QUANTIFICATION OF THE PRODUCT EMISSIONS BY … documents/EPHECT... · QUANTIFICATION OF THE PRODUCT...

EPHECT is co-funded by European Union (Executive Agency for Health and Consumers- EAHC)

framework of the Health Programmes 2006-2013

QUANTIFICATION OF THE PRODUCT

EMISSIONS BY LABORATORY TESTING

WP6

PART II RESULTS OF PRODUCT TESTING EXPERIMENTS

Marianne Stranger, Frederick Maes, Eddy Goelen (VITO)

Asger W. Nørgaard, Peder Wolkoff (NRCWE)

Gabriela Ventura, Eduardo de Oliveira Fernandes (IDMEC)

Evangelos Tolis, George Efthimiou, Krystallia Kalimeri, John Bartzis (UOWM)

Thomas Letzel (TUM)

April 2013

EVALUATOR

The present report has been evaluated by Reinhard Oppl and A.I.S.E.

“© VITO, NRCWE, IDMEC, UOWM, TUM

All rights on the materials described in this document rest with VITO, NRCWE, UOWM, IDMEC and TUM.

This document is produced in the frame of the EPHECT –project. The EPHECT-project is co-funded by the European

Union in the framework of the health Programmes 2006-2013. The information and views set out in this document

are those of the author(s) and do not necessarily reflect the official opinion of the European Union. Neither the

European Union institutions and bodies nor any person acting on their behalf, nor the authors may be held

responsible for the use which may be made of the information contained herein.

Reproduction is authorized provided the source is acknowledged.”

Distribution List

III

DISTRIBUTION LIST

Vlaamse Instelling voor Technologisch Onderzoek , Mol, Belgium

University of Western Macedonia, Kozani, Greece

Agence Nationale de Sécurité Sanitaire, Alimentation, Environnement, Travail, Paris, France

Technische Universität München, Germany

The National Research Centre for the Working Environment, Copenhagen, Denmark

Instituto de Engenharia Mecanica Environment, Porto, Portugal

Universita Degli Studi di Milano, Italy

Ipsos Belgium, Waterloo, Belgium

Summary

IV

Table of contents

V

TABLE OF CONTENTS

Distribution List _________________________________________________________________ III

Table of contents ________________________________________________________________ V

List of figures ___________________________________________________________________ VII

List of tables __________________________________________________________________ VIII

List of acronyms _________________________________________________________________ X

CHAPTER 1 Product testing strategy _______________________________________________ 1

1.1. Structure of the report “Part II product testing experiments” 1

1.2. Test chamber experiments of the 15 product classes 1

CHAPTER 2 Assessment of the composition of selected consumer products (TUM) _________ 3

2.1 Information on product composition 3 2.1.1 Information on product label ___________________________________________ 7 2.1.2 Information directly by company ________________________________________ 7 2.1.3 Information available online ____________________________________________ 8 2.1.4 Consumer product composition analysis in EPHECT __________________________ 9 2.1.5 Sample and compound selection for (TUM) laboratory studies _________________ 9 2.1.6 Sample preparation and solid phase micro extraction (SPME) method ___________ 9 2.1.7 Analytical method ___________________________________________________ 10 2.1.8 Terpenoid and Aromate Determination __________________________________ 10 2.1.9 Open access data on consumer product composition versus analysis ___________ 11

CHAPTER 3 consumer product emission testing _____________________________________ 15

3.1 Emission testing at VITO 15 3.1.1 Laboratory facilities __________________________________________________ 15 3.1.2 Test Conditions _____________________________________________________ 15 3.1.3 Use scenario simulations ______________________________________________ 16

3.2 Emission testing at NRCWE 18 3.2.1 Laboratory facilities __________________________________________________ 18 3.2.2 Use scenario simulations ______________________________________________ 20

3.3 Emission testing at IDMEC 21 3.3.1 Laboratory facilities __________________________________________________ 21 3.3.2 Test conditions _____________________________________________________ 22 3.3.3 Use scenario simulations ______________________________________________ 23

3.4 Emission testing at UOWM 24 3.4.1 Laboratory facilities __________________________________________________ 24 3.4.2 Test conditions _____________________________________________________ 24 3.4.3 Use scenario simulations ______________________________________________ 25

Table of contents

VI

CHAPTER 4 Intercomparison experiment and QA/QC in EPHECT _______________________ 27

4.1 Intercomparison of the consumer product emission tests 27

4.1.1 Introduction 27

4.1.2 Experimental test conditions 27

4.1.3 Specific emission rate calculations based on test chamber concentrations 28

4.1.4 Emissions behaviour in the intercomparison studies (first preliminary report – UOWM)36

4.2 Quality assurance and quality control in EPHECT 52

4.2.1 Introduction 52

4.2.2 Quality Control of the analytical system of VOCs and aldehydes– 1st Phase, Autumn 2011 52

3.4.1 Quality Control of the analytical system of VOCs and aldehydes– 1st Phase 52

3.4.2 Quality Control of the analytical system of VOCs and aldehydes – 2nd phase 58

CHAPTER 5 EPHECT consumer product emission tests ________________________________ 69

5.1 Calculating the SER of the tested consumer products 69

5.2 Consumer product emissions, beyond EHPECT key compounds 70

CHAPTER 6 Conclusion quantification of product emissions by laboratory testing _________ 83

References_____________________________________________________________________ 85

Annex 1 _______________________________________________________________________ 87

Source strength determination (NRCWE) 87

Annex 2 _______________________________________________________________________ 92

Specific emission rate calculations based on test chamber concentrations (VITO) 92

Annex 3 _______________________________________________________________________ 99

Specific emission rate calculations of EPHECT consumer products, based on test chamber concentrations 99

Annex 4 ______________________________________________________________________ 101

Comparison of the A.I.S.E. candle emission test protocol (in 0.913 m³) with the EPHECT candle emission test at VITO (0.913 m³), at IDMEC (0.05 m³) 101

List of figures

VII

LIST OF FIGURES

Figure 1 Vötsch VCE 1000 Classic emission test chamber at VITO ___________________________ 15 Figure 2 Emission testing of a spray product using an automatic sprayer _____________________ 17 Figure 3 Outside the NRCWE chamber.________________________________________________ 18 Figure 4 Inside the NRCWE chamber _________________________________________________ 19 Figure 5 A) Test chamber used for candle emissions. B) Test chamber used for consumer products

emissions. __________________________________________________________________ 21 Figure 6 Climtech small chamber test at UOWM (CLIMPAQ) _______________________________ 24 Figure 7 Specific emission rates calculated based on test room concentrations. _______________ 34 Figure 8 Estimated total emission factors of dihydromyrcenol and limonene in kitchen cleaning agent

(see table 7 for description of the experiments) _____________________________________ 40 Figure 9 Estimated total emission factors of other emitted compounds from in kitchen cleaning agent

(see table 7 for description of the experiments) _____________________________________ 40 Figure 10 Decay constant of the 4 kitchen cleaning agents experiments, at VITO and NRCWE_____ 41 Figure 11 Estimated total emission factors of limonene, linalool and α-pinene in perfume _______ 45 Figure 12 Estimated average emission factors electrical air freshener (see table 9 for description of

the experiments) _____________________________________________________________ 49 Figure 13 Limonene emission rates per mass electrical air freshener (see table 9 for description of the

experiments) ________________________________________________________________ 49 Figure 14 α-pinene emission rates per mass electrical air freshener (see table 9 for description of the

experiments) ________________________________________________________________ 50 Figure 15 Dihydromyrcemol emission rates per mass electrical air freshener (see table 9 for

description of the experiments) _________________________________________________ 50 Figure 16 Linalool emission rates per mass electrical air freshener (see table 9 for description of the

experiments) ________________________________________________________________ 50 Figure 17 Ratio of the 8h average pollutant concentrations (Caver8) to the 24h average pollutant

concentrations (C24) (see table 9 for description of the experiments) ___________________ 51 Figure 18 Average results of the partners for toluene, m/p-xylene and styrene, with indication of the

reference values (lines). _______________________________________________________ 56

Figure 19 Average results of the partners for -pinene, -pinene and 3-carene, with indication of the reference values (lines). _______________________________________________________ 57

Figure 20 Average results of the partners for limonene, naphtalene and longifolene, with indication of the reference values (lines). __________________________________________________ 57

Figure 21 Average results of the partners for formaldehyde and acetaldehyde derivatives hydrazones, with indication of the reference values (lines). ______________________________________ 58

Figure 22 Example, passive air freshener gel tested by VITO _______________________________ 94 Figure 23 Example of the THC profile of a perfume, tested at VITO __________________________ 98

List of tables

VIII

LIST OF TABLES

Table 1 Test chamber experiments of the EPHECT consumer and personal care products _________ 2 Table 2a Overview of the product information regarding the ingredient composition directly on the

label, from the manufacturer (via contact or internet) and the composing agents identified in EPHECT. _____________________________________________________________________ 4

Table 3 a. Climate chamber specifications; Kitchen cleaning agent. _________________________ 27 Table 4 Specific emission rate calculation of kitchen cleaning agent, based on test room

concentrations _______________________________________________________________ 31 Table 5 Within laboratory repeatability: specific emission rate comparison for furniture polish: the

same product in the same laboratory _____________________________________________ 32 Table 6 Specific emission rate calculation of perfume, based on test room concentrations _______ 32 Table 7 Specific emission rate calculation of an electrical air freshener, based on test room

concentrations _______________________________________________________________ 32 Table 8 Emission results for kitchen cleaning agent (A2) __________________________________ 37 Table 9 Emission results for perfumes (A15) ___________________________________________ 43 Table 10 Emission results for electrical air fresheners (A11) _______________________________ 46 Table 11 Compounds and respective concentrations, present in the blind solution of VOCs. ______ 52 Table 12 Compounds and respective concentrations, present in the blind solution of aldehydes-DNPH

derivatives. _________________________________________________________________ 53 Table 13 Results of partner A for the concentration levels assessed in the blind solutions ________ 54 Table 14 Results of partner B for the concentration levels assessed in the blind standard solutions 54 Table 15 Results of partner C for the concentration levels assessed in the blind standard solutions 55 Table 16 Results of partner D for the concentration levels assessed in the blind standard solutions. 55 Table 17 Compounds and respective concentrations, present in the blind solution of VOCs,. _____ 58 Table 18 Compounds and respective concentrations present in the blind solution of aldehydes-DNPH

derivatives __________________________________________________________________ 59 Table 19 Results of partner A for the assessment of the concentrations of compounds present in the

blind standard solutions (2nd phase) ______________________________________________ 59 Table 20 Results of partner B for the assessment of the concentrations of compounds present in the

blind standard solutions (2nd phase) ______________________________________________ 60 Table 21 Results of partner C for the assessment of the concentrations of compounds present in the

blind standard solutions (2nd phase) ______________________________________________ 61 Table 22 Results of partner D for the assessment of the concentrations of compounds present in the

blind standard solutions (2nd phase) ______________________________________________ 62 Table 23 Identification of the compounds present in the spiked solution of VOCs, and respective

concentration. _______________________________________________________________ 63 Table 24 Results from partner A of the levels of concentration of compounds present in the tubes

spiked and statistical parameters obtained: average, relative standard deviation, total uncertainty. _________________________________________________________________ 63

Table 25 Results from partner B of the levels of concentration of compounds present in the tubes spiked and statistical parameters obtained: average, relative standard deviation, total uncertainty. _________________________________________________________________ 64

Table 26 Results from partner C of the levels of concentration of compounds present in the tubes spiked and statistical parameters obtained: average, relative standard deviation, total uncertainty. _________________________________________________________________ 64

List of tables

IX

Table 27 Results from partner D of the levels of concentration of compounds present in the tubes spiked and statistical parameters obtained: average, relative standard deviation, total uncertainty. _________________________________________________________________ 65

Table 28 Results from partner V of the levels of concentration of compounds present in the tubes spiked in September 2012 and statistical parameters obtained: average, relative standard deviation, total uncertainty. ____________________________________________________ 66

Table 29 Results from partner A of the levels of concentration of aldehydes present in the solution and comparison with reference value. ____________________________________________ 66

Table 30 Results from partner B of the levels of concentration of aldehydes present in the solution and comparison with reference value. ____________________________________________ 67

Table 31 Results from partner C of the levels of concentration of aldehydes present in the solution and comparison with reference value. ____________________________________________ 67

Table 32 Results from partner D of the levels of concentration of aldehydes present in the solution and comparison with reference value. ____________________________________________ 67

Table 33 Overview of the room concentration samples screened more in detail in this chapter (in a 0,913 m³) ___________________________________________________________________ 71

Table 34 Overview of room concentrations of contact allergens in the peak/steady state samples (in a 0,913 m³ room) ______________________________________________________________ 72

Table 35 AgBB compounds in the emission test room air when testing a candle (in a 0,913 m³ chamber); sample 0-420 min ___________________________________________________ 73

Table 36 AgBB compounds in the emission test room air when testing kitchen cleaning agent (in a 0,913 m³ room); sample 0-30 min. _______________________________________________ 73

Table 37 AgBB compounds in the emission test room when testing hair styling spray(in a 0,913 m³ room) ; sample 0-30 min. ______________________________________________________ 73

Table 38 AgBB compounds in the emission test room when testing deodorant spray (in a 0,913 m³ room) ; sample 0-30 min. ______________________________________________________ 74

Table 39 AgBB compounds in the emission test room when testing deodorant spray (in a 0,913 m³ room) ; sample 0-30 min. ______________________________________________________ 74

Table 40 AgBB compounds in the emission test room when testing glass and window cleaning agent (in a 0,913 m³ room); sample 0-30 min. ___________________________________________ 74

Table 41 AgBB compounds in the emission test room when testing air freshener spray (in a 0,913 m³ room) ; sample 0-30 min. ______________________________________________________ 75

Table 42 AgBB compounds in the emission test room when testing perfume (in a 0,913 m³ room) ; sample 0-30 min. _____________________________________________________________ 75

Table 43 AgBB compounds in the emission test room when testing a passive air freshener (in a 0,913 m³ room); sample 300-330 min. _________________________________________________ 76

Table 44 AgBB compounds in the emission test room when testing electrical air freshener 1 (in a 0,913 m³ room); sample 300-330 min. ____________________________________________ 76

Table 45 AgBB compounds in the emission test room when testing electrical air freshener 2 (in a 0,913 m³ room); sample 300-330 min. ____________________________________________ 77

Table 46 TVOC concentrations of peak or steady state test room air (in a 0,913 m³ room) _______ 78 Table 47 Full overview of all gaseous compounds, emitted by a passive air freshener, 2 (in a 0,913 m³

room); sample 300-330 min. ___________________________________________________ 79 Table 48 Full overview of all gaseous compounds, emitted by electrical air freshener 1, 2 (in a 0,913

m³ room); sample 300-330 min _________________________________________________ 80 Table 49 Full overview of all gaseous compounds, emitted by electrical air freshener 1, 2 (in a 0,913

m³ room); sample 300-330 min _________________________________________________ 81

List of acronyms

X

LIST OF ACRONYMS

THC Total Hydrocarbon FID Flame Ionisation Detector TD-GC-MS Thermo desorption – gas chromatography- mass spectrometry HC Hydrocarbon RSD Relative standard deviation

Chapter 1 Definition

1

CHAPTER 1 PRODUCT TESTING STRATEGY

The document “Quantification of the product emissions by laboratory testing WP6 - Part I Consumer

product test protocol” formulated a strategy for the lab testing experiments in EPHECT WP6. This

protocol aimed at harmonizing emission test experiments in the involved laboratories and included:

(1) Protocols for test chamber experiments for each product type/package, (2) a list of priority

compounds for each product class focussing on respiratory health, (3) methodology for sampling and

analysis and (4) strategy for quality control and assurance and an overall plan of work, distributing

the laboratory testing experiments and the sample analysis amongst WP6 partners. The

implementation of the strategy as described in Part I, is reported in this document.

1.1. Structure of the report “Part II product testing experiments”

This report contains: (1) a brief overview on the products/brands tested by the different laboratories;

(2) description of the availability and content of open access information on product composition as

well as the outcomes of the assessment of consumer product compositions in EPHECT; (3) details on

the practical implementation of the EPHECT umbrella for consumer product testing in the involved

laboratories; (4) reporting on the intercomparison experiment and on QA/QC of the laboratory

testing experiments in different laboratories; (5) EPHECT consumer product emission data sheets; (6)

conclusion.

1.2. Test chamber experiments of the 15 product classes

Table 1 shows the EPHECT consumer product classes that are studied in WP6. Since different test

chambers are used in the laboratories, there will be variations in the outcomes from testing of an

arbitrary product. Thus, in order to assess this issue, specific products from three product classes

(kitchen cleaning agent, electrical air freshener and perfume) have been tested more in detail in each

laboratory (see Chapter 4).

Chapter 1 Definition

2

Table 1 Test chamber experiments of the EPHECT consumer and personal care products

Product class

NRCWE VITO UOWM IDMEC

Product class tested in more than 1 lab

A1 all purpose cleaner X X X

A2 kitchen cleaning agent X X

A3 floor cleaning agent X X X

A4 glass and window cleaner X

A5 bathroom cleaning agent X

A6 furniture polish X X X

A7 floor polish X X X

A8 combustible air fresheners X X X

A9 air fresheners (spray) X X X

A10 passive units X X X X

A11 electric units X X

A12 coating products X

A13 hair styling products X

A14 deodorants (sprays) X

A15 perfumes X X

One selected product tested in all laboratories X this product class is tested by one or a few laboratories, may be different brands in different laboratories

The brand and product type selection for EPHECT product testing experiments is based on the IPSOS

market study on EU uses and use patterns (EPHECT WP 5). This market study took place in 2011 in 4

EU regions, and let to the identification of the most used product brand and type in all 4 regions and

in the EU. The following strategy has been followed:

Selection of product 1: EU most used

For each EPHECT product class, the most popular brand in EU is tested applying the EPHECT

umbrella for product testing

Selection of product 2

For the majority of the product classes (10 out of 15, see Table 1) the emissions of a second

product brand are assessed, applying the same specified emission test protocol in a different

laboratory, using a test chamber with different dimensions. This second product is selected from

the most popular brands in the region of the analysing laboratory.

Inter-laboratory comparison study

For three product classes (indicated with ‘’ in Table 1), namely kitchen cleaning agents, electrical

air fresheners and perfumes, the same product is exchanged (the same brand and type, bought

centrally and distributed among the EPHECT WP6 participants) and emission are tested in each

involved laboratory, allowing an intercomparison of the obtained emission results.

Chapter 2 Description

3

CHAPTER 2 ASSESSMENT OF THE COMPOSITION OF SELECTED CONSUMER PRODUCTS (TUM)

2.1 Information on product composition

Information on product composition of consumer products in general is often communicated by

manufacturers. For detergents, the European Detergents Regulation No. 648/2004 of March the

31st, 2004, annex VII makes reporting of certain ingredients and their abundance in detergents

compulsory. More specifically this applies to fragrance substances (list of 26 contact allergic

fragrance substances) and preservation agents that may be present in the detergents. Medical

personnel should also be able to obtain from the manufacturer upon request a full listing of all

ingredients of a detergent to assist them investigate whether a causal link exists between the

development of an allergic response and exposure to a particular chemical substance. Also, for

cosmetic products, Directive 2003/15/EC (7th amendment to the Cosmetics Directive 76/768/EEC,

annex III, part I) and regulation (EC) No 1223/2009 (will replace the Cosmetics Directive on July 11th

2013) of the European Parliament and of the council of 30 November 2009 on cosmetic products, set

guidelines on labelling 26 contact allergic substances, prohibit the use of CNR substances

(carcinogenic, mutagenic or toxic for reproduction) category A1, B1 and 2 in cosmetic products, and

set guidelines and restrictions on the use of ingredients that are likely to cause allergic reactions. For

consumer products, like for instance air fresheners or coating products however, such a specific

regulation is not available. However, the presence of certain ingredients in the product composition

is made available to the consumer either under a general legislation or by voluntary industry

initiatives such as the A.I.S.E. Air Freshener Product Stewardship programme. The general legislation

includes REACH (Regulation No 1907/2006 of the European Parliament and of the Council of 18

December 2006 concerning the Registration, Evaluation, Authorisation and Restriction of Chemicals:

regulation of the European Union, adopted to improve the protection of human health and the

environment from the risks that can be posed by chemicals, while enhancing the competitiveness of

the EU chemicals industry. It also promotes alternative methods for the hazard assessment of

substances in order to reduce the number of tests on animals) and CLP (Regulation (EC) No

1272/2008 on the classification, labelling and packaging of substances and mixtures: regulation

which ensures that the hazards presented by chemicals are clearly communicated to workers and

consumers in the European Union through classification and labelling of chemicals).

