hexadecane Sample volume: 0,9 – 2,5 l air



Blank Exposed Increase Increase Blank Exposed Blank Exposed ng ng ng µg/m³ µg/m³ µg/m³ µg/m³ µg/m³ New tubes 1 ol ol ol ol ol ol ol ol 2 0,5 1,1 0,6 0,6 0,6 1,5 nd nd 3 0,8 2,0 1,3 0,8 0,6 1,2 nd nd 4 0,9 1,2 0,3 0,1 0,3 1,0 nd nd 5 0,4 1,1 0,8 0,3 0,3 0,3 nd nd Re-used tubes 6 ol ol ol ol ol ol ol ol 7 0 0,9 0,9 1,0 0,8 1,4 nd nd 8 0,9 0,9 0 0 0,4 1,1 nd nd 9 0,6 1,0 0,5 0,3 0,3 0,8 nd nd 10 0 0,8 0,8 0,5 0,3 0,7 nd nd

ol: tubes were overloaded with other substances and did not give meaningful results nd: not determined, as xylene was present in the sampled atmosphere CEN/TC 35

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A.4.6.1.2 Details – benzene artifact test (continued) Lab: Lab 6 Main VOC: Decane, dodecane, and traces of more VOCs Sample volume: 4 l air



Blank Exposed Increase Increase Blank Exposed Blank Exposed ng ng ng µg/m³ µg/m³ µg/m³ µg/m³ µg/m³ New tubes 1 9,1 13 4,1 1,0 3,0 21 1,8 7,1 2 4,3 11 6,7 1,7 1,2 17 0,7 5,5 3 2,1 14 12 3,1 2,5 21 1,1 6,2 4 2,3 7,6 5,2 1,3 0,7 14 0,5 5,0 5 2,4 8,4 6,0 1,5 1,0 15 0,9 5,5 Re-used tubes 6 0,1 6,9 6,8 1,7 4,3 13 4,2 4,6 7 0,1 13 13 3,3 1,5 17 2,2 6,7 8 1,8 10 8,6 2,2 0,5 18 0,3 5,5 9 5,3 8,2 2,9 0,7 2,5 17 2,0 6,4 10 1,9 8,7 6,8 1,7 0,4 17 <0,1 5,8

Lab: Lab 7 Main VOC: Propylene glycol, C10-C16 alkanes Sample volume: 5,4 l air



Blank Exposed Increase Increase Blank Exposed Blank Exposed ng ng ng µg/m³ µg/m³ µg/m³ µg/m³ µg/m³ New tubes 1 2,0 2,0 0 0 < 0,1 < 0,1 < 0,1 < 0,1 2 2,0 2,5 0,5 0,1 < 0,1 < 0,1 < 0,1 < 0,1 3 2,0 1,0 -1,0 -0,2 < 0,1 < 0,1 < 0,1 < 0,1 4 2,0 2,0 0 0 < 0,1 < 0,1 < 0,1 < 0,1 5 1,5 1,0 -0,5 -0,1 < 0,1 < 0,1 < 0,1 < 0,1 Re-used tubes 6 1,0 2,0 1,0 0,2 < 0,1 < 0,1 < 0,1 < 0,1 7 1,0 1,5 0,5 0,1 < 0,1 < 0,1 < 0,1 < 0,1 8 1,0 2,0 1,0 0,2 < 0,1 < 0,1 < 0,1 < 0,1 9 1,0 1,5 0,5 0,1 < 0,1 < 0,1 < 0,1 < 0,1 10 1,5 1,5 0 0 < 0,1 < 0,1 < 0,1 < 0,1

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A.4.6.1.2 Details – benzene artifact test (continued) Lab: Lab 8 Main VOC: Organic acids and aldehydes Sample volume: 4,3 - 4,7 l air



Blank Exposed Increase Increase Blank Exposed Blank ExposedRe-used tubes 1 < 1 3,5 2,5 0,6 < 1 < 1 < 1 < 1 2 < 1 2,9 1,9 0,4 < 1 < 1 < 1 < 1 3 < 1 2,6 1,6 0,4 < 1 < 1 < 1 < 1 4 < 1 3,5 2,5 0,5 < 1 < 1 < 1 < 1 5 < 1 3,6 2,6 0,6 < 1 < 1 < 1 < 1 6 < 1 3,1 2,1 0,4 < 1 < 1 < 1 < 1 7 < 1 3,7 2,7 0,6 < 1 < 1 < 1 < 1 8 < 1 3,4 2,4 0,6 < 1 < 1 < 1 < 1 9 < 1 3,8 2,8 0,6 < 1 < 1 < 1 < 1 10 < 1 3,9 2,9 0,7 < 1 < 1 < 1 < 1

Increase of benzene was calculated by subtracting 1 ng. Lab: Lab 9 Main VOC: α-pinene, acetone Sample volume: 6 l air



Blank Exposed Increase Increase Blank Exposed Blank Exposed ng ng ng µg/m³ µg/m³ µg/m³ µg/m³ µg/m³ Re-used tubes 1 1,0 2,4 1,4 0,2 < 0,2 < 0,2 < 0,2 < 0,2 2 1,0 2,4 1,4 0,2 < 0,2 < 0,2 < 0,2 < 0,2 3 2,0 2,4 0,4 0,1 < 0,2 < 0,2 < 0,2 < 0,2 4 1,0 1,8 0,8 0,1 < 0,2 < 0,2 < 0,2 < 0,2 5 1,0 2,4 1,4 0,2 < 0,2 < 0,2 < 0,2 < 0,2 6 2,0 2,4 0,4 0,1 < 0,2 < 0,2 < 0,2 < 0,2 7 1,0 2,4 1,4 0,2 < 0,2 < 0,2 < 0,2 < 0,2 8 1,0 2,4 1,4 0,2 < 0,2 < 0,2 < 0,2 < 0,2 9 2,0 2,4 0,4 0,1 < 0,2 < 0,2 < 0,2 < 0,2 10 2,0 2,4 0,4 0,1 < 0,2 < 0,2 < 0,2 < 0,2

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robustness validation of methods developed by cen/tc 351 ......validation of cen/tc 351/wg 2 draft...

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