The overview of information on the consumer product composition of the products studied in this

project is discussed in this chapter. Information on composition, available on the product label, on

the manufacturers’ websites and provided in manufacturers’ personal answers is summarized in

Complementary to the lab testing experiments on product emissions, selected compounds (allergic

fragrances and aromates) were identified and quantified in 16 product samples from the 28 tested

consumer products in the EPHECT product emission experiments (see Table 2a). Additionally, 10 all


4

purpose cleaners available on the German market have been selected at random for a detailed

analysis and comparison of variations in their composition (see Table 2b). The identified molecules,

of which the quantitative composition in the product was determined, are indicated in the last

column of more detailed information on the studied composing agents can be found in Tables 3-5.

Table 2a Overview of the product information regarding the ingredient composition directly on the label, from the manufacturer (via contact or internet) and the composing agents identified in EPHECT.

Product Class (Total Product

Number)

Selected brands Product Label contains

information about:

Availability of information on

composition (IL , MSDS)

Quantitative Terpenoid and Aromates Analysis

in EPHECT (details in Tables 3 and 5)

All purpose cleaner (1)

(2)

(3)

all purpose cleaner 1 all purpose cleaner 2 all purpose cleaner 3

General substance classes (like ‘Fragrances’) General substance classes and allergenic compounds General substance classes (like ‘Surfactants’)

IL and MSDS available- IL available online MSDS for a similar product IL and MSDS available online

Linalool (not declared) and Terpineol Linalool and Limonene (both declared), Geraniol and Terpineol Geraniol and Naphthalene

Kitchen cleaning agent

(4)

(5)

Kitchen cleaning agent 1 Kitchen cleaning agent 2

General substance classes and allergenic compound Limonene General substance classes

IL available online IL and MSDS available online for a similar product

n.a.

Studied compounds not present

Floor cleaning agent

(6)

(7)

(8)

Floor cleaning agent 1 Floor cleaning agent 2 Floor cleaning agent 3

General substance classes (like ‘Surface-Active Compounds’) General substance classes (like ‘Fragrances’) General substance classes (like ‘Fragrances’)

IL available online IL contains allergenic comp. MSDS online of a similar product; - IL and MSDS (both similar products) available from the company

Linalool (declared in IL) and Geraniol Linalool (not declared), Geraniol and Terpineol p-Xylene

Glass and window cleaner

(9) Glass and window cleaner 1)

General substance classes (like ‘Parfume')

IL and MSDS available online -

Linalool

Bathroom cleaning agent

(10)

Bathroom cleaning agent 1

General substance classes (like ‘Fragrances’)

IL and MSDS (later for similar product) available

Studied compounds not present

Furniture polish (11)

(12)

Furniture polish 1 Furniture polish 2

General substance classes and allergenic compounds General substance classes

IL and MSDS available online for a similar product; MSDS available

Linalool, Limonene, Naphthalene (all declared) and Geraniol n.a.


5

(like ‘Surfactants’)

Floor polish (13)

Floor polish 1

General substance classes and allergenic compound Limonene

IL and MSDS (both similar products) available online (

Linalool, Geraniol, Terpineol and Naphthalene No Limonene detected

Combustible air fresheners

(14)

Scented candle

General allergenic class (3 compounds)

IL available online

n.a.

Air fresheners (spray) (15)

Air freshener spray 1

No ingredient list ('about 5% burning compounds')

IL and MSDS (both similar products) available online

n.a.

Passive units (16)

(17)

Passive air freshener 1 Passive air freshener 2

Detailed substance classes and allergenic compounds Detailed substance classes and allergenic compounds

IL available online and MSDS IL available online and MSDS (both similar prod.)

n.a.

Linalool, Geraniol, Terpineol (all declared) and Naphthalene

Electric units (18)

(19)

Electrical air freshener 1 Electrical air freshener 2


IL and MSDS not available online; IL available online

Linalool, Limonene, Pinene (matrix problems) n.a.

Coating products (20)

Textile coating product 1

No information on the package

IL and MSDS not available online)

Naphthalene

Hair styling products (21)

Hair spray 1

Detailed substance classes and allergenic compounds

IL available online IL contains allergenic comp.

n.a.

Deodorants (sprays) (22)

Deodorant spray 1


IL and MSDS available online IL contains allergenic comp.

n.a.

(23) Deodorant spray 2


MSDS online available n.a.

Perfumes (24)

(25)

Perfume 1 Perfume 2


MSDS online available IL and MSDS available online ( –

Linalool, Limonene, Pinene (matrix problems), geraniol (declared) and Naphthalene Linalool, Limonene, Pinene (matrix problems), and Naphthalene

+ IL = ingredient lists and MSDS = Material Safety Data Sheet


6

Table 2b Overview of the product information regarding the ingredient composition directly on the label, from the enterprise and exemplary compounds found in the TUM All Purpose Cleaner study on composition in EPHECT.

Product Class (Total Product Number)

Selected brands Product Label contains

information about

Information on composition* available

(IL , MSDS ;

online, by company)+

Terpenoid and Aromates Analysis

in EPHECT (details in Tables 3 and 4)

All purpose cleaners used for in depth study on composing agents (from Table 2a) (Nos. 1-3, 10)

see Table 2a)

see Table 2a)

see Table2a)

(26)

(27)

(28)

(29)

(30)

(31)

(32)

(33)

(34)

(35)

All-purpose cleaner 4 All-purpose cleaner 5 All-purpose cleaner 6 All-purpose cleaner 7 All-purpose cleaner 8 All-purpose cleaner 9 All-purpose cleaner 10 All-purpose cleaner 11 All-purpose cleaner 12 All-purpose cleaner 13

General substance classes and allergenic compounds General substance classes and allergenic compounds General substance classes and allergenic compounds General substance classes and allergenic compounds General substance classes (like ‘Fragrances’) General substance classes and allergenic compounds General substance classes (like ‘Fragrances’) General substance classes and allergenic compounds General substance classes and allergenic compounds General substance classes and allergenic compounds

IL and MSDS available online IL and MSDS available online IL available online; IL contains allergenic comp. IL available online and MSDS from the company IL available online IL and MSDS available from the company IL and MSDS available from the company IL and MSDS available online IL and MSDS available online and from the company IL and MSDS available online

Linalool (declared) and Terpineol, Pinene Linalool (declared) and Terpineol, Pinene are present Limonene (declared), Linalool and Terpineol are present Linalool, Geraniol (both declared) and Terpineol No studied compound present Linalool, Limonene (declared) and Geraniol Terpineol Linalool, Limonene (declared) Geraniol (not declared) and Terpineol Linalool, Limonene and Geraniol(declared) and Terpineol Linalool, Limonene (decl). Geraniol(not declared) and Terpineol


7

2.1.1 Information on product label

Typically, the studied cleaning products that are defined as a detergents1 such as all-purpose

cleaners, contain on the product label the names of general chemical or functional groups like

'additives', 'aliphatic hydrocarbons', 'aromas', 'colorants', 'disinfectant', 'fragrances', 'perfumes',

'phosphonic compounds', 'polycarboxylates', 'soap', 'surface-active compounds', 'surfactants', and

'tensides', which is in agreement with Regulation EC 648/2004 (v.19.04.2012). The description of the

compounds gives no detailed information about the contained molecules, but on their properties in a

consumer focused manner.

Further, some cleaning products contain detailed chemical names and concentration levels of

ingredients on the product label (without describing their function), as for product No. 2

(iodopropynyl butylcarbamate < 5%, methylchloroisothiazolinone < 5%, methylisothiazolinone < 5%,

octylisothiazolinone < 5%, linalool < 5%, limonene < 5%, citral < 5%, and citronellol < 5%) or for

product 26 (Glutaral, Methylchloroisothiazolinone, Methylisothiazolinone, Octylisothiazolinone,

Butylphenyl Methylpropional, Linalool, Citronellol). Hereby, the all-purpose-cleaners Nos. 26/27/29-

35 contain the most information about allergens, although not all detected allergenic compounds are

covered on the labels.

However, some products are defined in EPHECT as cleaning agents although they are not defined as a

detergent according to definition of ‘detergent’1 in Regulation EC 648/2004 (v.19.04.2012). This

applies e.g. on furniture polish or coating products. As a consequence the product labeling should

not be according to the before mentioned EU regulation and therefore, several cleaning products do

not contain detailed chemical information neither detailed information about all the 26 fragrance

allergens.

Some air fresheners (Nos. 14-19 in Table 2) chosen in this project do not contain product label with

detailed consumer information. Other air fresheners contain detailed information about allergens.

There may be a valid reason that allergens are not declared on the label - for example: the

concentration of the allergens in the product may be less than the declaration limit. In addition Air

Freshener manufacturers who participate in the AISE Air fresheners Product Stewardship Program

also provide Air Freshener compositional information on all their websites.

Personal care products (Nos 21-25 in Table 2) contain very detailed information on the label about

the included chemical substances with regard to the European Union cosmetics and detergents

directive.

2.1.2 Information directly by company

Overall 28 different consumer products of 14 suppliers were studied in the EPHECT emission test

chamber (Table 2a). The TUM partner contacted the manufacturers of most studied products, with

always the same request for an answer containing ingredients list and MSDS for each product.

Unfortunately 12 times the supplier did not answer anyhow, whilst 11 times the supplier did answer.

Of these 11 answers, 6 times the supplier answered without further help. These latter wrote answers

1 EC 648/2004 (v.19.04.2012) definition of detergent: “detergent means any substance or mixture containing

soaps and/or other surfactants intended for washing and cleaning processes. Detergents may be in any form (liquid, powder, paste, par, cake, moulded poece, shape etc.) and marketed for or used in household, or institutional or industrial processes”.


8

like 'We cannot assist your request (in giving ingredient list and MSDS) due to large number of

inquiries'.

On the other hand 6 suppliers did send the requested information about the products (sometimes by

sending data on similar products or by sending a link to the webpage with IL or MSDS).

Possibly, the companies may not have answered because the request was in English, and for local

companies it might be difficult to understand. However, the high number of international acting

enterprises in this project should not lead to lingual problems. Another reason may be the contacting

strategy via e-mail.

Besides the EPHECT consumer products, also for the 10 more products available on the German

market, the 8 involved German suppliers were contacted in the same way as the other suppliers. The

partner TUM contacted the companies also in English with the request for an answer containing

ingredients list and MSDS. 7 out of 8 answered with help and only one did answer without help.

2.1.3 Information available online

In general, the information of the ingredient lists and MSDS was very variable via internet and

homepages.

Whereas some companies delivered both the detailed IL and MSDS of the products, others give

detailed IL and MSDS of a similar product, whilst others provide a general IL and MSDS of the product

or both an IL and MSDS of a similar products.

The provided information strongly depends on the language and the country of the product. For

some products detailed ingredient information was received, however for 11 products no detailed

information could be obtained via internet. It should be noted that 3 out of the last 11 products did

have all detailed information available on the product label.

The obtained product information on chemical composition was very diverse, and needed people-

intensive search conditions. Overall the personal care products are labelled in the clearest way

(regarding allergenic fragrances on product label as well as IL and MSDS). Especially for the cleaning

agents that are not a detergent and for air fresheners the outcome was very company dependent. In

order to encourage communication on air freshener ingredients, A.I.S.E. has organized the voluntary

initiative “Air Fresheners Product Stewardship Programme” (since 2007), to involve companies to provide

on their website information on the ingredients composition according to the product as per Detergent

Regulation.

This is conform with the findings of the American 'Environmental Working Group (EWG)' stating the

same behaviour for American companies and their products.2

2

http://www.ewg.org/guides/cleaners/content/methodology (12.03.2012)

Here are the sources we used to compile the ingredient information in EWG’s Guide to Healthy Cleaning:

Labels. EWG examined more than 1,000 package labels and found that the ingredient information for 48 percent listed three or fewer ingredients on the label.

Product websites and ingredient disclosure documents. Most manufacturers provide some ingredient information on their official websites. EWG visited almost 200 brand websites to

supplement the sparse package label data. Some online ingredient lists appeared to be specific and complete, but others provided a minimum of often-vague information, such as identifying

only broad chemical classes (eg. “alcohol ethoxylates”) or functional classes (eg. “preservatives”). The degree of complete and specific identification of ingredients varied from company to

company and product to product.

Material Safety Data Sheets. The federal Occupational Safety and Health Administration requires companies to furnish Material Safety Data Sheets to alert their workers to potentially

harmful substances in the workplace. Since cleaners are widely used by custodial staffs, OSHA also requires that cleaning products sold for professional use be accompanied by MSDSs.


9

2.1.4 Consumer product composition analysis in EPHECT

In a next step, the occurrence of representative compounds was verified in several consumer

products and compared with the information on chemical composition that was made available by

the enterprises. The results obtained by the TUM lab for exemplary allergens and aromatics that

were contained in the products, are shown in Table 2 (right column).

Each analysis of the products was performed with headspace SPME and GC-EI-ToF-MS analysis. The

molecules linalool, limonene, geraniol, α-terpineol, and α-pinene were quantified using the internal

standards Linalool-d3 and α-Terpineol-d3 (as well as using RI and the accurate mass of molecule ions

and fragments). The fragrances alpha-iso-methylionone, Citral (Neral + Geranial), Citronellol, and

Lilial were analysed qualitatively (using RI and accurate mass of the molecule ion and fragments). The

aromatics naphthalene, toluene and p-xylene were quantified with an external calibration.

2.1.5 Sample and compound selection for (TUM) laboratory studies

16 of the 28 consumer products that were also subject to emission chamber experiments were

tested with headspace SPME and GC-EI-ToF-MS analysis.

The remaining 12 tested consumer products have not been subjected to the headspace analysis for

various reasons, which are listed below.

No results could be obtained for the spray products (Nos. 15, 21-23) due to ‘Explosion’ during

opening the vials in the TUM laboratory. Even when storing the samples under iced conditions, the

samples could not be transferred quantitatively to the headspace vial. Also the solid products

(passive air freshener and candles ...) were not studied on their product composition either due to

handling and extraction problems loosing quantitative conditions.

The measurements of allergens and aromatics via the presented technique were characterised by a

high uncertainty, for the following product classes. Products like perfumes, oil based liquids

(furniture polish) and electric units (electrical air fresheners) could not be measured adequately (or

molecules out of) because of a low reproducibility of the results, caused by matrix compounds.

Additionally to the study on the composition of the consumer products that were part of the EPHECT

product emission tests, the variation of the product composing agents was studied more in detail for

one product class. Based on the IL and MSDS information (Table 2), the composition of these 3 all

purpose cleaners seemed to vary considerably within the product class. In order to study these

differences in composition more in detail, an additional experiment was initiated to study the

variation within the product class of the all purpose cleaners. Therefore, 10 different all-purpose

cleaners, available on the German market, were selected and subjected to a screening on present

allergenic compounds and aromatics. The results of this experiment are discussed below as well.

2.1.6 Sample preparation and solid phase micro extraction (SPME) method

Samples (i.e. No. 1-35 in Table 2; excluding the ones described in 2.2.1) were successfully diluted in

pure water 1:500 before analyzing 1 mL of the diluted sample. An appropriate amount of the internal

Many manufacturers post these documents on their websites, too, though in some cases EWG contacted companies to get copies. These documents are not provided to consumers, even

when they buy products identical to those used by custodial staff.

Although hazardous ingredients are usually listed in a specific ingredients section on an MSDS sheet, they sometimes appear in a section titled “Regulatory Information” at the end of the document

because of state regulations that apply to some specific chemicals and ingredients, typically byproducts or contaminants. In some cases, EWG found harmful chemicals listed in these sections that

did not appear anywhere else.


10

standards and 0.3 g sodium chloride were mixed in a 20 mL headspace vial. The vial was closed very

quickly and the samples were incubated with a 50/30 µm DVB/Carboxen/PDMS (1cm) SPME fibre for

30 min at room temperature. After incubation, the fibre was manually injected to the GC injection

port with a desorption time period of 30 sec. Prior to the next analysis, the fibre was reconditioned

15 min at 250 °C to ensure no carry-over of compounds from the previous sample. This was verified

with a validation study.

2.1.7 Analytical method

The GC was equipped with a DB-5 column of 30 m length, an inner diameter of 0.25 mm and a film

thickness of 0.25 µm. Helium was used as a carrier gas with a constant flow rate at 1.5 mL min-1. The

inlet temperature was set to 250°C. The oven temperature was programmed starting with 60°C hold

for 5 min, ramped at 2°C min-1 to 220°C and hold for 15 min. The injection was done manually with a

split ratio of 1:10. Mass spectrometric data was recorded using a Time-of-Flight mass spectrometer.

The ToF System operated in the EI ionization mode with 70eV. The ion source was set to 200°C and

transfer line to 220°C. Data were collected using a scan range between m/z 35 and m/z 600.

2.1.8 Terpenoid and Aromate Determination

Quantitative Terpenoid analysis

Stock solutions of each selected terpenoid standard (Linalool, Geraniol, α-Terpineol) and the internal

standards Linalool-d3 and α-Terpineol-d3 with a concentration of 1% were prepared in 60% Ethanol.

The terpenoids Limonene and α-Pinene were prepared in 100% Ethanol.

Mixtures of calibration standards were prepared in pure water with the following concentrations:

0.001‰, 0.0005‰, 0.0001‰, 0.000025‰, 0.00002‰, 0.00001‰, of each analyte, and 0.00005‰ of

both internal standards. Further solutions containing 0.000005‰, 0.000003‰ and 0.0000025‰ with

0.000075‰ of each internal standard were measured. The solutions were frozen until measurement.

The quantification of Linalool, Limonene and α-Pinene was performed with the recovery factor usage

of the internal standard Linalool-d3, the quantification of Geraniol and α-Terpineol with the recovery

factor usage of α-Terpineol-d3 with a subsequent application of the appropriate calibration curve.

The data is shown in Table 3.

Qualitative analysis of further contact allergic fragrances

The experimental runs of each sample were screened for the presence of further contact allergic

fragrances contained in the products. Citronellol, citral (neral + geranial), alpha-iso-methylionone,

lilial can be compounds in several product classes and have to be labeled on the products.

These compounds were identified without reference standards. Therefore C8-C20 alkanes were

measured by GC-MS and each compound was normalized by these alkane data set to 'retention

index' (RI) values. The RIs of the molecule of interest and its mass spectrum obtained by EI-ToF-MS

was compared with the NIST database and/or literature (i.e. a) Adams, R.P. 1995. Identification of

essential oil components by gas chromatography/ mass spectroscopy. Allured Publ. Corp., Carol

Stream, IL., USA; b) Adams, R.P. 2001. Identification of essential oil components by gas

chromatography /quadrupole spectroscopy, Allured Publ. Corp., Carol Stream, IL., USA; c) Tudor, E.

1997. Temperature dependence of the retention index for perfumery compounds on a SE-30 glass

capillary column I. Linear equations, J. Chromatography A 779: 287-297).


11

The identified molecules of the samples are shown in Table 4.

Quantitative Aromatics Analysis

Stock solutions of the two aromatic standards toluene and p-Xylene were prepared in 60% Ethanol

with a concentration of 1%. The stock solution of Naphthalene was prepared in pentene also with a

concentration of 1%. Mixtures of calibration standards were prepared in pure water with the

following concentrations: 0.0001‰, 0.00001‰, 0.000005‰ and 0.0000025‰ for each analyte.

The quantification of the samples were performed using external standards and their calibration

curves. The data is shown in Table 5.

2.1.9 Open access data on consumer product composition versus analysis

Linalool, limonene, geraniol, α-terpineol, and α-pinene

The contact allergens linalool, limonene and geraniol have to be indicated on the product label (i.e.

on the product package), in case they are present in the product in a concentration level higher than

0.01 % (100ppm; in agreement with the European Union cosmetics and detergents directive

76/768/EEC-7th amendment -Council Directive 2003/15/EC-; official journal of the European Union.

Brussels, Belgium. 2003). According to the Directive, the compounds α-terpineol and α-pinene don’t

have to be indicated on the product label.

The results of the linalool, limonene, geraniol, terpineol and α-pinene-screening of the EPHECT

studied products are shown in Table 3.

The table uses the following legend:

A concentration smaller than 0.005% is marked with <<,

A concentration between 0.005% and 0.029% is marked with ~,

A concentration higher than: 0.030% is marked with >>.

As a consequence, the sign ‘>>’ indicates a significantly higher concentration of the corresponding

compound present in the product (following the Cosmetics Directive, 7th amendment).

Furthermore, the red colour in Table 3 marks a not indicated compound (on the product label) that

occurs in concentrations highly above the reporting limit of the Directive, the blue colour marks a

compound, indicated on the product label and occurring in a concentration highly above reporting

limit, and a yellow colour marks a not indicated compound close to reporting limit. For the

compounds that don’t need to be reported according to the directive, a green colour marks a

compound that should not be reported according to the Directive, but does occurs close to or highly

above the 0.01% reporting limit from linalool, limonene and geraniol..


12

Table 3: Quantitative results of linalool, limonene, geraniol, α-terpineol, and α-pinene with information on product labels.

The observations of this table are formulated below:

- Correct labelling

According to Regulation EC 648/2004 (v.19.04.2012), the allergenic fragrances linalool, limonene and

geraniol should be indicated on the product label in case the concentration in the product exceeds

0.01%.

Half of the studied products contained linalool and limonene, in a concentration that was

considerably higher than the reporting limit of 0.01%. However, the presence of the compounds was

reported on the product label, in agreement with the Directive (see blue marks in Table 3 column 4

and 5, respectively)

Furthermore, several products contained declarable compounds linalool and/or geraniol (this is, in a

concentration close to 0.01%, see yellow marks in Table 3). However, due to the concentration

range, which is close to the analytical limit of detection, it is acceptable that the compounds are not

reported in the product label.

The same was true for geraniol in several products, either it was declared or it was not considerably

above 0.01% (yellow marks).

Linalool Limonene Geraniol Terpineol Pinene

conc [%] conc [%] conc [%] conc [%] conc [%]

Ajax Universal (1) all purpose cleaner - >> 0.01 << 0.01 << 0.01 >> 0.01 << 0.01

AZAX classic (2) all purpose cleaner Linalool, Limonene >> 0.01 >> 0.01 ~ 0.01 >> 0.01 << 0.01

KH-7 Quitagrasas (3) all purpose cleaner - << 0.01 << 0.01 ~ 0.01 << 0.01 << 0.01

Dr. Beckmann (5) kitchen cleaning agent - << 0.01 << 0.01 << 0.01 << 0.01 << 0.01

Overlay (6) floor cleaning agent Linalool >> 0.01 << 0.01 ~ 0.01 << 0.01 << 0.01

Probat natural soap (7) floor cleaning agent - >> 0.01 < 0.01 ~ 0.01 >> 0.01 << 0.01

Ajax lemon (8) floor cleaning agent - << 0.01 << 0.01 << 0.01 << 0.01 << 0.01

Ajax triple Action (9) glass and window cleaner- ~ 0.01 << 0.01 << 0.01 << 0.01 << 0.01

Ajax prof. ultra bathroom (10) bathroom cleaning agent - << 0.01 << 0.01 << 0.01 << 0.01 << 0.01

Pronto Muebles (11) furniture polish Linalool, Limonene >> 0.01 ~ 0.01 >> 0.01 << 0.01 << 0.01

AS Floor polish (13) floor polish Limonene ~ 0.01 << 0.01 ~ 0.01 ~ 0.01 << 0.01

Air Wick Aqua Mist (17) passive units Linalool, Geraniol (similar IL) >> 0.01 << 0.01 >> 0.01 >> 0.01 << 0.01

AmbiPur pink (18a) electric units - no result no result << 0.01 << 0.01 no result

AmbiPur purple (18b) electric units - no result no result << 0.01 << 0.01 no result

AmbiPur Lpurple (18c) electric units - no result no result << 0.01 << 0.01 no result

Nanocover Textile (20) coating products - << 0.01 << 0.01 << 0.01 << 0.01 << 0.01

Hugo Boss (24) perfumes Linalool, Limonene, Geraniol no result no result >> 0.01 << 0.01 no result

Chanel Chance (25) perfumes Linalool, Limonene, Geraniol no result no result << 0.01 << 0.01 no result

Linalool Limonene Geraniol Terpineol Pinene

conc [%] conc [%] conc [%] conc [%] conc [%]

Ajax Frischeduft MG I (26) all purpose cleaner Linalool >> 0.01 << 0.01 << 0.01 >> 0.01 ~ 0.01

Ajax Frischeduft MG II (27) all purpose cleaner Linalool >> 0.01 << 0.01 << 0.01 >> 0.01 ~ 0.01

Blink Allzweck Citrus (28) all purpose cleaner Limonene ~ 0.01 ~ 0.01 << 0.01 ~ 0.01 << 0.01

Blink Bio Allzweck GF (29) all purpose cleaner Linalool, Geraniol >> 0.01 << 0.01 >> 0.01 ~ 0.01 << 0.01

DenkMit Allzweck Citrus (30) all purpose cleaner - << 0.01 << 0.01 << 0.01 << 0.01 << 0.01

Frosch Universal Orange (31) all purpose cleaner Linalool, Limonene >> 0.01 >> 0.01 ~ 0.01 << 0.01 << 0.01

Ja! Allzweck Limone (32) all purpose cleaner - << 0.01 << 0.01 << 0.01 ~ 0.01 << 0.01

M. Proper Allzweck Citrus (33) all purpose cleaner Linalool, Limonene >> 0.01 ~ 0.01 >> 0.01 >> 0.01 << 0.01

Sagrotan Allzweck Citrus (34) all purpose cleaner Linalool, Limonene, Geraniol >> 0.01 >> 0.01 >> 0.01 >> 0.01 << 0.01

Terra Universal (35) all purpose cleaner Linalool, Limonene >> 0.01 ~ 0.01 ~ 0.01 ~ 0.01 << 0.01

product name (No. in Table 2b) category labeled terpenoids

mandatory identification > 0.01% no labeling required

product name (No. in Table 2a) category labeled terpenoids


13

- Incorrect labelling

Although one of the all-purpose cleaners, and one floor cleaning agent had no linalool labelled on the

product bottle, the amount appeared to be considerably higher than the reporting limit of 0.01% (see

red marks in Table 3 column 4). A similar finding was made for one furniture polish and one all-

purpose cleaner, where geraniol was not indicated on the product label, although the geraniol

concentration levels appeared to be considerably higher than 0.01% (see red marks in Table 3

column 6).

- Other observations

It is not compulsory to report the presence and concentration level of terpineol and pinene on the

product label. However, several all-purpose cleaners contained α-terpineol at concentrations

considerably higher than 0.01% (see red marks which has not to be declared).

This was noticed for the 6 out of the 13 tested all-purpose cleaners, for one floor cleaning agent, and

for one passive air freshener. They all contained an α-Terpineol concentration, which was

considerably higher than 0.01% (see green marks in Table 3 column 8).

Alpha-iso-methylionone, citronellol, citral (Neral + Geranial), and lilial

Other contact allergic fragrances were observed by RI and mass spectrometric comparisons with the

NIST database (Table 4). Several compounds could be identified. However, due to the missing

quantitative or semi-quantitative information, no statements on the labelling could be formulated.

Table 4: Qualitative results of other allergic fragrances (i.e. citronellol, citral (neral + geranial), alpha-iso-methylionone, lilial)

product name category additionally labeled terpenoids Further fragance allergens, -Idendity, qualitative results- GC-MS comp.

(No. in Table 2a) on product label (i.e. compound is contained, but no quantitative statement) (tot.amount [n])

Ajax Universal (1) all purpose cleaner - - 14

AZAX classic (2) all purpose cleaner Citronellol,Citral Citronellol, Citral (Neral + Geranial) 36

KH-7 Quitagrasas (3) all purpose cleaner - Lilial 8

Dr. Beckmann (5) kitchen cleaning agent - - 5

Overlay (6) floor cleaning agent - Lilial 24

Probat natural soap (7) floor cleaning agent - - 29

Ajax lemon (8) floor cleaning agent - - 15

Ajax triple Action (9) glass and window cleaner - Citronellol, Citral (Neral + Geranial) 21

Ajax prof. ultra bathroom (10) bathroom cleaning agent - alpha-iso-methylionone 25

Pronto Muebles (11) furniture polish - Citronellol, Lilial 9

AS Floor polish (13) floor polish - - 18

Air Wick Aqua Mist (17) passive units - Citronellol, Lilial 22

AmbiPur pink (18a) electric units - Citronellol, Lilial 23

AmbiPur purple (18b) electric units - Citronellol, Lilial 27

AmbiPur L.purple (18c) electric units - Lilial 19

Nanocover Textile (20) coating products - - n.d.

Hugo Boss (24) perfumes Citronellol, Citral, etc. Citronellol, Citral 23

Chanel Chance (25) perfumes Citronellol, Citral, etc. Citronellol, Citral, Lilial 23

product name category additionally labeled terpenoids Further fragance allergens, -Idendity, qualitative results- GC-MS comp.

(No. in Table 2a) on product label (i.e. compound is contained, but no quantitative statement) (tot.amount [n])

Ajax Frischeduft MG I + II (26/27) all purpose cleaner Citronellol and others Citronellol, Citral (Neral + Geranial), alpha-iso-methylionone, Lilial 32

Blink Allzweck Citrus (28) all purpose cleaner - Citronellol, Citral (Neral + Geranial) 23

Blink Bio Allzweck GF (29) all purpose cleaner

Benzisothiazolinone,

Methylisothiazolinone and others alpha-iso-methylionone 22

DenkMit Allzweck Citrus (30) all purpose cleaner - Citral (Neral + Geranial) 22

Frosch Universal Orange (31) all purpose cleaner - Citronellol, Citral (Neral + Geranial) 27

Ja! Allzweck Limone (32) all purpose cleaner - Citral (Neral + Geranial) 29

M. Proper Allzweck Citrus (33) all purpose cleaner Citronellol, Citral and others Citronellol, Citral (Neral + Geranial) 28

Sagrotan Allzweck Citrus (34) all purpose cleaner - - 13

Terra Universal (35) all purpose cleaner - Citral (Neral + Geranial) 30


14

As can be seen in the table, almost all tested products contain other allergenic fragrances, thus a

quantitative study of the emitted compounds in the test chamber experiments is of interest for these

compounds.

Besides these allergenic compounds, also other organic molecules could be identified by GC-MS. In

some cases they were numerous (Table 4, last column). Although these other organic compounds

have not been identified nor quantified in this experiment, their numerous presence indicates the

relevance of emission test experiments to assess the impact of these products on the indoor air

quality.

Aromatics

The results for naphthalene, toluene and p-xylene are shown in Table 5. The limits of detection in the

applied GC-MS system were used as lowest limit for the presence of aromatics.

Table 5: Quantitative results of studied aromatics

The red marks indicate a significantly higher concentration; the yellow marks indicate no significant difference from the acceptable limit. * Declaration 'Naphta' on IL and MSDS

In three products, namely one passive air freshener, one coating product and one perfume,

naphthalene was found in concentrations exceeding 0.0001%. One floor cleaning agent contained p-

xylene in a considerably higher concentration than 0.0001 %.

Naphthalene was also identified in 5 other products. However, the concentration range was close to

the detection limit of the technique.

Naphthalene Toluene p-Xylene

conc [%] conc [%] conc [%]

Ajax Universal (1) all purpose cleaner < 0.0001 < 0.0001 < 0.0001

AZAX classic (2) all purpose cleaner ~ 0.0001 < 0.0001 < 0.0001

KH-7 Quitagrasas (3) all purpose cleaner ~ 0.0001 < 0.0001 < 0.0001

Dr. Beckmann (5) kitchen cleaning agent < 0.0001 < 0.0001 < 0.0001

Overlay (6) floor cleaning agent < 0.0001 < 0.0001 < 0.0001

Probat natural soap (7) floor cleaning agent < 0.0001 < 0.0001 < 0.0001

Ajax lemon (8) floor cleaning agent < 0.0001 < 0.0001 > 0.0001

Ajax triple Action (9) glass and window cleaner < 0.0001 < 0.0001 < 0.0001

Ajax prof. ultra bathroom (10) bathroom cleaning agent < 0.0001 < 0.0001 < 0.0001

Pronto Muebles (11) furniture polish ~ 0.0001* < 0.0001 < 0.0001

AS Floor polish (13) floor polish ~ 0.0001 < 0.0001 < 0.0001

Air Wick Aqua Mist (17) passive units > 0.0001 < 0.0001 < 0.0001

AmbiPur pink (18a) electric units < 0.0001 < 0.0001 < 0.0001

AmbiPur purple (18b) electric units < 0.0001 < 0.0001 < 0.0001

AmbiPur Lpurple (18c) electric units < 0.0001 < 0.0001 < 0.0001

Nanocover Textile (20) coating products > 0.0001 < 0.0001 < 0.0001

Hugo Boss (24) perfumes ~ 0.0001 < 0.0001 < 0.0001

Chanel Chance (25) perfumes > 0.0001 < 0.0001 < 0.0001

Naphthalene Toluene p-Xylene

conc [%] conc [%] conc [%]

Ajax Frischeduft MG I (26) all purpose cleaner < 0.0001 < 0.0001 < 0.0001

Ajax Frischeduft MG II (27) all purpose cleaner < 0.0001 < 0.0001 < 0.0001

Blink Allzweck Citrus (28) all purpose cleaner < 0.0001 < 0.0001 < 0.0001

Blink Bio Allzweck GF (29) all purpose cleaner < 0.0001 < 0.0001 < 0.0001

DenkMit Allzweck Citrus (30) all purpose cleaner < 0.0001 < 0.0001 < 0.0001

Frosch Universal Orange (31) all purpose cleaner < 0.0001 < 0.0001 < 0.0001

Ja! Allzweck Limone (32) all purpose cleaner < 0.0001 < 0.0001 < 0.0001

M. Proper Allzweck Citrus (33) all purpose cleaner < 0.0001 < 0.0001 < 0.0001

Sagrotan Allzweck Citrus (34) all purpose cleaner < 0.0001 < 0.0001 < 0.0001

Terra Universal (35) all purpose cleaner < 0.0001 < 0.0001 < 0.0001

* 'Naphta' on IL and MSDS

product name (No. in Table 2b) category

product name (No. in Table 2a) Category

Chapter 3 Consumer product emission testing

15

CHAPTER 3 CONSUMER PRODUCT EMISSION TESTING

This chapter summarizes emission test details of the laboratory testing experiments of the 15

EPHECT consumer product classes in the four involved laboratories. All laboratory facilities and

procedures are described separately.

3.1 Emission testing at VITO

3.1.1 Laboratory facilities

EPHECT consumer product emission tests at VITO have been performed inside a 0.916 m3 emission

test chamber (Vötsch VCE 1000 Classic), see Figure 1.

The stainless steel inside walls are electropolished and

pressure proof up to ± 10MBar. Temperature and

relative humidity are monitored using the capacitive

sensor of the test chamber, which is calibrated annually

by the manufacturer.

The total hydrocarbon (THC) concentration inside the

room is continuously monitored using a NGA 2000

Flame Ionisation Detector (FID) Hydrocarbon Analyzer

Module (Rosemount). Aerosols inside the room are

continuously monitored during experiments, using a

filter-check™" SubMicron Aerosol Spectrometer

(Grimm 1.108), which counts particles in 15 channels

and reports mass distribution in 15 classes (in the range

0.30-20 µm).

All samples are collected at the manifold of the test

chamber. VOCs are sampled on Tenax TA tubes 60/80

mesh (respecting ISO 16000-6), SVOC on PDMS/Tenax

and aldehydes on DNPH tubes (respecting ISO 16000-

3). Analysis of VOCs and SVOCs is performed on coupled TD-GC-MS (for VOC analysis: TD Markes

Ultra Unity – HP 6890 – HP 5973 and for SVOC analysis TD 100 Markes – Interscience DSQ II – Trance

GC Ultra). Aldehydes are analysed using a Water UPLC, with a PDA detector.

3.1.2 Test Conditions

All start-up conditions for emission tests have been set to the conditions defined in the EPHECT

umbrella for consumer product testing (see Part I EPHECT consumer product emission test protocol).

This implies an air exchange rate of 0.5/h and a sum of sampling air flows up to 80% of the intake

Figure 1 Vötsch VCE 1000 Classic emission test chamber at VITO


16

flow. The air velocity above the sample was set at 0.1-0.3 m/s. Recovery and sink has been evaluated

as described in the EPHECT umbrella.

The initial test conditions are set according to the EPHECT umbrella as well for all consumer product

emission tests. The initial temperature of all tests is set at 23°C ± 2°C (accuracy of 1.0°C). The relative

humidity of the supply air is regulated to obtain and maintain a relative humidity of 50% ± 5%

(accuracy of 3%) inside the test chamber (monitored inside the room). The supply air and background

concentrations have a TVOC concentration below 20 µg.m-3 and individual VOCs occur at

concentrations below 2 µg.m-3.

3.1.3 Use scenario simulations

Used quantities

All tested products have been weighted before and after the experiments, outside the test chamber.

The tested quantity of a product in a flask was selected with respect to the IPSOS market study. In

case the study indicated “quantity according to manufactures’ guidelines”, these were applied in the

emission tests. If the market study indicated that the majority of users used more, or less, of the

prescribed quantity, or if the expected TVOC levels were below the detection limits, the applied

quantities were adjusted accordingly.

For emission tests of products in a spray bottle, one spray was introduced to the test chamber,

independently of the use scenario (i.e. spraying on a surface or in the air). All spray events were

performed using an automatic sprayer, thus the test chamber door was not opened during the

spraying event. Exception was the emission test of the perfume: since this experiment was part of

the intercomparison experiment, the perfume was sprayed manually inside the room in order to

apply the same procedure as the other 3 partners.

Passive and electric air fresheners are tested during a fixed time period (according to the EPHECT

umbrella for consumer product testing); the applied quantity is thus proportional to the duration of

the emission test. The passive air freshener is fully unwrapped from its package; active air fresheners

with more than one position are always tested in maximum position.

For candle emission testing one candle is lighted inside the room, the room is then closed after

lighting the candle. The candle was extinguished after 6 hours.

Bringing the product in the test room

A2: Kitchen cleaning agent: This product in a flask was applied on an aluminium surface inside the

room, corresponding to a loading factor of 0.4 m2/m3. The door was opened during the application of

a known quantity of the product. The product was spread out over the surface with a cloth, covering

the surface as much as possible. The cloth was taken out of the room after the application and

weighted before and after simulating this use scenario. The kitchen cleaning agent was not rinsed

and was left to dry during the emission test.

A9: air freshener spray; A13: hair styling spray. All but one spray bottle consumer products are tested

using an automatic sprayer (perfume was sprayed manually), placed inside the test chamber, as

shown in Figure 2. For each emission test of a spray bottle, the spray bottle as well as the automatic


17

sprayer were placed inside the room to equilibrate for at least 12 hours before the experiment was

initiated. All spray experiments thus have been performed without opening the test chamber door

before or during the test.

A4: Glass and window cleaner spray; A14: deodorant sprays. If the use scenario implies spraying on a

surface, the surface material is selected according to the product purpose: glass and window cleaner

was sprayed on a glass surface of 0.07m2/m3 placed at a distance of 15-20 cm according to the user

guidelines; a similar scenario was applied for deodorant, using a paper tissue.

A15: Perfumes. For emission testing of perfumes, the automatic spray was not used for perfume

emission testing (with the aim to apply the same procedure as the other partners in the

intercomparison experiment). This experiment was performed by opening the test chamber door,

spraying manually once on a cotton tissue.

Figure 2 Emission testing of a spray product using an automatic sprayer

A8: Combustible air fresheners. For candle emission tests, the candle was placed inside the room and

immediately lighted using a gas lighter. In order to avoid the candle to extinguish as a result of the

inside wind speed caused by the ventilator, a U-shaped glass frame was placed at a distance of

approximately 15 cm from the candle, perpendicular to the air movement caused by the ventilator.

After 5 hours, the door was opened to extinguish the candle by gently blowing on it.

A10: Passive air fresheners. Passive air fresheners were placed inside the room just before the

experiment was initiated. According to the EPHECT umbrella for consumer product testing, the

sampler was left to equilibrate with the indoor test room environment for 3 hours. The device is

weight before and after the experiment.

A11: Electrical air freshener. For the emission tests of electric air fresheners, electricity supply is

inserted inside the test chamber. The device is weight before and after the experiment.

All measurements at steady state conditions (combustible air freshener, electrical air freshener and

passive air freshener) are performed after 3.25 air changes.


18

3.2 Emission testing at NRCWE


All emission testing at NRCWE was carried out in a full scale walk-in chamber with an ante-chamber.

Chamber dimensions: Height: 2.29 m; Length: 3.46 m; Width: 2.56. Total volume: 20.24 m3. Wall

material: Steel.

VOCs were sampled on Tenax TA (60-80 mesh) adsorbent tubes and measured by combined thermal

desorption with Perkin-Elmer ATD 400 and gas chromatography with a FID detector (HP 5890)

(Wolkoff 1998). Six-point calibration was applied (r2 > 0.999). Aldehydes (C1-C6) were sampled (ca.

120 l over 1 hr) on DNPH sampling cartridges (Supelco, LpDNPH S10). The cartridges were eluted

within 1 hour after sampling and analyzed immediately thereafter by HPLC using a diode array

detector using a standard mix (Supelco, Carbonyl-DNPH Mix 1) for six-point calibration (r2 > 0.999).

Additional adsorbent tubes were sampled for qualitative analysis on Varian 1200 QQQ equipped with

a CP-3800 GC and Perkin-Elmer ATD 400. VOC and aldehyde data are reported as mean of duplicates

and corrected for background air.

The TVOC development was monitored in real-time by use of a PID detector (ppbRAE).

VOCs and aldehydes were sampled through a sampling manifold (see Figure 3). The manifold

sampled air from about 5 cm from the chamber wall. Ammonia, disinfectants, SVOCS, total VOCs and

gravimetric sampling of particles on Teflon filters were sampled in the center of the chamber (see

Figure 4). Pumps and tubing were placed inside the chamber.

Figure 3 Outside the NRCWE chamber.


19

Figure 4 Inside the NRCWE chamber

Several real-time instruments were applied for particle measurements. TSI FMPS Model 3091, which

measures the electrical mobility particle size (Dm) in 32 channels with midpoints ranging from 6 to

523 nm. The FMPS was operated with the column heater at 50C and sampling was conducted

through the standard FMPS cyclone Model 1031083 (d50 = 1 µm). Particles for the FMPS were

sampled at a position placed 5 cm from the chamber wall (See Figure 3) by use of 1/4" conducting

flexible tube (70 cm) connected to the manifold. A Dekati ELPI+ (size range: 6 nm – 10 µm) was

placed inside the chamber in order to have two particle sampling locations. Both instruments

operated at a sampling frequency of 1 sec and the sample flows were 10 l/min for both instruments.

The sample flow from the FMPS was lead back to the chamber.


20

The test conditions were generally: Temperature 23 ± 1C, relative humidity 23 ± 5% (due to break-

down in the humidifying system), air exchange rate 0.5 ± 0.1 h-1. The ozone background was 10 ± 5

ppb. The chamber was lighted with two fluorescent lamps in the ceiling. Recovery and sink was

evaluated as described in the EPHECT umbrella.


Used quantities


The amount applied was in accordance with the recommended prescription for the product.


In general, all procedures were manually carried out in the chamber by one person in accordance

with the product recommendations. The person left the chamber and closed the door immediately

after the end of the procedure. After application/spray the chamber air was mixed for 60 seconds

after which sampling was initiated.

A2: Kitchen cleaning agent: The product was added to a 1 m2 stainless steel plate and distributed

with a cotton cloth. Product flask and cloth were weighed before and after application.

A3. Floor cleaning agent A: 30 ml diluted in 2.5 l of lukewarm water (ca. 40 °C). 250 ml was

distributed on 5 m2 of stainless steel (chamber floor) by the means of a wet mop. The mop was

weighed before and after application.

A3. Floor cleaning agent B: One cap diluted in 2 l of lukewarm water (ca. 40 °C). 250 ml was

distributed on 5 m2 of stainless steel (chamber floor) by the means of a wet mop. The mop was

weighed before and after application.

A5. Bathroom cleaning agent: The product was sprayed on 1 m2 of stainless steel and distributed

with a cotton cloth. The flask and cloth were weighed before and after application.

A6. Furniture polish: The product was applied to a 50 x 120 cm lacquered, wooden table by means of

a cotton cloth. The cloth was weighed before and after application. Deviation from product manual:

The table was not polished after application.

A7. Floor polish: Diluted according to product manual: 1/2 cap diluted in 4 l of lukewarm water (ca.

40 °C). 250 ml was distributed on 5 m2 of stainless steel (chamber floor) by the means of wet mop.

The mop was weighed before and after application.

A9. Air freshener (spray): The product was sprayed (ca. 3 sec spray) into the chamber air. The flask

was weighed before and after spraying.

A10. Passive air freshener: The air freshener was placed inside the chamber and allowed to

equilibrate for 18 hours before sampling was initiated. The mass of released water and VOCs (in

grams/hour) was determined by weighing the air freshener before and after the experiment.


21

A11. Air freshener (electric unit): The unit was placed inside the chamber and turned on (maximum

setting). Sampling was carried out continuously over a period of 5 hours; stable VOC concentrations

were not reached after 3 hours. The unit was weighed before and after the experiment.

A12. Shoe coating product: The product was applied to a pair of shoes size EUR 45 (US 11) placed

inside the chamber. The flask was weighed before and after use.

A15 A,B. Perfume: The perfume was sprayed (2 pumps) at a cotton t-shirt placed inside the chamber.

The flask was weighed before and after the experiment.

Measurements at steady state conditions for product A10-A12 are performed after an air change

rate of 2.5/h.

3.3 Emission testing at IDMEC


EPHECT consumer product emission tests at IDMEC have been performed using two different test

chambers. For candles a cylindrical glass chamber with 47.9 litters was used (Figure 5A), installed in

agreement with Wasson et al. 2002 and Derudi et al. 2012. For the other consumer products a 0.255

m3 emission test chamber made of stainless steel was used (Figure 5B). Both test chambers have

control of temperature, relative humidity and air exchange rate.

Figure 5 A) Test chamber used for candle emissions. B) Test chamber used for consumer products emissions.

For the determination of VOCs, air samples were collected from the test chamber in stainless steel

tubes with Tenax TA, 60/80 mesh, from Supelco, using personal air pumps, from Casella, with flow

rates in the range of 60-135 mL/min, provided with on line flow meters, from Cole-Parmer. The tubes

were after subjected to thermal desorption through a thermal desorption system (TDS) DANI model

A) B)


22

STD 33.50 coupled to a gas chromatography (Agilent Technologies 6890N) and the identification and

quantification was performed by a mass selective detector (Agilent Technologies 5973). Compound

concentrations were calculated based on the response factor of the compound itself, and in the case

of no existing standard, the response factor of toluene was used. An internal standard, cyclodecane,

was always injected simultaneously in order to assess the loss of VOCs in the desorption process.

For the determination of aldehydes air samples were collected from the test chamber in DNPH

cartridges from Waters, using personal air pumps, from SKC, with flow rates in the range of 120-450

mL/min. The air flow were adjusted and read with a Calibrator Sensydine. The cartridges were after

subjected to solvent extraction with acetonitrile and analysed by HPLC (Agilent Technologies 1220

Infinity LC). Compound concentrations were calculated based on the response factor of the

compound itself.

For ammonia collection, a personal sampling pump was used to draw a known volume of air through

a glass tube containing carbon beads impregnated with sulphuric acid (CISA). Ammonia was collected

and converted to ammonium sulphate. Samples are then desorbed using a known volume of

deionized warter and analysed by ion selective electrode (ISE).

Simultaneously size-segregated mass fraction concentrations corresponding to PM1, PM2.5,

Respirable, PM10, and Total PM size fractions was performed with a Dust Track DRX Aerosol Monitor

model 8533.

Temperature and Relative Humidity were continuously monitored with data logger Testo 175-H2.

Carbon monoxide, carbon dioxide and oxygen were continuously monitored with a Madur GA-

40Tplus. NO2 was continuously monitored with a Gray Wolf Model TG-502 Toxic Gas Probe.

3.3.2 Test conditions

The ambient test conditions were also established in agreement with ISO 16000-9: T = 23°C ± 2°C and

RH = 50% ± 5% (relative humidity of the supply air is regulated in order to obtain a 50% inside the

test chamber). However it was observed an increase of RH above the range defined when assessing

the emissions of the diluted floor polish. A deviation also occurred for the temperature values inside

the test chamber during the burning process of the candle, with values above the range defined in

the last 2 hours of the test. The relative humidity presented also some values above the range

defined, but always much below 75%, as advised by AISE protocol for candle emission. The outlet

oxygen concentration was monitored and did not present a decrease more that 2% compared to the

inlet oxygen concentration (AISE protocol for candle emission).

The air exchange rate of the test chamber for all the experiments was higher than the 0.5h-1 defined

in protocol. It was used a value of about 0.85 h-1 in order to have an inlet flow rate superior to the

sum of the simultaneous sampling air flow rates.


23


Used quantities

All tested products have been weighted before and after the experiments. The amount applied was

in accordance with the recommended prescription for the product. For candle and electric air

freshener emission testing one unit was placed inside the test chamber.


In general, all procedures of preparation of the products were done in the shorter period of time

possible, in order to minimize the impact in the compound emission. The cover of the test chamber

was open the minimum space possible to allow the introduction of the hand of the operator and the

application of the product.

A1: All purpose cleaning agent: The product was applied directly on 0.222 m2 ceramic tiles and

distributed with a cotton cloth. Product flask was weighed before and after application. In the two

tests performed the conditions were the same.

A2. Kitchen cleaning agent: The product was applied directly on 0.122 m2 stainless steel plate and

distributed with a cotton cloth. Product flask and cloth were weighed before and after application.

A6. Furniture polish: The product was applied directly on 0.111 m2 wood tiles, and spread with a

cotton cloth. Product flask was weighed before and after application. In the two tests performed the

conditions were the same.

A7. Floor polish: Diluted according to product manual (1 to 2 cap diluted in 5 l of water), 100 ml was

distributed on 0,177 m2 of wood tile using a cotton cloth. Product flask was weighed before and after

experiment. It was used cold water, contrary to the normal use of consumers presented in IPSOS

report that use warm water.

A8. Candle: The candle was inserted in the test chamber with the air flow on and lighted with a gas

lighter. After 6 hours the candle was extinguished, and the concentrations monitored during more 1

hour. The candle was weighed before and after the experiment. A control candle was burned in a

room, during the same time.

A11. Air freshener (electric unit): The unit was placed inside the chamber and turned on (maximum

setting). The unit was weighed before and after the experiment.

A15. Perfume: One of the tests was done applying 2 sprays directly to the air of the test chamber, the

second test was done applying 2 sprays of perfume on a cotton cloth placed inside the chamber. In

both tests, the flask was weighed before and after the experiment.

Measurements at steady state conditions of products A8-A15, are performed after an air change rate

of 5.4/h.


24

3.4 Emission testing at UOWM


The consumer product emission tests were conducted at CLIMPAQ test chamber with dimensions:

1005mm (length) x 250mm (wide) x 220mm (height) and total volume of 50,9lt (Climtech), see Figure

6. It is made mainly from glass with some stainless steel parts.

VOCs were sampled on Tenax TA (Supelco, Gerstel) adsorbent tubes and measured by combined

thermal desorption (GERSTEL TDSA) and gas chromatography (Agilent Technologies 6890N) with a

MSD detector (Agilent Technologies 5973 Network). Three-point calibration was applied (r2 > 0.999).

Aldehydes-ketones were sampled on DNPH sampling cartridges (Waters, Sep-Pak). The cartridges

were stored at 4oC prior to extraction. They eluted with 2 ml of CH3CN and analyzed immediately

thereafter by HPLC using a diode array detector (Agilent Technologies 1100 Series) using a standard

mix (Supelco, Carbonyl-DNPH Mix 1) for three-point calibration (r2 > 0.999). VOC and aldehyde data

are corrected for background air. The sampling was done by pumps through holes at the lid of the

chamber test (see figure 1). The sampling flow rates were adjusted in order not to extend the 80% of

the supply flow.

Figure 6 Climtech small chamber test at UOWM (CLIMPAQ)

3.4.2 Test conditions

All start-up conditions for emission tests have been set to the conditions defined in the EPHECT

umbrella for consumer product testing (see Part I EPHECT consumer product emission test protocol).

This implies an air exchange rate of 0.5/h and a sum of sampling air flows up to 80% of the intake

flow. The air velocity above the sample were 0.06-0.12 m/s measured with hot-wire anemometer

(Delta Ohm HD2303).

The initial test conditions are set according to the EPHECT umbrella as well for all consumer product

emission tests. The initial temperature of all tests is set at 23°C ± 2°C (accuracy of 1.0°C). The initial

relative humidity for the supply air is set at 50% ± 5% (accuracy of 3%), during the experiments it was

not monitored inside the chamber.


25


Used quantities


The amount applied and the type of application was in accordance with the recommended

prescription for the product and IPSOS survey.

Passive deodorizer and electric air freshener are tested during a fixed time period (according to the

EPHECT umbrella for consumer product testing); the applied quantity is thus proportional to the

duration of the emission test. The passive air freshener is fully unscrewed from its closed position;

electric air freshener with more than one position is always tested in maximum position.


In general, all procedures were manually carried out outside the chamber by one person in

accordance with the product recommendations. The person opened the chamber lid, placed the

substrate/product inside and closed the lid immediately after the end of the procedure.

A1: all purpose cleaner: The product was added to 0,04m2 glass substrate and distributed with a

sponge outside of chamber test. Product flask and sponge were weighed before and after

application.

A2: Kitchen cleaning agent A: The product was added to 0,04m2 stainless steel substrate and

distributed with a sponge outside of chamber test. Product flask and sponge were weighed before

and after application.

A2: Kitchen cleaning agent B: The product was added to 0,04m2 glass substrate and distributed with a

sponge outside of chamber test. Product flask and sponge were weighed before and after

application.

A3. Floor cleaning agent: The product (one cap) was diluted in warm water (5l) and 20ml of this

solution was added to 0,04m2 glass substrate and distributed with a sponge outside of chamber test.

Product flask and sponge were weighed before and after application.

A11. Air freshener (electric unit): The product was directly placed inside the chamber operated at the

maximum position. The product flask was weighed before and after use.

A15. Perfume: The perfume was sprayed (2 pumps) at a cotton t-shirt placed inside the chamber. The

flask was weighed before and after the experiment.

A17. Deodorizer: The product directly placed inside the chamber test and operated in the maximum

scale. Product was weighed before and after application.

A19. Magazines: The whole product was directly placed inside the chamber test.

Chapter 4 Intercomparison experiment and QA/QC in Ephect

27

CHAPTER 4 INTERCOMPARISON EXPERIMENT AND QA/QC IN EPHECT

4.1 Intercomparison of the consumer product emission tests

4.1.1 Introduction

In addition to the individual testing of selected consumer products, it was decided to carry out

a comparison between all four partners (in the consumer product emission tests) by testing the

same three consumer products in different test chambers. The selected products were a

kitchen cleaning agent (A2), an electrical air freshener (A11), and a perfume (A15). According to

anticipated best practice and feasibility, the products were applied and tested according to the

EPHECT consumer product test protocol.

4.1.2 Experimental test conditions

Table 3a to Table 3c show the climate chamber specifications and test conditions that were

used in the different laboratories. The following is observed:

The chamber volumes varied about two orders of magnitude, i.e. from walk-in to one-quarter of m3.

The air exchange rates ranged between 0.5 and 0.9 per hour.

One chamber had a relative humidity lower than 50 %.

The air velocity varied up to a factor of 600 between lowest and highest. The applied air velocity is within the ISO 16000-9 standard recommendations. However, it is questioned how this window reflects real scenario conditions.

The amount of product applied and normalized relative to the chamber volume varied about a factor of 35 from lowest to highest.

The sampling periods differed between laboratories.

Table 3 a. Climate chamber specifications; Kitchen cleaning agent.

Laboratory NRCWE VITO UOWM IDMEC Chamber vol, m

3 20.24 0.916 0.0509 0.255

Air exchange rate, h-1

0.5 0.5 0.5 0.87

Temperature, C 23 23 23 22

Rel Humidity, % 18 50 50 49 Air velocity, cm/s 0.05 30 9 12 Amount used, g 104.6 0.43 0.96 0.81 Amount per vol, g/m

3 5.2 0.47 18.9 3.2

Ozone, ppb <10


28

Table 3b. Climate chamber specifications; Air freshener, electrical. Laboratory NRCWE VITO UOWM IDMEC Chamber vol, m

3 20.24 0.916 0.0509 0.255


0.5 0.5 0.5 0.87



3 0.02 0.29 9.4 2.5

Ozone, ppb 10 < 0.4

Table 3c. Climate chamber specifications; Perfume. Laboratory NRCWE VITO UOWM IDMEC Chamber vol, m

3 20.24 0.916 0.0509 0.255


0.5 0.5 0.5 0.84



3 0.01 0.067 3.06 0.27

Ozone, ppb 10

In summary, although tentative guidance for the application of each product type in the

emission test room has been developed, in practice, it turned out to be rather difficult to apply

a similar usage.

For comparative purposes, an attempt was carried out to determine the source strength

normalized to per gram consumer product (µg/hour per gram) applied for selected key

pollutants at different time intervals and for the entire test period. The source strength for a

given key pollutant was then determined as the chamber concentration at a given sampling

period multiplied with the air exchange rate (AER) and multiplied with the chamber volume

and divided with the amount of product applied. The outcomes are reported in Annex 1.

4.1.3 Specific emission rate calculations based on test chamber concentrations

This first and most simple approach was applied in order to compare the test chamber

concentrations resulting from the different laboratories, by taking into account the sample size

and the chamber air exchange rate to estimate the emission factors, i.e. emission rates,

normalized to per gram consumer product (expressed µg/hour per gram) or per product unit

(expressed in µg/hour per unit).

The deviation of the applied equations is shown in Annex 2 of this document and is based on

the following documents:


29

ASTM 5116-10 – Standard Guide for small-scale environmental chamber

determinations of organic emissions from indoor materials/products.

Evaluation of VOC Emissions from building products, Sold Flooring material. ECA report

18, 1997.

Influence of Air Fresheners on the Indoor Air Quality. Study ordered by the Federal

Public Service of Helath; Food Chain Savety and Environment. M. Spruyt et al. 2006.

Organic Indoor Air Pollutants; Occurence, Measurement, Evaluation, second edition.

Tunga Salthammer and Erik Uhde. Wiley-VCH, Weinheim 2009.

Standard ECMA-328 – Determination of chemical emission rates from electronic

equipment, 5th edition 2010.

The equations take into account any influence of incomplete air mixing in the room, when

measuring the peak room concentration early in the emission test experiment, and respect the

fact that the room concentrations of the studied pollutants were not assessed by online

measurements, where the concentration C(t) is determined at a certain point in time t. In fact,

most concentration measurements in EPHECT have been performed offline, so a measured

concentration applies to a certain time interval, which may vary between the laboratories. Two

types of formulae have been deviated: (1) for the situation of a decaying concentration and (2)

for a constant emission source, leading to a steady state condition in the test chamber.

The outcomes of these equations, when applied on the room concentrations of the emission

tests from the 3 intercomparison products (kitchen cleaning agent, perfume and electrical air

freshener), are discussed separately. It should be mentioned that the somehow deviating

results, determined in the smallest test room of 0.05 m³, will not be discussed in this

paragraph. For an explanation of these outcomes is referred to section 0.

Kitchen cleaning agent

Table 4 shows the calculated peak emission rate and the average emission rate of each

experiment. The peak specific emission rates (SERpeak) presented here are calculated based on

the highest room concentration, measured in the experiment by each laboratory. The average

specific emission rates (SERaverage) are calculated based on the average room concentration that

was measured by each laboratory in the experiment; this average room concentration was

assessed by collecting a sample from time t0 until the end of the experiment (average sample

collection time of 5 to 7 hours).

It should be noted that this particular experiment to assess the emission rate of a creamy

kitchen cleaning agent was repeated 4 times by each laboratory. The first experiment was

executed without strict agreements between the different labs, neither on the quantity to be

used, nor on the surface or the thickness of the layer to be applied. The second and third

experiments were based on strict agreements on (1) loading factors, (2) thickness of the layer

and (3) sampling times and durations.

The outcomes indicate the difficulties of performing emission tests of this kind of creamy

cleaning product. Not only the loading factor (g/m³) seems to influence the room

concentrations, also the size of the covered surface and thus the thickness of the layer seem to


30

impact. It can be noticed that the first experiment did not lead to any agreeing result between

the laboratories’ outcomes. The subsequent repeats of the experiment, with more strict

agreements on the simulated use scenario, showed agreeing as well as deviating SERpeak and

SERaverage for certain compounds between the laboratories, but did lead to a relatively good

repeatability within the individual laboratories. For instance, the relative standard deviation of

the limonene peak emission rates within the laboratories range from 6% (for VITO) to 40% (for

IDMEC).

The within laboratory repeatability was also studied by repeating emission tests in the same

laboratory. This is illustrated for furniture polish in Table 5. As a result of the application mode

(e.g. use scenario simulation, closure of the test chamber door) and the loading (influence of

the layer thickness and covered surface on the internal and external emissions), the peak SERs

of certain compounds deviated on average 54% within the laboratory (ranging from 10-83%).

However, the average specific emission rates showed a satisfying agreement, characterized by

an average relative standard deviation of 14%, ranging from 1% to 34%.


31

Table 4 Specific emission rate calculation of kitchen cleaning agent, based on test room concentrations

room size AER L surface SER(tpeak) SER (average) L surface SER(tpeak) SER (average)

[m³] [/h] [g/m³] [m²/m³] [µg/g.h] [µg/g.h] [g/m³] [m²/m³] [µg/g.h] [µg/g.h]

Kitchen cleaning product VITO 0,916 0,5 0,5 0,44 1.965 22,9 1,9 0,44 145.014 92

LIMONENE NRCWE 20,24 0,5 5,2 0,05 16.450 0 0,9 0,07 83.494 45,4

IDMEC 0,255 0,86 3,2 0,48 13.467 44,7 3,6 0,25 140.027 62

UOWM 0,051 0,5 18,8 0,79 2 1,3 4,5 0,20 128 1,8



Kitchen cleaning product VITO 0,916 0,5 0,5 0,44 1,9 0,44 83.949 64

DIHYDROMYCENOL NRCWE 20,24 0,5 5,2 0,05 4.650 0 0,9 0,07 22.403 33,3

IDMEC 0,255 0,86 3,2 0,48 1.435 2,8 3,6 0,25 24.422 25

UOWM 0,051 0,5 18,8 0,79 4,5 0,20 4 0,4



Kitchen cleaning product VITO 0,916 0,5 2,1 0,33 131.655 89 1,5 0,33 129.349 115

LIMONENE NRCWE 20,24 0,5 2,0 0,05 52.875 41 2,1 0,10 69.626 34

IDMEC 0,255 0,86 5,7 0,48 238.702 68 3,4 0,48 113.565 70

UOWM 0,051 0,5 1,4 0,29 15,4 3,6



Kitchen cleaning product VITO 0,916 0,5 2,1 0,33 35.494 33 1,5 0,33 61.307 72

DIHYDROMYCENOL NRCWE 20,24 0,5 2,0 0,05 4.297 23,0 2,1 0,10 14.071 22,6

IDMEC 0,255 0,86 5,7 0,48 55.152 38 3,4 0,48 22.315 23

UOWM 0,051 0,5 1,4 0,29 0,0 0,0

Experiment 1 Experiment 2

Experiment 3 Experiment 4


32

Table 5 Within laboratory repeatability: specific emission rate comparison for furniture polish: the same product in the same laboratory

Table 6 Specific emission rate calculation of perfume, based on test room concentrations

Table 7 Specific emission rate calculation of an electrical air freshener, based on test room concentrations

room size AER mass L SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average)

[m³] [/h] [g] [g/m³] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g]

0,255 0,84 1,84 7,2 28.425 31 126.687 104 94.420 116 165.757 137 15.340 17 5.002 7 202 - 2.271 3 22 -

0,255 0,87 2,51 9,8 15.138 42 55.706 148 40.301 128 70.618 135 13.269 28 2.131 7 77 - 938 4 85 -

RSD 43% 23% 55% 25% 57% 7% 57% 1% 10% 34% 57% 4% 63% - 59% 6% 83% -

linalole a-terpeniol Linalyl anthranilate formaldehydenonane propilcyclohexaneoctane decane limonene

room size AER mass L SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average)

[m³] [/h] [g] [g/m³] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g]

VITO 0,916 0,5 0,06 0,1 5.168 221 1.561 66 8.196 526

NRCWE 20,24 0,5 0,20 0,01 5.776 153 - - - -

IDMEC 0,255 0,86 0,07 0,3 5.042 157 1.728 55 14.719 476

UOWM 0,051 0,5 0,16 3,1 1,4 1,4 4,2 3,6 - -

Limonene β-pinene linalool

room size AER mass L SER(teq) SER (average) SER(teq) SER (average) SER(teq) SER (average) SER(teq) SER (average) SER(teq) SER (average)

[m³] [/h] [g] [g/m³] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g]

VITO 0,916 0,5 0,27 0,3 28 31 32 44 59 80 2.059 1.588 - -

NRCWE 20,24 0,5 0,40 0,02 56 159 265 0 - - 4.394 5.645 - -

IDMEC 0,255 0,86 0,64 2,5 - 57 68 9 82 63 2.090 1.127 4.951 1.792

UOWM 0,051 0,5 0,48 9,4 0,2 0,4 4,1 3,9 2,1 1,6 0,5 0,7 - -

linaloolLimonene α-pinene β-pinene geraniol


33

Although in some cases emission rates from a comparable magnitude are calculated for peak

emission rates as well as for the average emission rates in a comparison between the

laboratories, a clear pattern of well-agreeing results cannot be identified.

It can be noted however in Table 4 that the lowest peak and average emission rates are

calculated for the experiments in which the smallest surface per volume unit was covered with

the kitchen cleaning agent (e.g. NRCWE experiments ≤ 0.1 m²/m³ leads to lowest calculated

emission rates).

Perfume

Table 6 shows the calculated peak and the average emission rates of perfume, tested by each

laboratory. The peak emission rates (SERpeak) presented here are calculated based on the

highest room concentration, measured in the experiment by each laboratory. The average

emission rates (SERaverage) are calculated based on the average room concentration that was

measured by each laboratory in the experiment; this average room concentration was assessed

by collecting a sample from time t0 until the end of the experiment (average sample collection

time of 5 to 7 hours).

Contrary to the emission test of the creamy kitchen cleaning agent, the use scenario that was

applied for the perfume emission test was characterized by far less degrees of freedom. In this

scenario, the perfume was sprayed (2 pumps) on a cotton t-shirt that was placed inside the

chamber. The flask was weighed before and after the experiment. This lower degree of

freedom to apply the product in the room, clearly affected the repeatability of the results

between the laboratories in a positive way. For instance for limonene, the relative standard

deviation of the peak specific emission rates between the laboratories (NRCWE, VITO, and

IDMEC) was only 7%. For the limonene average emission rates, a between laboratory relative

standard deviation of 22% was obtained. A similar repeatability was found for the other

identified compounds.


34

Limonene specific emission rates β-pinene specific emission rates

Linalool specific emission rates

Figure 7 Specific emission rates calculated based on test room concentrations.

The results are visualized in Figure 7. It should be noted however that the same two pufs of

perfume obviously led to lower room concentrations in the large test chamber that was used

by NRCWE. Since the specific emission rate computation includes a loading factor correction,

any impact should be covered in the calculation process. However, in this case the low loading

factor that was used in the largest test room (0.01 g/m³, which is 10 times lower than the

loading factor applied by VITO), led to room concentrations below the limit of detection.

Therefore, compounds that are emitted in relatively high concentrations can be traced when

applying lower loading factors (e.g. limonene in this experiment), but compounds occurring at

lower concentrations cannot be detected (e.g. β-pinene).

As can be noticed in Figure 7, the average emission rates of IDMEC, VITO and NRCWE coincide.

Electrical air freshener

Table 7 shows the calculated specific emission rates of the electrical air freshener. In this table

the specific emission rate at steady state conditions (SEReq) is calculated based on the room

concentration after 7 hours of an operating electrical air freshener on maximum position. The

average specific emission rate (SERaverage) calculation is based on the average room

concentration that was initiated 3 hours after starting up the electrical air freshener and

sampled until the end of the experiment (4 hours in total).

According to Table 7 it can be noticed that the variation between the laboratories is higher

than when spraying a perfume. However in this experiment, the best agreeing results are found

between the laboratories of VITO and IDMEC. This can be noticed especially for compounds

0

1000

2000

3000

4000

5000

6000

0 200 400 600

Emis

sio

n f

acto

r [µ

g/gh

]

Time [min]

VITO

NRCWE

IDMEC

VITO average

IDMEC average

0

200

400

600

800

1000

1200

1400

1600

1800

0 200 400 600

Emis

sio

n f

acto

r [µ

g/gh

]

Time [min]

VITO

IDMEC

VITO average

IDMEC average

0

2000

4000

6000

8000

10000

12000

14000

16000

0 200 400 600

Emis

sio

n f

acto

r [µ

g/gh

]

Time [min]

VITO

IDMEC

VITO average

IDMEC average


35

with a higher emission rate (in this case linalool), which then generate a room concentration

that considerably exceeds the detection limits of the techniques. The impact of a very small

loading factor (0.02 g/m³) at NRCWE compared to VITO (0.3 g/m³) and IDMEC (2.5 g/m³) led to

the generation of room concentrations of a few µg’s at NRCWE which probably caused the

unexpected pattern of SEReq relative to SERaverage and relative to the specific emission rates

from other laboratories.

The fact that geraniol was not detected by VITO or NRCWE is most probable also related to the

test room volumes, leading to undetectable trace concentrations of geraniol. Because of the

smaller room volume (and thus the higher loading factor), the compound could be identified

and quantified by IDMEC.

It should also be noted that, although the use scenario of this electrical air freshener is straight

forward (to be installed in the test room, plugged in and switched on), leaving only few degrees

of freedom to modify the use scenario in different laboratories, there has not been a study on

the consistency of the process of diffusing the liquid air freshener over longer periods of time.

Also the impact of the quantity of solution that is left in the flask, on the product emissions, has

not been studied in EPHECT. At IDMEC and VITO the experiment was repeated a second time,

by using the previously used flask again. The outcomes are discussed in next paragraph

(Chapter 0)

Conclusion

In general this first and simple approach to analyse the intercomparison experiment has led to

the following conclusions:

- Although a specific emission rate is a value that is corrected for the loading factor as

well as for the air exchange rate that were applied in the experiment, the loading factor

may still influence the determined specific emission rates in case the used quantity was

too low to generate room concentrations at detectable levels. Therefore, if very low

loading factors are applied as under realistic conditions (e.g. one air freshener in a

walk-in room, certain compounds may not occur in detectable levels in the emission

test room.

- The more repeatable the use scenario, the smaller the relative standard deviation of

the specific emission rates between different laboratory outcomes. E.g. a perfume

spray led to low between-laboratory variations; whilst the application of a creamy

kitchen cleaning agent led to considerably higher between-laboratory variations.

- Testing consumer products like creamy kitchen cleaning agents, leads to a higher

amount of degrees of freedom in applying the scenario in the test room. In fact, the

loading factor, interpreted as the mass of the product, used per unit of volume, is not

the only determining parameter in this case. Also the covered surface per volume

unity, and thus also the thickness of the cleaning agent layer in the test room, influence

the room concentrations.

A more detailed analysis of the emission behaviour in this intercomparison study is discusses in

4.1.4.


36

4.1.4 Emissions behaviour in the intercomparison studies (first preliminary report – UOWM)

For the selected products (A2-kitchen cleaning agent, A11-electrical air freshener, A15-

perfume), as described above, a comparison on the emission behaviour as measured in the

various laboratories is presented.

A2-kitchen cleaning agent

A synopsis of the experimental setup parameterization and the emission results are given in

Table 8. It should be mentioned that the kitchen cleaning agent emission test has been

repeated 4 times in every laboratory. The 3 last repetitions were organized with more fixed

application guidelines between the laboratories (focussing on applied quantity, covered surface

as well as measuring time and duration).


37

Table 8 Emission results for kitchen cleaning agent (A2)

Compound INSTITUTION/

ORGANIZATION

Chamber

Volume

[m3]

Area [m2]

Mean Air

Velocity

[m/s]

Air

Exchange

Rate λ [1/h]

Product Amount

used m [g]

TOTAL EMISSION

FACTOR [μg/g]

PEAK

EMISSION

FACTOR

[μg/gh]

EMISSION RATE FACTOR [μg/gh]

EMISSION DURATION [h] EXPONENTIAL AVERAGE (Calculation Time h)

acetaldehyde IDMEC – 0 0.26 0.12 0.12 0.86 0.81 19.55 4.55 - 3.45 (7.00) > 7.00

NRCWE – 0 20.24 1 0.0005 0.5 104.6 1.32 0.5 0.50*exp(-0.38t) - ~5.3

α-pinene

IDMEC – 0 0.26 0.12 0.12 0.86 0.81 4.2 - Nearly instantaneous (k > 4 [h-1]) - < 0.5

NRCWE – 0 20.24 1 0.0005 0.5 104.6 7.34 6.27 6.27*exp(-0.85t) - ~2.4

UOWM – 0 0.05 0.04 0.09 0.5 0.96 0.52 0.15 - 0.07 (6.95) > 6.95

dihydromyrcenol

NRCWE – 0 20.24 1 0.0005 0.5 104.6 427.82 100.66 100.66*exp(-0.24t) - ~8.5

VITO – 1 0.92 0.3 0.3 0.5 1.33 358.72 - Nearly instantaneous (k > 4 [h-1]) - < 0.5


NRCWE – 1 20.24 1.5 0.0005 0.6 17.5 246 - Nearly instantaneous (k > 4 [h-1]) - < 0.5

UOWM – 1 0.05 0.01 0.09 0.56 0.0907 SMALL - - - -



NRCWE – 2 20.24 1 0.0005 0.6 39.8 166.39 162.56 162.56*exp(-0.98t) - ~2.1

UOWM – 2 0.05 0.01 0.09 0.56 0.2288 1.28 1.14 - 0.18 (7.17) > 7.17

VITO – 3 0.92 0.3 0.3 0.5 1.94 304.24 883.26 883.26*exp(-2.90t) - ~0.7


NRCWE – 3 20.24 2 0.0005 0.6 42.04 125.26 - Nearly instantaneous (k > 4 [h-1]) - < 0.5


formaldehyde NRCWE – 0 20.24 1 0.0005 0.5 104.6 0.69 0.23 - 0.13 (5.13) > 5.13

limonene


NRCWE – 0 20.24 1 0.0005 0.5 104.6 805.16 977.58 977.58*exp(-1.21t) - ~1.6

UOWM – 0 0.05 0.04 0.09 0.5 0.96 0.78 0.21 - 0.11 (6.95) > 6.95



NRCWE – 1 20.24 1.5 0.0005 0.6 17.5 526.37 - Nearly instantaneous (k > 4 [h-1]) - < 0.5

UOWM – 1 0.05 0.01 0.09 0.56 0.0907 SMALL - - - -




UOWM – 2 0.05 0.01 0.09 0.56 0.2288 8.52 7.7 - 1.19 (7.17) > 7.17



38



UOWM – 3 0.05 0.015 0.09 0.56 0.07 5.34 1.67 1.67*exp(-0.31t) - ~6.5



m,p-xylene IDMEC – 0 0.26 0.12 0.12 0.86 0.81 5.06 14.58 14.58*exp(-2.88t) - ~0.7

toluene IDMEC – 0 0.26 0.12 0.12 0.86 0.81 3.38 10.86 10.86*exp(-3.22t) - ~0.6

NRCWE – 0 20.24 1 0.0005 0.5 104.6 0.41 0.45 - 0.08 (5.13) > 5.13


39

For this type of products, one expects the pollutants’ emission rate to decay. For this reason an

additional effort was to model emission rates as a decaying exponential function according to

the ASTM D5116-10 standard guide where this was applicable.

i.e. )exp()( 0 ktEtE

In this case the exponential fit was accepted if the R2 value was higher than 70%.

For the substances of which the emission rate shows an exponentially decaying behaviour with

the decay rate constant k ≥ 4 h-1, the release has been characterised as ‘nearly instantaneous’.

The value k ≥4 h-1 corresponds practically to an emission duration time of less than 0.5 hours.

This is suggested due to the fact that the concentration measurements time resolution is of the

order of 1 hour and emission durations of less than 1 hour are not expected to give fairly

accurate decay rate constants.

The estimated total emissions factors are illustrated in Figure 8 and Figure 9.

It is clear from Figure 8 and Figure 9 as well as from Table 8 that there is a variability of the

results of the estimated total emissions that depends not only on the laboratory, but also on

the experimental set up parameterization (i.e. room volume, ventilation, air velocity, product

mass, aspect ratio).

The small chamber of 0.05 m3 (UOWM) produces substantially lower total emissions (more

than one order of magnitude), making it problematic for testing such type of products. The

reason seems to be the limited mass transfer capability, caused by the very small volume. All

other chamber volumes show similar behaviour making the size of the volume less dependent

in this case.

Concerning the intercomparisons for toluene and acetaldehyde, several NRCWE concentration

measurements are were of the order of 1 μg/m3 and less. One expects in such a low level a

relatively large experimental error in sample analysis. One can conclude however that this

particular product can be characterised as a low emitter for toluene, acetaldehyde and a-

pinene. The product can be also characterised for elevated emissions of limonene and

dihydromyrcenol. If we exclude the small chamber measurements (UOWM), the individual

levels for these substances differ of the order of 3.5 for dihydromyrcenol and 4 for limonene.

In testing the kitchen cleaning agent, considerable differences occur even within the same

laboratory. For example in the estimated total emission factors of limonene the differences are

of the order of 1.7 for IDMEC, 3.8 for VITO and 2.5 for NRCWE.

The emission rate factors vary not only as a function of the test chamber volume but also on

experimental setup parameterization.


40

Figure 8 Estimated total emission factors of dihydromyrcenol and limonene in kitchen cleaning agent (see table 7 for description of the experiments)

Figure 9 Estimated total emission factors of other emitted compounds from in kitchen cleaning agent (see table 7 for description of the experiments)

In the Figure 10, the emission rate decay factors of the kitchen cleaning agent emission tests

are shown for VITO and NRCWE as a function of the parameter m/A which is proportional of

the material layer thickness on the surface of the product application. The results suggest that

for sufficiently thin layers of kitchen cleaning agent, the emission could be instantaneous.

However, if the layer thickness is increased considerably, it could lead to lower pollutant

release times due to some degree of internal diffusion rather than external diffusion.

0.1

1

10

100

1000

Dihydromyrcenol Limonene

Tota

l Em

issi

on

Fac

tor

[μg/

g]

Compount

UOWM - 0

UOWM - 1

UOWM - 2

UOWM - 3

IDMEC - 0

IDMEC - 1

IDMEC - 2

IDMEC - 3

VITO - 0

VITO - 1

VITO - 2

VITO - 3

NRCWE - 0

NRCWE - 1

NRCWE - 2

NRCWE - 3

NRCWE - 4

0.1

1

10

100

Toluene αpinene acetaldehyde

Tota

l Em

issi

on

Fac

tor

[μg/

g]

Compount

UOWM - 0

IDMEC - 0

NRCWE - 0

41

Figure 10 Decay constant of the 4 kitchen cleaning agents experiments, at VITO and NRCWE

Kitchen cleaning agent (A2) Decay constant VITO limonene

Kitchen cleaning agent (A2) Decay constant NRCWE limonene

y = -14.526x + 180.25R² = 0.8247

0.00

50.00

100.00

150.00

200.00

0 5 10 15

k [1

/h]

m/A [g/m2]

Kitchen cleaning agent (A2) - CIFDecay rate constant

VITO-Limonene

Limonene

Γραμμική (Limonene)

y = -0.8391x + 157.71R² = 0.6146

0.00

50.00

100.00

150.00

200.00

0 100 200 300

k [1

/h]

m/A [g/m2]

Kitchen cleaning agent (A2) - CIFDecay rate constantNRCWE-Limonene

Limonene

Γραμμική (Limonene)

42

A15-perfumes


Table 9. From this table it can be seen that not all laboratories measure the same pollutants.

In fact, the only compound, measured by all laboratories, is limonene.

Concerning the terpenes, the emission rates can be approximated by an exponential

decaying function as expected.

Formaldehyde, acetaldehyde and toluene were measured only by IDMEC and –surprisingly-

the emission rate does not fall exponentially but shows a more stable behaviour. Further

investigation is needed for this emission behaviour.

The estimated emission factor picture (Figure 11) of the terpenes is similar to the kitchen

cleaning agent product. The small chamber of 0.05 m3 (UOWM) produces also substantially

lower total emissions (more than one order of magnitude difference) making it problematic

for testing these products as well.

The degree of variability per laboratory per experimental set up is similar with the cleaning

agent case, taking into consideration much less cases studied. For example for limonene

(except UOWM) there is a difference of the order of 2 between the laboratories.

43

Table 9 Emission results for perfumes (A15)

Compound INSTITUTION/

ORGANIZATION

Chamber

Volume [m3]

Mean Air

Velocity [m/s]

Air

Exchange

Rate λ [1/h]

Product Amount

used m [g]

TOTAL EMISSION

FACTOR [μg/g]

PEAK

EMISSION

FACTOR

[μg/gh]

EMISSION RATE FACTOR [μg/gh] EMISSION

DURATION [h] EXPONENTIAL AVERAGE

(Calculation Time h)

acetaldehyde IDMEC – 0 0.26 0.13 0.91 0.07 119.22 89.37 - 22.78 (5.23) 5.23

α-pinene

IDMEC – 0 0.26 0.13 0.91 0.07 33.68 - Nearly instantaneous (k > 4 [h-1]) - < 0.5


UOWM 0.05 0.09 0.5 0.16 3.77 0.66 - 0.54 (6.95) > 6.95

dihydromyrcenol IDMEC – 0 0.26 0.13 0.91 0.07 7482.14 - Nearly instantaneous (k > 4 [h-1]) - < 0.5

IDMEC – 1 0.26 0.13 0.84 0.1 4976.79 7227.24 7227.24*exp(-1.45t) - ~1.4

formaldehyde IDMEC – 0 0.26 0.13 0.91 0.07 21.15 19.11 - 6.07 (3.48) 3.48

IDMEC – 1 0.26 0.13 0.84 0.1 114.67 19.97 - 16.23 (7.07) > 7.07

geraniol VITO 0.92 0.3 0.5 0.06 901.05 2034.81 2034.81*exp(-2.26t) - ~0.9

limonene



NRCWE 20.24 0.0005 0.5 0.2 610.6 - Nearly instantaneous (k > 4 [h-1]) - < 0.5

UOWM 0.05 0.09 0.5 0.16 3.99 1.8 - 0.57 (6.95) > 6.95

VITO 0.92 0.3 0.5 0.06 1276.65 - Nearly instantaneous (k > 4 [h-1]) - < 0.5

linalool


IDMEC – 1 0.26 0.13 0.84 0.1 2053.36 2982.98 2640.37*exp(-1.29t) - ~1.6

VITO 0.92 0.3 0.5 0.06 3017.33 10404.35 10404.35*exp(-3.45t) - ~0.6

44

m,p-xylene IDMEC – 0 0.26 0.13 0.91 0.07 26.67 - Nearly instantaneous (k > 4 [h-1]) - < 0.5

toluene IDMEC – 0 0.26 0.13 0.91 0.07 48.06 28.2 - 9.30 (5.17) 5.17

45

Figure 11 Estimated total emission factors of limonene, linalool and α-pinene in perfume

A11-electrical air fresheners


Table 10.

The small chamber of 0.05 m3 (UOWM) measurements produces also for the electrical air

freshener emission test results that are substantially lower total emissions for the terpenes.

The situation is better for acetaldehyde.

Excluding these data, the results for the emission rates show a significant variation per

laboratory and experimental set up. The results for α-pinene are quite disperse. Another

parameter that adds to the variability is the earlier use of the product (the second

experiments of VITO and IDMEC were performed with a used air freshener. Further studies

are needed to clarify this variation.

1

10

100

1000

10000

Limonene Linalool αpinene

Tota

l Em

issi

on

Fac

tor

[μg/

g]

Compount

IDMEC - 0

IDMEC - 1

NRCWE

UOWM

VITO

46

Table 10 Emission results for electrical air fresheners (A11)

Compound

INSTITUTION/

ORGANIZATIO

N

Chamber

Volume [m3]

Mean Air Velocity

[m/s]

Air Exchange Rate

λ [1/h]

Product Amount

used m [g] TOTAL EMISSION FACTOR [μg/g] PEAK EMISSION FACTOR [μg/gh]

AVERAGE EMISSION RATE FACTOR

[μg/gh] (Calculation Time [h])

α-pinene

IDMEC – 0 0.26 - 0.87 0.64 312.5 95.48 51.51 (6.07)

IDMEC – 1 0.26 - 0.87 1.25 17.58 3.57 2.15 (8.17)

UOWM – 0 0.05 0.09 0.5 0.48 16.63 4.51 2.39 (6.95)

UOWM – 1 0.05 0.09 0.557 1.45 2.45 0.63 0.31 (8.17)

VITO – 0 0.92 0.3 0.5 0.27 230.69 86.52 35.49 (6.50)

VITO – 1 0.92 0.3 0.55 1.44 68.95 20.1 8.44 (8.17)

α-terpineol

IDMEC – 0 0.26 - 0.87 0.64 17278.15 3826.56 2848.05 (6.07)

UOWM – 0 0.05 0.09 0.5 0.48 0.33 0.11 0.05 (6.95)

NRCWE 20.24 0.0005 0.5 0.41 28506.78 8772.19 5626.34 (5.07)

acetaldehyde IDMEC – 0 0.26 - 0.87 0.64 31.22 5.12 4.88 (6.40)

UOWM – 0 0.05 0.09 0.5 0.48 22.01 4.5 3.30 (6.67)

dihydromyrcenol

IDMEC – 0 0.26 - 0.87 0.64 25145.13 5100 4144.80 (6.07)

IDMEC – 1 0.26 - 0.87 1.25 20158.07 3497.82 2468.33 (8.17)

UOWM – 1 0.05 0.09 0.557 1.45 4.36 1.91 0.54 (8.17)

VITO – 1 0.91 0.3 0.55 1.44 7735.64 1361.5 947.22 (8.17)

NRCWE 20.24 0.0005 0.5 0.41 25377.09 6760.36 5005.34 (5.07)

formaldehyde IDMEC – 0 0.26 - 0.87 0.64 3.76 2.31 0.59 (6.40)

47

geraniol

IDMEC – 0 0.26 - 0.87 0.64 22872.43 5482.81 3770.18 (6.07)

VITO – 0 0.92 0.3 0.5 0.27 2320.28 540 421.87 (5.50)

NRCWE 20.24 0.0005 0.5 0.41 1951.29 1835.55 1603.80 (1.22)

limonene

IDMEC – 0 0.26 - 0.87 0.64 734.52 132.33 121.08 (6.07)

IDMEC – 1 0.26 - 0.87 1.25 205.65 39.44 25.18 (8.17)

UOWM – 0 0.05 0.09 0.5 0.48 1.4 0.5 0.20 (6.95)

UOWM – 1 0.05 0.09 0.557 1.45 0.78 0.35 0.10 (8.17)

VITO – 0 0.92 0.3 0.5 0.27 191.84 142.41 29.51 (6.50)

VITO – 1 0.92 0.3 0.55 1.44 211.25 48.76 25.87 (8.17)

NRCWE 20.24 0.0005 0.5 0.41 510.96 245.32 120.23 (4.25)

linalool

IDMEC – 0 0.26 - 0.87 0.64 19482.62 4060.94 3211.42 (6.07)

IDMEC – 1 0.26 - 0.87 1.25 12771.38 2217.23 1563.84 (8.17)

UOWM – 0 0.05 0.09 0.5 0.48 2.23 0.77 0.32 (6.95)

UOWM – 1 0.05 0.09 0.557 1.45 4.39 1.68 0.55 (8.17)

VITO – 0 0.92 0.3 0.5 0.27 11052.21 2252.59 1700.34 (6.50)

VITO – 1 0.91 0.3 0.55 1.44 5914.88 955.6 724.27 (8.17)

NRCWE 20.24 0.0005 0.5 0.41 26034.61 7241.12 5138.41 (5.07)

m,p-xylene IDMEC – 0 0.26 - 0.87 0.64 26.58 6.38 4.38 (6.07)

NRCWE 20.24 0.0005 0.5 0.41 915.36 508.14 180.54 (5.07)

+

toluene IDMEC – 0 0.26 - 0.87 0.64 15.32 3.62 2.53 (6.07)

49

Figure 12 Estimated average emission factors electrical air freshener (see table 9 for description of the experiments)

Figure 13 Limonene emission rates per mass electrical air freshener (see table 9 for description of the experiments)

0.01

0.1

1

10

100

1000

10000

Ave

rage

Em

issi

on

Fac

tor

[μg/

gh]

Compount

UOWM - 0

UOWM - 1

IDMEC - 0

IDMEC - 1

VITO - 0

VITO - 1

NRCWE

1

10

100

1000

0 2 4 6 8

Emis

sio

n R

ate

pe

r m

ass

[μg/

gh]

Time [h]

IDMEC - 0

IDMEC - 1

VITO - 0

VITO - 1

50

Figure 14 α-pinene emission rates per mass electrical air freshener (see table 9 for description of the experiments)

Figure 15 Dihydromyrcemol emission rates per mass electrical air freshener (see table 9 for description of the experiments)

Figure 16 Linalool emission rates per mass electrical air freshener (see table 9 for description of the experiments)

1

10

100

0 2 4 6 8

Emis

sio

n R

ate

pe

r m

ass

[μg/

gh]

Time [h]

IDMEC - 0

IDMEC - 1

VITO - 0

VITO - 1

10

100

1000

10000

0 2 4 6 8

Emis

sio

n R

ate

pe

r m

ass

[μg/

gh]

Time [h]

IDMEC - 0

IDMEC - 1

VITO - 1

10

100

1000

10000

0 2 4 6 8

Emis

sio

n R

ate

pe

r m

ass

[μg/

gh]

Time [h]

IDMEC - 0

IDMEC - 1

VITO - 0

VITO - 1

51

Another characteristic of the above results is that for certain pollutants the emission rates can be

hardly characterized as steady state especially in the early times. Figure 17 below shows the

pollutant concentrations after 24hours operation compared to the first 8hr average. This may

suggests a lower emission rate variability as the operation time proceeds.

Figure 17 Ratio of the 8h average pollutant concentrations (Caver8) to the 24h average pollutant concentrations (C24) (see table 9 for description of the experiments)

Conclusions

Based on the above emission intercomparison results one can draw the following preliminary

conclusions.

1. The small chamber volume 0.05m3 is not suitable for emission estimations for terpenes. For

aldehydes further investigation is needed

2. The emission estimation results show significant variation on emission rates. This variability

does not depend only on chamber volumes but also on the experimental preparation and

experimental set-up parameterization (product mass, area of application, ventilation, wind

velocity and chemical characteristics, and not to forget sink wall effects etc). Thin product

layers seem to accelerate the emission release whereas relatively thick layers could delay the

emission release considerably. For the electrical unit an additional factor of variation seems

to be the product re-use.

3. Further studies are needed to standardize emission estimations in consumer products.

0

0.2

0.4

0.6

0.8

1

1.2

C2

4/C

ave

r8

Compount

IDMEC - 1

VITO - 1

52

4.2 Quality assurance and quality control in EPHECT

4.2.1 Introduction

An important aspect of the document ‘Quantification of the product emissions by laboratory testing

WP6 - Part I Consumer product test protocol’ was the description of a strategy for quality control and

assurance and the formulation of an overall plan of work, distributing the laboratory testing

experiments and the sample analysis amongst WP6 partners.

In this plan of work, certain sample analysis activities were distributed amongst WP6 partners and

other sample analysis activities were organized in every laboratory (like VOC and aldehyde analysis).

This made a reliable quality control of the obtained results indispensable, especially because all

outcomes will be reported together and because intercomparisons in emission test experiments was

organized.

In order to achieve the objective, the first step of quality assurance/control was initiated in Autumn

2011:

1. Analysis of blind standard solutions of VOCs and aldehydes (formaldehyde-DNPH and

acetaldehyde-DNPH) prepared by IDMEC and sent for analysis to all partners

In view of the results obtained, it was decided in Spring 2012 to repeat the previous step and

introduce new two more steps:

2. Analysis of spiked tubes for VOCs prepared by IDMEC and sent for analysis to all partners

3. Analysis of formaldehyde and acrolein loaded DNPH cartridges (Supelco for NCRWE, VITO),

Waters (UOWM) generated and desorbed by VITO and sent for analysis to all partners

The results obtained in the two phases are presented in the following paragraphs.

4.2.2 Quality Control of the analytical system of VOCs and aldehydes– 1st Phase, Autumn 2011

3.4.1 Quality Control of the analytical system of VOCs and aldehydes– 1st Phase

Blind standard solutions, prepared by IDMEC, were sent to all partners in 28th September. The blind

solution of VOCs was prepared in methanol and contained various compounds in different

concentrations, in the range 70 - 250 ng/µl, as listed in Table 11.

Table 11 Compounds and respective concentrations, present in the blind solution of VOCs.

Compound CAS C [ng/µl]

toluene 108-88-3 82,9

m-xylene 108-38-3 131,4

53

styrene 100-42-5 84,6

α-pinene 80-56-8 216,9

-pinene 127-91-3 157,9

(+)-3-carene 498-15-7 98,0

R(+)-limonene 5989-27-5 75,2

naphthalene 91-20-3 177,2

(+)-longifolene 475-20-7 245,8

The blind solution of aldehydes-DNPH derivatives was prepared in acetonitrile and contained

compounds presented in different concentration, in the range 1 - 10 ng/µl, presented in Table 12.

Table 12 Compounds and respective concentrations, present in the blind solution of aldehydes-DNPH derivatives.

Compound CAS C (ng/l)

Formaldehyde-2,4-Dinitrophenylhydrazone 1081-15-8 1,632

Acetaldehyde-2,4-Dinitrophenylhydrazone 1019-57-4 3,632

All the partners reported their results (three concordant results) in an excel file, sent by e-mail to

each partner to insert the obtained results.

The results of each partner are presented in next tables, as well the statistical parameters obtained:

average, relative standard deviation, as well as total uncertainty as defined in ‘Quantification of the

product emissions by laboratory testing WP6 - Part I Consumer product test protocol’:

Where: Xr = the reference value x = is the average of the analysis performed in the laboratory s = the standard deviation of the individual results This formula is extracted from EN 482:2005. To achieve an acceptable level of quality, it is advisable that the obtained values are less than 30%.

54

Table 13 Results of partner A for the concentration levels assessed in the blind solutions

Compound Run 1

(ng/l)

Run 2

(ng/l)

Run 3

(ng/l)

Average

(ng/l)

Relative Standard

deviation (%)

Reference Value

(ng/l)

Total Uncertainty

(%)

toluene 89,0 93,3 94,8 92,4 3,3% 82,9 19%

m-xylene 146 145 153 148 2,9% 131 19%

styrene 93,0 89,2 92,9 91,7 2,4% 84,6 14%

-pinene 232 236 245 237 2,7% 217 15%

-pinene 169 169 174 171 1,7% 158 12%

(+)-3-carene 108 109 112 110 2,0% 98,0 17%

R(+)-limonene 83,2 82,9 85,5 83,9 1,7% 75,2 15%

naphthalene 180 178 187 182 2,6% 177 7.8%

(+)-longifolene* 430 445 438 438 1,8% 246 ----

Formaldehyde-DNPH 1,62 1,62 1,60 1,61 0,6% 1,63 2.2%

Acetaldehyde-DNPH 3,88 3,85 3,83 3,85 0,7% 3,63 7.5%

* calculated with response factor of toluene

Table 14 Results of partner B for the concentration levels assessed in the blind standard solutions

Compound Run 1

(ng/l)

Run 2

(ng/l)

Run 3

(ng/l)

Average

(ng/l)

Relative Standard

deviation (%)

Reference Value

(ng/l)

Total Uncertainty

(%)

toluene 82,1 82,5 82,4 82,3 0,2% 82,9 1,0%

m-xylene 127 129 130 129 1,3% 131 4,7%

styrene 79,1 80,9 81,5 80,5 1,5% 84,6 7,7%

-pinene 217 218 220 219 0,7% 217 2,2%

-pinene 198 201 203 200 1,2% 158 30%

(+)-3-carene 98,3 103 104 102 2,8% 98,0 9,4%

R(+)-limonene 80,8 87,2 85,1 84,3 3,9% 75,2 21%

naphthalene 167 191 181 180 6,7% 177 15%

(+)-longifolene 324 342 380 349 8,3% 246 65%

(+)-longifolene* 134 127 169 144 15.6%

Formaldehyde-DNPH 1,21 1,22 1,22 1,22 0,4% 1,63 26%

Acetaldehyde-DNPH 3,22 3,24 3,22 3,23 0,4% 3,63 12%


55

Table 15 Results of partner C for the concentration levels assessed in the blind standard solutions

Compound Run 1

(ng/l)

Run 2

(ng/l)

Run 3

(ng/l)

Average

(ng/l)

Relative Standard

deviation (%)

Reference Value

(ng/l)

Total Uncertainty

(%)

toluene 102 103 81,5 103 13% 82,9 45%

m-xylene 141 140 127 140 5,5% 131 18%

styrene 89,9 88,8 81,1 88,8 5,4% 84,6 17%

-pinene 247 242 216 242 6,9% 217 28%

-pinene 177 159 156 159 7,2% 158 15%

(+)-3-carene 96,0 92,5 85,0 92,5 6,0% 98,0 15%

R(+)-limonene 78,2 80,3 70,0 80,3 6,9% 75,2 20%

naphthalene 164 168 149 168 6,0% 177 18%

(+)-longifolene* 257 258 280 258 5,0% 246 ----

Formaldehyde-DNPH 1,01 1,01 1,01 1,01 0,3% 1,63 38%

Acetaldehyde-DNPH 2,37 2,37 2,35 2,36 0,6% 3,63 36%


Table 16 Results of partner D for the concentration levels assessed in the blind standard solutions.

Compound Run 1

(ng/l)

Run 2

(ng/l)

Run 3

(ng/l)

Average

(ng/l)

Relative Standard

deviation (%)

Reference Value

(ng/l)

Total Uncertainty

(%)

toluene 89,4 86,4 89,1 88,3 1,9% 82,9 11%

m-xylene 130 125 133 129 3,1% 131 7,6%

styrene 90,2 85,6 87,2 87,7 2,7% 84,6 9,1%

-pinene 216 202 225 214 5,3% 217 12%

-pinene 150 137 156 148 6,9% 158 19%

(+)-3-carene 99,6 90,6 100,2 96,8 5,6% 98,0 12%

R(+)-limonene 76,5 71,2 77,5 75,1 4,5% 75,2 9,2%

naphthalene 163 163 161 163 0,6% 177 9,4%

(+)-longifolene 252 242 248 247 2,1% 246 4,9%

(+)-longifolene* 304 291 298 298 2,1%

Formaldehyde-DNPH 1,64 1,64 1,64 1,64 0,2% 1,63 0,9%

Acetaldehyde-DNPH 3,61 3,60 3,62 3,61 0,2% 3,63 1,1%


56

It can be noticed that the individual values of VOCs reported by all the partners have a standard

relative deviation below 15%, as advised by ISO 16000:6. In the case of aldehydes-derivatives these

values are much lower, with values below 1%.

Concerning the comparison with the Reference Values, there are some differences in some of the

results reported. The results can be observed in Figure 18 until Figure 21 for VOCs and aldehydes-

derivatives, in which also the reference value is indicated. The reported deviations are expressed as

the Total Uncertainty, and it can be seen that some of the results present values higher than 30%.The

high values of TU indicate that something happened during the analysis. There may be several

reasons for those deviations: contamination of the tubes, incomplete desorption, errors due to

calibration solutions, errors due to calculation mistakes. The calibration curves of those compounds

have been revised, using fresh solutions.

Figure 18 Average results of the partners for toluene, m/p-xylene and styrene, with indication of the reference values (lines).

0,00

20,00

40,00

60,00

80,00

100,00

120,00

140,00

160,00

partner A partner B partner C partner D

C (

ng

/ul)

toluene

m/p-xylene

styrene

reference value toluene

reference value xylene

reference value styrene

57

Figure 19 Average results of the partners for -pinene, -pinene and 3-carene, with indication of the reference values (lines).

Figure 20 Average results of the partners for limonene, naphtalene and longifolene, with indication of the reference values (lines).

0

50

100

150

200

250

300


C (

ng

/ul)

a-pinene

b-pinene

carene

reference value a-pinene

reference value carene

reference value styrene

0

50

100

150

200

250

300

350

400


C (

ng

/ul)

limonene

naphtalene

longifolene

reference value limonene

reference value naphtalene

reference value longifolene

58

Figure 21 Average results of the partners for formaldehyde and acetaldehyde derivatives hydrazones, with indication of the reference values (lines).

3.4.2 Quality Control of the analytical system of VOCs and aldehydes – 2nd phase

Step 1: Analysis of blind standard solutions of VOCs and aldehydes-DNPH derivative

Blind standard solutions, prepared by IDMEC, were sent to all partners in 13th of June. The blind

solution of VOCs was prepared in methanol and containing different compounds present in different

concentrations, in the range of 50 - 500 ng/l as listed in Table 17.

Table 17 Compounds and respective concentrations, present in the blind solution of VOCs,.

Compound CAS toluene 108-88-3 164 m-xylene 108-38-3 112 styrene 100-42-5 207 α-pinene 80-56-8 151 β-pinene 127-91-3 170 (+)-3-carene 498-15-7 208 R(+)-limonene 5989-27-5 138 naphthalene 91-20-3 109 geraniol 106-24-1 124 α-terpineol 98-55-5 127

The blind solution of aldehydes-DNPH derivatives was prepared in acetonitrile and contained

compounds presented in different concentrations, in the range of 1 - 10 ng/l, as listed in table 8.

0,00

0,50

1,00

1,50

2,00

2,50

3,00

3,50

4,00

4,50


C a

ldeh

yd

es-D

NP

H (

ng

/ul)

formaldehyde-DNPH

acetaldehyde-DNPH

reference value F

reference value A

59

Table 18 Compounds and respective concentrations present in the blind solution of aldehydes-DNPH derivatives

Compound CAS

Formaldehyde-2,4-Dinitrophenylhydrazone 1081-15-8 7,44

Acetaldehyde-2,4-Dinitrophenylhydrazone 1019-57-4 1,84

The results of all the partners are presented in next tables.

Table 19 Results of partner A for the assessment of the concentrations of compounds present in the blind standard solutions (2

nd phase)

Compound Run 1

(ng/µl)

Run 2

(ng/µl)

Run 3

(ng/µl)

Average

(ng/µl)

Relative Standard deviation (%)

Reference Value (ng/µl)

Total Uncertainty (%)

toluene 202 208 219 210 4,1% 164 38%

m-xylene 125 122 122 123 1,5% 112 13%

styrene 235 237 232 235 0,9% 207 15%

α-pinene 185 187 183 185 1,2% 151 26%

β-pinene 203 184 201 196 5,3% 170 28%

(+)-3-carene 259 262 256 259 1,2% 208 28%

R(+)-limonene 169 194 162 175 9,5% 138 51%

naphthalene 133 130 131 132 1,1% 109 23%

geraniol ---* ---* ---* --- --- 124 ---

α-terpineol 166 ---* 167 166 0,4% 127 32%

Formaldehyde-DNPH

6,95 ---* ---* --- --- 7,44 ---

Acetaldehyde-DNPH

1,82 ---* ---* --- --- 1,84 ---

* Value not reported

It can be seen that the individual values of VOCs reported by partner A have a relative standard

deviation below 15%, as advised by ISO 16000:6. Concerning the comparison with the Reference

Values, there are some differences in the results reported for VOCs. There was a problem with the

results obtained by the partner, as in the first quality control all the values were within the

acceptable limits, as can be observed in Table 13. So, it can be concluded that the participation in the

step 1 was performed with success.

60

Table 20 Results of partner B for the assessment of the concentrations of compounds present in the blind standard solutions (2

nd phase)

Compound Run 1

(ng/µl)

Run 2

(ng/µl)

Run 3

(ng/µl)

Average

(ng/µl)

Relative Standard

deviation (%)

Reference Value

(ng/µl)

Total Uncertainty

(%)

toluene 167 167 165 166 0,6% 164 2,4%

m-xylene 115 115 114 114 0,6% 112 3,1%

styrene 217 220 241 226 5,7% 207 21,5%

α-pinene 143 144 138 142 2,3% 151 10,2%

β-pinene 176 177 177 177 0,3% 170 4,9%

(+)-3-carene 212 217 214 214 1,1% 208 5,4%

R(+)-limonene 140 143 141 141 0,9% 138 4,3%

naphthalene 107 108 107 107 0,9% 109 3,3%

geraniol 122 126 122 123 1,9% 124 4,8%

α-terpineol 130 132 130 131 0,9% 127 4,8%

Formaldehyde-DNPH 7,49 7,51 7,60 7,53 0,8% 7,44 2,9% Acetaldehyde-DNPH 1,94 1,95 1,97 1,95 0,8% 1,84 7,8%

It can be seen that the individual values of VOC reported by Partner B have a relative standard

deviation below 15%, as advised by ISO 16000:6. In the major part of the results obtained these

values are much lower, with values below 1%.Concerning the comparison with the Reference Values,

there are very little differences in the results reported. There was an improvement in results

obtained by the partner, comparing with the first quality control (Table 14). It can be observed that

the participation in the step 1 was concluded with success.

61

Table 21 Results of partner C for the assessment of the concentrations of compounds present in the blind standard solutions (2

nd phase)

Compound Run 1

(ng/µl)

Run 2

(ng/µl)

Run 3

(ng/µl)

Average

(ng/µl)

Relative Standard

deviation (%)

Reference Value

(ng/µl)

Total Uncertainty

(%)

toluene 169 172 174 172 1,3% 164 7,2%

m-xylene 121 119 120 120 0,9% 112 8,4%

styrene 220 216 214 218 1,5% 207 8,3%

α-pinene 161 161 161 161 0,2% 151 6,9%

β-pinene 177 177 178 177 0,4% 170 5,2%

(+)-3-carene 215 217 213 216 0,9% 208 5,8%

R(+)-limonene 137 138 139 138 0,7% 138 1,7%

naphthalene 111 110 110 110 0,6% 109 2,4%

geraniol 136 135 134 136 0,7% 124 10,4%

α-terpineol 127 129 128 128 0,9% 127 2,5%

Formaldehyde-DNPH 6,08 6,12 6,08 6,10 0,4% 7,44 19% Acetaldehyde-DNPH 1,55 1,55 1,56 1,55 0,4% 1,84 16%

It can be seen that the individual values of VOC reported by partner C have a relative standard

deviation below 15%, as advised by ISO 16000:6. In the major part of the results obtained these

values are much lower, with values below 1%.Concerning the comparison with the Reference Values,

there are very little differences in the results reported for VOCs, being these differences higher in the

case of aldehydes. There was an improvement in results obtained by the partner, comparing with the

first quality control (see Table 15). It can be observed that the participation in the step 1 was

concluded with success.

62

Table 22 Results of partner D for the assessment of the concentrations of compounds present in the blind standard solutions (2

nd phase)

Compound Run 1

Run 2

Run 3

Average

Relative Standard

deviation (%)

Reference

Value

Total Uncertainty

(%)

toluene 151 172 164 162 6,5% 164 14,1%

m-xylene 100 114 111 108 6,7% 112 16,5%

styrene 192 212 214 206 5,7% 207 12,0%

α-pinene 140 160 157 153 7,2% 151 15,7%

β-pinene 160 175 173 169 4,9% 170 10,0%

(+)-3-carene 178 208 217 201 10,1% 208 22,9%

R(+)-limonene 125 141 138 135 6,0% 138 14,2%

naphthalene 97 108 116 107 8,6% 109 18,9%

geraniol 132 145 158 145 9,1% 124 37,7%

α-terpineol 119 130 124 124 4,4% 127 10,8%

Formaldehyde-DNPH 7,61 7,57 7,56 7,58 0,4% 7,44 2,6% Acetaldehyde-DNPH 1,81 1,81 1,80 1,81 0,4% 1,84 2,5%

It can be seen that the individual values of VOCs and aldehydes reported by partner D have a relative

standard deviation below 15%, as advised by ISO 16000:6, being however the values much lower for

aldehydes. Concerning the comparison with the Reference Values, there are very little differences in

the results reported for aldehydes and for VOCs, with exception of geraniol. There was a problem

with the results for this compound obtained by the partner, as in the first quality control all the

values were within the acceptable limits, as can be observed in Table 16. So, it can be concluded that

the participation in the step 1 was performed with success.

Step 2: Analysis of spiked tubes of VOCs

The tubes from partners have arrived to IDMEC between 30 May and 13 June. In 13th June three

tubes from each partner were spiked with a solution prepared by IDMEC. One of the tubes, the

blank, was maintained unopened. The spike solution of VOCs was prepared in methanol and

contained different compounds present in different concentrations, in the range 50 ng/l - 500

ng/l, presented in table 13.

63

Table 23 Identification of the compounds present in the spiked solution of VOCs, and respective concentration.

Compound CAS C (ng/l)

toluene 108-88-3 126

m-xylene 108-38-3 127

styrene 100-42-5 173

-pinene 80-56-8 123

-pinene 127-91-3 162

(+)-3-carene 498-15-7 106

R(+)-limonene 5989-27-5 151

naphthalene 91-20-3 174

geraniol 106-24-1 140

-terpineol 98-55-5 175

All the partners reported their results in an excel file sent by e-mail to each partner to insert the

results obtained.

Table 24 Results from partner A of the levels of concentration of compounds present in the tubes spiked and statistical parameters obtained: average, relative standard deviation, total uncertainty.

Compound Run 1

(ng/µl)

Run 2

(ng/µl)

Run 3

(ng/µl)

Average

(ng/µl)

Relative Standard

deviation (%)

Reference Value

(ng/µl)

Total Uncertainty

(%)

toluene 118 113 111 114 3,2% 126 16%

m-xylene 108 105 102 105 2,9% 127 22%

styrene 168 164 160 164 2,6% 173 10%

α-pinene 122 119 115 119 2,8% 123 9%

β-pinene 153 145 144 147 3,2% 162 15%

(+)-3-carene 97 92 93 94 2,8% 106 16%

R(+)-limonene 161 157 155 158 1,9% 151 8%

naphthalene 163 159 154 159 2,8% 174 14%

geraniol 151 156 150 152 2,0% 140 13%

α-terpineol 184 178 175 179 2,6% 175 7%

64

Table 25 Results from partner B of the levels of concentration of compounds present in the tubes spiked and statistical parameters obtained: average, relative standard deviation, total uncertainty.

Compound Run 1

(ng/µl)

Run 2

(ng/µl)

Run 3

(ng/µ)

Average

(ng/µl)

Relative Standard

deviation (%)

Reference Value

(ng/µl)

Total Uncertainty

(%)

toluene 123 123 120 122 1,4% 126 6%

m-xylene 127 126 123 125 1,5% 127 4%

styrene 192 192 188 191 1,4% 173 13%

α-pinene 110 110 104 108 3,4% 123 18%

β-pinene 163 162 144 156 7,1% 162 17%

(+)-3-carene 105 103 85 98 11,4% 106 29%

R(+)-limonene 156 155 150 153 2,0% 151 5%

naphthalene 169 169 164 167 1,7% 174 7%

geraniol 149 148 145 148 1,3% 140 8%

α-terpineol 172 172 161 168 3,8% 175 11%

Table 26 Results from partner C of the levels of concentration of compounds present in the tubes spiked and statistical parameters obtained: average, relative standard deviation, total uncertainty.

Compound Run 1

(ng/µl)

Run 2

(ng/µl)

Run 3

(ng/µl)

Average

(ng/µl)

Relative Standard

deviation (%)

Reference Value

(ng/µl)

Total Uncertainty

(%)

toluene 108 111 107 108 2% 126 17%

m-xylene 101 115 110 108 6,7% 127 26%

styrene 140 150 148 145 3,7% 173 22%

α-pinene 97 111 106 104 6,6% 123 27%

β-pinene 150 141 144 142 3,2% 162 18%

(+)-3-carene 82 89 88 86 4,4% 106 26%

R(+)-limonene 116 126 124 121 4,5% 151 27%

naphthalene 134 144 142 139 3,8% 174 26%

geraniol 144 134 137 139 3,7% 140 8%

α-terpineol 174 169 167 171 2,0% 175 5%

65

Table 27 Results from partner D of the levels of concentration of compounds present in the tubes spiked and statistical parameters obtained: average, relative standard deviation, total uncertainty.

Compound Run 1

(ng/µl)

Run 2

(ng/µl)

Run 3

(ng/µl)

Average

(ng/µl)

Relative Standard

deviation (%)

Reference Value

(ng/µl)

Total Uncertainty

(%)

toluene 128 133 123 128 4,2% 126 10%

m-xylene 129 134 126 130 3,2% 127 9%

styrene 178 185 175 179 2,7% 173 9%

α-pinene 126 129 127 127 1,2% 123 6%

β-pinene 155 161 162 159 2,2% 162 6%

(+)-3-carene 93 101 106 100 6,5% 106 18%

R(+)-limonene 149 160 152 153 3,8% 151 9%

naphthalene 180 192 177 183 4,3% 174 15%

geraniol 127 129 136 131 3,6% 140 13%

α-terpineol 172 183 178 178 2,9% 175 8%

It can be seen that the individual values of VOCs reported by all the partners have a standard relative

deviation below 15%, as advised by ISO 16000:6. Concerning the comparison with the Reference

Values, there are few differences in some of the results reported, but in the case of partner C tubes,

those differences are higher. An explanation could be advanced for this, taking in account the good

results obtained by partner C in step 1: their tubes were from Gerstel and the tubes from the other

partners were from Perkin Elmer or equivalent. The injection was performed by IDMEC using the

same procedure for all the tubes, but perhaps the fact of the Gerstel tubes are so different could

provoke some losses during the injection.

In order to obtain confirmation of the results, the injection was repeated by IDMEC in the partner C

tubes, following precise instructions that should be provided by him. The tubes arrived 14 September

and were spiked in 18 September. The results are presented in Table 28, and show that an increase

of the quality of the results was obtained.

Concluding, all the partners have performed step 2 with success.

66

Table 28 Results from partner V of the levels of concentration of compounds present in the tubes spiked in September 2012 and statistical parameters obtained: average, relative standard deviation, total uncertainty.

Compound Run 1

(ng/µl)

Run 2

(ng/µl)

Run 3

(ng/µl)

Average

(ng/µl)

Relative Standard

deviation (%)

Reference Value

(ng/µl)

Total Uncertainty

(%)

toluene 130 128 126 128 1,8% 126 5%

m-xylene 129 129 124 127 2,2% 127 5%

styrene 171 176 172 173 1,6% 173 3%

α-pinene 133 136 132 133 1,6% 123 12%

β-pinene 153 158 157 156 1,9% 162 8%

(+)-3-carene 96 99 98 98 1,4% 106 10%

R(+)-limonene 141 145 141 142 1,8% 151 9%

naphthalene 176 173 166 172 3,0% 174 7%

geraniol 158 158 153 156 2,0% 140 16%

α-terpineol 124 127 130 127 2,3% 175 30%

Step 3: Analysis of spiked tubes of VOCs

All partners sent to VITO four DNPH cartridges (Supelco for NCRWE and VITO, Waters for UOWM and

IDMEC) in order to be exposed to an atmosphere of known concentration of formaldehyde and

acrolein. The cartridges were desorbed by VITO and the solution was sent for analysis to all partners.

The results obtained by all partners are presented in tables 19 to 22.

Table 29 Results from partner A of the levels of concentration of aldehydes present in the solution and comparison with reference value.

Formaldehyde Result

(g/g)

Reference Value

(g/g)

Deviation (%)

Acrolein Result (g/g) Reference

Value (g/g)

Deviation (%)

Run 1 3,32 3,38 -1,8% Run 1 2,32 6,60 -65% Run 2 3,28 3,46 -5,1% Run 2 2,25 6,75 -67% Run 3 3,34 3,42 -2,2% Run 3 2,36 6,67 -65%

67

Table 30 Results from partner B of the levels of concentration of aldehydes present in the solution and comparison with

reference value.

Formaldehyde Result

(g/g)

Reference Value

(g/g)

Deviation (%)


Value (g/g)

Deviation (%)

Run 1 2,82 3,01 -6,3% Run 1 3,14 5,87 -47% Run 2 2,95 3,16 -6,5% Run 2 2,87 6,16 -53% Run 3 2,73 3,15 -13% Run 3 2,87 6,15 -53%

Table 31 Results from partner C of the levels of concentration of aldehydes present in the solution and comparison with reference value.

Formaldehyde Result

(g/g)

Reference Value

(g/g)

Deviation (%)


Value (g/g)

Deviation (%)

Run 1 2,82 3,20 -12% Run 1 2,82 6,24 -55% Run 2 2,88 3,34 -14% Run 2 3,11 6,53 -52% Run 3 2,99 3,29 -9,2% Run 3 3,29 6,43 -49%

Table 32 Results from partner D of the levels of concentration of aldehydes present in the solution and comparison with reference value.

Formaldehyde Result

(g/g)

Reference Value

(g/g)

Deviation (%)


Value (g/g)

Deviation (%)

Run 1 3,27 3,50 -6,5% Run 1 2,00 6,83 -71% Run 2 3,33 3,51 -5,2% Run 2 2,03 6,86 -70% Run 3 3,37 3,45 -2,4% Run 3 1,92 6,74 -72%

It can be seen that the values of formaldehyde concentration reported by all the partners have a

deviation below 15%.

Acrolein presents a high deviation, but there is some similarity in the results obtained by all partners,

which indicate that there is not a problem of analysis, but a problem of the derivatisation method

that is not suitable for acrolein. To note that it was already studied by Ho et al, 2011, and they

conclude that this method is not suitable for unsaturated carbonyls as acrolein, crotonaldehyde,

methacrolein and methyl vinyl ketone. It seems that after sampling continuous polimerization occurs,

and dimers and trimers can be formed depending on the time between sampling and extraction. It

can be concluded that all acrolein results reported in the project are affected by an error and the real

values should be higher than the obtained.

Chapter 5 Ephect consumer product emission tests

69

CHAPTER 5 EPHECT CONSUMER PRODUCT EMISSION TESTS

The assessment of product emissions in WP6 went beyond the determination of the EPHECT key

compounds (acrolein, formaldehyde, naphthalene, d-limonene, α-pinene). In agreement with the

EPHECT objectives, these latter compounds have been identified based on their respiratory health

relevance, and will be studied in the assessment of the exposure and health risk related to the

household use of the consumer products (WP7). It should be emphasized however that also other

emission products have been identified and quantified. Although these compounds may not be

respiratory health relevant, their occurrence in the consumer product emission tests is reported.

An overview of all identified and (semi-)quantified compounds is made for every tested consumer

product in EPHECT. This overview is formulated as an excel worksheet, which summarizes the

following information:

- Details on the experimental set-up: used brand/product type, emission test room

dimensions, wall type, room temperature, air exchange rate, relative humidity, air velocity,

use scenario applied for product testing, used mass, covered surface (if applicable), loading

factor

- A list of the 10 most abundant compounds present in the peak sample, analysed with GC-MS

using the NIST library, as well as the TVOC concentration of the peak sample. The quantity is

expressed by area fraction and by quantitative/semi-quantitative assessment.

- A list of composing agents of the product (if available)

- Identified and quantified compounds per sample (at different points in time, offline

measurements), and the standard deviation hereof

- THC-profile of the emission test

- Particulate matter profile of the emission test (if applicable) expressed as PM1, PM2.5, total

particle number per particle geometrical diameter over time, as well as a visualisation of the

PM emission profile.

The excel sheets with the overview of the EPHECT product emissions can be downloaded from the

EPHECT website, after registration.

5.1 Calculating the SER of the tested consumer products

Based on the equations, reported in Annex 1 of this document, the specific emission rates of the

consumer products have been calculated for the peak and the average sample in case of decaying

emission profiles, and for the steady state sample and average sample in case of constant emitting

sources. The outcomes of all SER-calculations of all consumer products, tested in EPHECT, are

reported in Annex 2 of this document.


70

Note that specific emission rates, resulting from emission tests of different products (possibly in a

different laboratory, and thus different room dimensions), are indicated in this table in Annex 2. If

the reported SER’s result from testing the same product in different laboratories, no indication of

using a different product is added to the table.

Especially for the candle emission testing, an additional evaluation of the emissions is made for one

specific candle (EU most used according to the market study) which is tested in more than one way:

(1) the EPHECT candle emission protocol, applied in the VITO test room (0.913 m³), (2) the A.I.S.E.

candle emission test protocol, applied in the VITO test room (0.913 m³) and (3) the EPHECT candle

emission test protocol, adapted to a test room size of 0.05 m³ at IDMEC (built according to Wason et

al. 2002 and Derudi et al. 2012). Room concentrations have been used to calculate:

- the emission rate (respecting the A.I.S.E. definition ER = C.n.V/a; with a = the amount of

candles), for samples that have been collected before the candle was extinguished,

- the emission rate corrected for lost mass (ER/Ϫm)

- the A.I.S.E. normalized emission rate (emission rate / burning rate).

- the SER, applying the EPHECT deviated formulae as reported in Annex 1.

The results indicated the most satisfying relative standard deviation (RSD) between the different

tests, when the reported emission rates were corrected for more confounding factors: the RSD

decreases from the A.I.S.E. emission rate, to the A.I.S.E. normalized emission rate, and further to

the A.I.S.E. emission rate corrected for lost mass during the sampling time. The lowest RSD’s

were found in case the EPHECT formulae were used for SER-calculations (5% for formaldehyde).

It should be noted that, in spite of the very reproducible SER’s for formaldehyde emissions, a less

satisfying result was found for benzene (between room variation

5.2 Consumer product emissions, beyond EHPECT key compounds

In order to illustrate the emissions of substances, other than the EPHECT key compounds, the peak

samples of 10 EPHECT consumer product classes were screened for the occurrence of other health

relevant substances. This paragraph reports on the screening data of EPHECT 11 consumer products.

The tables below list the occurrence of relevant compounds, such as (1) contact allergens3, (2)

carcinogenic substances4, (3) AgBB list, in the test room air of the peak sample.

Table 33 shows an overview of the samples that were subjected to the more thorough screening.

Note that for decaying emission profiles, the peak sample was studied; for constant emission

sources, the steady state sample was studied.

3 List of EU contact allergenic substances, EU Directvie 2003/15/EC, 76/768/EEC

4 Carcinogenics listed in EU Directive Nr. 618/2012 10th of July 2012


71

Table 33 Overview of the room concentration samples screened more in detail in this chapter (in a 0,913 m³)

Tested product Use scenario Screened sample Timing

Air freshener spray Approx. 1 spray / m³ peak room concentration 0-30 min

Hair styling spray Approx. 1 spray / m³ peak room concentration 0-30 min

Deodorant men Approx. 1 spray / m³ peak room concentration 0-30 min

Deodorant women Approx. 1 spray / m³ peak room concentration 0-30 min

Glass & window cleaner Approx. 1 spray / m³ peak room concentration 0-30 min

Perfume Approx. 1 spray / m³ peak room concentration 0-30 min

Kitchen cleaning agent mass applied on surface peak room concentration 0-30 min

Passive air freshener 1 air freshener steady state room concentration 300-330 min

Electrical air freshener 1 1 air freshener, max position steady state room concentration 300-330 min

Electrical air freshener 2 1 air freshener, max position steady state room concentration 300-330 min

Candle burning one candle + extinguishment

average room concentration 0-420 min (in order to include extinction)

As shown in Table 34 limonene, linalool and to a lesser extend geraniol, are the contact allergens that

are most commonly measured and occur in the highest levels in the reported room concentrations.

The highest concentrations of the 3 substrates are measured in the emissions of an electrical air

freshener. Other contact allergenic substances occur in low concentration levels.

Screening the samples on the presence of carcinogenic substances led to the identification of

benzene (14 µg/m³) in the average room concentration of the candle emission test. Also naphthalene

(EU carc. 2) was identified at a low concentration level (0,13 µg/m³).


72

Table 34 Overview of room concentrations of contact allergens in the peak/steady state samples (in a 0,913 m³ room)

Air freshener spray

Hair spray Deodorant men

Deodorant spray women

glass and window cleaner

perfume kitchen cleaning

agent

passive air freshener

electrical air freshener 1

electrical air freshener 2

scented candle

µg/m³ µg/m³ µg/m³ µg/m³ µg/m³ µg/m³ µg/m³ µg/m³ µg/m³ µg/m³ µg/m³

D-limoneen 61,3 11,8 144,9

10,9 67,2 81,6 351* 685 14,8 9,4

linalool 255* 25,6* 6,8 19,9 19,7 106

255* 4222 1109 21,5

citronellol 1

789

2-(4-tert-Butylbenzyl)propionaldehyde 0 0

1,08

Hydroxy-citronellal

>2% area

fraction

citral

0

0

135

geraniol

33,6 26

52,2*

249,7* 251,8

cinnamal

17,7

* Standard deviation exceeding 20% # semi-quantitative assessment, relative to 2-fluorotoluene


73

Thirdly, the screening of the test room air on the presence of substrates from the AgBB library, led to

the identification of several additional compounds. The present compounds are listed in Table 35 to

Table 45; each table reports decreasing concentration levels (quantitatively or semi-quantitatively

relative to 2-fluorotoluene). When comparing test room concentrations of different product emission

tests it should be noted that, as listed in Table 33, the reported concentration levels originate from

peak samples as well as steady state samples.

Table 35 AgBB compounds in the emission test room air when testing a candle (in a 0,913 m³ chamber); sample 0-420 min

Candle emitted compounds

CAS-number Concentration [µg/m³]

Explicitly in AgBB

Group named in AgBB

α-pinene 80-56-8 51,3 quant. X

bicyclo(3.1.1)hept-3-en-2-one,4,6,6-trimethyl-,(1S)-

1196-01-6 34,3 semi-quant. Other terpene HC

benzene,1-methyl-3-(1-methylethyl)-

535-77-3 31,0 semi-quant. X

beta-phellandrene 555-10-2 23,5 semi-quant. Other terpene HC

β-Pinene 127-91-3 20,9 quant. X

toluene 108-88-3 10,7 quant. X

Limonene 138-86-3 9,37 quant. X

m/p-xylene 106-42-3/108-38-3

2,74 quant. X

styrene 100-42-5 1,65 quant. X

phenylethyne 536-74-3 1,42 semi-quant. X

ethylbenzene 100-41-4 0,56 semi-quant. X

camphene 79-92-5 0,52 semi-quant. Other terpene HC

alpha-phellandrene 99-83-2 0,03 semi-quant. Other terpene HC

1,4-cyclohexadiëne, 1-methyl-4-(1-methylethyl)-


Table 36 AgBB compounds in the emission test room air when testing kitchen cleaning agent (in a 0,913 m³ room); sample 0-30 min.

Kitchen cleaning agent Emitted compound

CAS-number

Concentration [µg/m³]

Explicitly in AgBB

Group named in AgBB


benzene,1-methyl-3-(1-methylethyl)- 535-77-3 0,65 semi-quant.

X

octanal 124-13-0 0,25 semi-quant. X

1,4-cyclohexadiëne, 1-methyl-4-(1-methylethyl)- 99-85-4 0,15 semi-quant.

Other terpene HC


Table 37 AgBB compounds in the emission test room when testing hair styling spray(in a 0,913 m³ room) ; sample 0-30 min.

Hair styling spray Emitted compound


Explicitly in AgBB

Group named in AgBB

Limonene 138-86-3 67.2 quant. X

1,4-cyclohexadiëne, 1-methyl-

4-(1-methylethyl)- 99-85-4 0,1 semi-quant.

Other terpene HC


74

Table 38 AgBB compounds in the emission test room when testing deodorant spray (in a 0,913 m³ room) ; sample 0-30 min.

Deodorant men compound

CAS-number


Explicitly in AgBB

Group named in AgBB

Limonene 138-86-3 145 quant. X

β-Pinene 127-91-3 14,1* quant. X


benzene,1-methyl-3-

(1methylethyl)- 535-77-3 1,98 semi-quant.

X

1,3,7-octatriene,3,7-dimethyl- 502-99-8 1,27 semi-quant. Other terpene HC

dipropylene glycol 25265-71-8 0,85 semi-quant. X

2-propanol,1,1'-oxybis- 110-98-5 0,51 semi-quant. X


Table 39 AgBB compounds in the emission test room when testing deodorant spray (in a 0,913 m³ room) ; sample 0-30 min.

Deodorant women compound

CAS-number


Explicitly in AgBB

Group named in AgBB

Decamethylcyclopentasiloxane* 541-02-6 721,4 quant. X

Dodecamethylcyclohexasiloxane 540-97-6 169,1 quant. X

Octamethylcyclotetrasiloxane 556-67-2 67,5 quant. X

nonanal 124-19-6 1,2 semi-quant. X

nonane 111-84-2 0,9 semi-quant.

Other saturated

aliphatic HC, up

to C8

decanal 112-31-2 0,7 semi-quant. X

octanal 124-13-0 0,4 semi-quant. X

acetophenon 98-86-2 0,2 semi-quant. X

Table 40 AgBB compounds in the emission test room when testing glass and window cleaning agent (in a 0,913 m³ room); sample 0-30 min.

Glass and window cleaning agent compound


Explicitly in AgBB

Group named in AgBB


cyclotetrasiloxane, octamethyl- 556-67-2 3,6 semi-quant. X


75

Table 41 AgBB compounds in the emission test room when testing air freshener spray (in a 0,913 m³ room) ; sample 0-30 min.

Air freshener spray compound


Explicitly in AgBB

Group named in AgBB


propylene glycol 57-55-6 2,0 semi-quant. X

benzene,1-methyl-3-


X

6-octen-1-ol,3,7-dimethyl-,(R)- 1117-61-9 1,1 semi-quant. Other terpene HC

nonanal 124-19-6 1,1 semi-quant. X

2-propanol,1,1'-oxybis- 110-98-5 0,8 semi-quant. X

1-hexanol,2-ethyl- 104-76-7 0,6 semi-quant. X

1,4-cyclohexadiëne, 1-methyl-4-

(1-methylethyl)- 99-85-4 0,5 semi-quant.

Other terpene HC


dipropylene glycol 25265-71-8 0,3 semi-quant. X

ethanol,2-(2-ethoxyethoxy)- 111-90-0 0,1 semi-quant. X


Table 42 AgBB compounds in the emission test room when testing perfume (in a 0,913 m³ room) ; sample 0-30 min.

Perfume compound


Explicitly in AgBB

Group named in AgBB



1,4-cyclohexadiene,1-methyl-4-(1-

methylethyl)- 99-85-4 1,02 semi-quant.

Other terpene HC

benzene,1-methyl-3-


X

1-hexanol,2-ethyl- 104-76-7 0,51 semi-quant. X




76

Table 43 AgBB compounds in the emission test room when testing a passive air freshener (in a 0,913 m³ room); sample 300-330 min.

Passive air freshener compound


Explicitly in AgBB

Group named in AgBB

Limonene 138-86-3 351,2* quant. X

α-pinene 80-56-8 175* quant. X

benzene,1-methyl-3-

(1methylethyl)- 535-77-3 591 semi-quant.

X

β-Pinene 127-91-3 276 quant. X

cyclohexanol,5-methyl-2-(1-

methylethyl)-

,(1.alpha.,2.beta.,5.alpha)-(+/-) 2216-51-5 246 semi-quant.

Other terpene HC


methylethyl)- 99-85-4 137 semi-quant.

X

toluene 108-88-3 114 quant. X

1,3,7-octatriene,3,7-dimethyl- 502-99-8 107 semi-quant. Other terpene HC



hexanal 66-25-1 46,8 semi-quant. X

3-carene 498-15-7 29,1 quant. X


1-hexanol 111-27-3 4,0 semi-quant. X

2-propanol,1-butoxy- 5131-66-8 3,0 semi-quant. X

Table 44 AgBB compounds in the emission test room when testing electrical air freshener 1 (in a 0,913 m³ room); sample 300-330 min.

Electrical air freshener 1 compound

CAS-number


Explicitly in AgBB

Group named in AgBB

2-propanol,1-(2-(2-methoxy-1-methylethoxdy)-1-methylethoxy)- 20324-33-8 3740 semi-quant.

X

Limonene 138-86-3 685* quant. X



1,4-cyclohexadiene,1-methyl-4-(1-methylethyl)- 99-85-4 129 semi-quant.

Other terpene HC



benzylalcohol 100-51-6 45,9 semi-quant. X

3-carene 498-15-7 21,8* quant. X


benzaldehyde 100-52-7 12,2 semi-quant. X


Isobutylacetate 110-19-0 5,0 semi-quant. X


77

Table 45 AgBB compounds in the emission test room when testing electrical air freshener 2 (in a 0,913 m³ room); sample 300-330 min.

Electrical air freshener 2 compound

CAS-number


Explicitly in AgBB

Group named in AgBB

2-propanol,1-(2-(2-methoxy-1-

methylethoxdy)-1-methylethoxy)- 20324-33-8 996 semi-quant. X

Terpeniol 98-55-5 652 quant. Other terpene HC



1,3,7-octatriene, 3,7-dimethyl- 502-99-8 27,6 semi-quant. Other terpene HC


methylethyl)- 99-85-4 21,5 semi-quant.

Other terpene HC



2-butoxyethanol 111-76-2 10,1 semi-quant. X

3-carene 498-15-7 8,4 semi-quant. X

1,4-methanoazulene,decahydro-4,8,8-

trimethyl-9-methylene-,(1S-

(1alpha,3a.be 475-20-7 5,7 semi-quant.

Other terpene HC

1-butoxypropanol 5131-66-8 2,0 semi-quant. X


78

Table 46 illustrates the TVOC concentration levels of the peak or steady state room concentrations,

in decreasing order. The reported TVOC concentration is the result of the integration of all peaks

from C6-C16 in the chromatogram, relatively to the internal standard 2-fluorotoluene. It should be

noted that the highest concentrations are obtained by products with a constant emission source, like

electric and passive air fresheners. According to these data, the tested passive air freshener leads to

the highest TVOC levels in the emission test room. Glass and window cleaning agent, followed by the

air freshener spray, led to the highest TVOC room concentrations for products with a decaying

emission profile. The lowest TVOC concentrations were measured in the test room concentration

when testing the kitchen cleaning agent.

Table 46 TVOC concentrations of peak or steady state test room air (in a 0,913 m³ room)

TVOC room concentration Timing

µg/m³

Electrical air freshener 1 28.859 300-330 min

Passive air freshener 23.057 300-330 min

Electrical air freshener 2 19.636 300-330 min

Candle 4.338 0-420 min

Glass and window cleaner 3.090 0-30 min

Air freshener spray 1.995 0-30 min

Hair styling spray 1.292 0-30 min

Deodorant women 1.138 0-30 min

Perfume 930 0-30 min

Deodorant men 793 0-30 min

Kitchen cleaning agent 512 0-30 min

A detailed, combined overview of all emitted gaseous compounds from one passive air freshener and

2 electrical air fresheners is shown in Table 47, Table 48 and Table 49.


79

Table 47 Full overview of all gaseous compounds, emitted by a passive air freshener, 2 (in a 0,913 m³ room); sample 300-330 min.

Compound CAS conc [µg/m³]

Explicitely in AgBB

AgBB group name Contact allergen

Carcinogen possible identifications, too low match factor

match too low (rt 21,48) 3713 semi-quant. chloroacetic acid, 2-ethylhexylester (match 43%) or cyclopentanecarboxylic acid,3-methylbutylester (match 38%)

Dihydromyrcenol 18479-58-8 2353 semi-quant.

Tripropylene glycol monomethylether 20324-33-8 1479 semi-quant.

Diisobutylcarbinol 108-82-7 1102 semi-quant.

match too low (rt 25,44) 938 semi-quant. tri(1.2-propylene glycol), monomethylether (match 64%)

Linalyl acetate 115-95-7 876 semi-quant.

cyclohexanone,5-methyl-2-(1-methylethyl)-

491-07-6 780 semi-quant.

benzene,1-methyl-3-(1methylethyl)- 535-77-3 591 semi-quant. X

Eucaliptol 470-82-6 361 quant.

Limonene 138-86-3 351 quant.* X X


Linalool 000078-70-6 255 quant.* X

cyclohexanol,5-methyl-2-(1-methylethyl)-,(1.alpha.,2.beta.,5.alpha)-(+/-)

2216-51-5 246 semi-quant. Other terpene HC

α-pinene 80-56-8 175 quant.* X

γ-Terpinene 99-85-4 137 semi-quant. Other terpene HC

toluene 108-88-3 114 quant. X




hexanal 66-25-1 46,8 semi-quant. X

3 - Carene 498-15-7 29,1 quant. X


1-hexanol 111-27-3 4,0 semi-quant. X

2-propanol,1-butoxy- 5131-66-8 3,0 semi-quant. X

TVOC 23057 semi-quant.


80

Table 48 Full overview of all gaseous compounds, emitted by electrical air freshener 1, 2 (in a 0,913 m³ room); sample 300-330 min

Compound CAS conc [µg/m³] Explicitely in AgBB AgBB group name Contact allergens

Carcinogens

phenylethylalcohol 60-12-8 4666 semi-quant.

Linalool 78-70-6 4222 quant. X

2-propanol,1-(2-(2-methoxy-1-methylethoxdy)-1-methylethoxy)- 20324-33-8 3740 semi-quant. X

Dihydromyrcenol 18479-58-8 1594 semi-quant.

Linalyl acetate 115-95-7 1533 semi-quant.

1-(2-Methoxypropoxy)-2-propanol 13429-07-7 1138 semi-quant.

1,2-dihydropyridine,1-(1-oxobutyl) 1000132-46-2

1092 semi-quant.

Benzyl acetate 140-11-4 963 semi-quant.

Citronellol 106-22-9 783 semi-quant. X

1-(2-Methoxy-1-methylethoxy)-2-propanol 20324-32-7 773 semi-quant.

Limonene 138-86-3 685 quant.* X X

Geraniol 106-24-1 250 quant.* X



1,4-cyclohexadiene,1-methyl-4-(1-methylethyl)- 99-85-4 129 semi-quant. Other terpene HC

α-pinene 80-56-8 75 quant. X

Eucaliptol 470-82-6 74,9 quant.


benzylalcohol 100-51-6 45,9 semi-quant. X

3-carene 498-15-7 21,8 quant.* X


benzaldehyde 100-52-7 12,2 semi-quant. X


Isobutylacetate 110-19-0 5,0 semi-quant. X

TVOC 28.859 semi-quant.

* standard deviation of more than 20%


81

Table 49 Full overview of all gaseous compounds, emitted by electrical air freshener 1, 2 (in a 0,913 m³ room); sample 300-330 min

Compound CAS conc [µg/m³]

Explicitely in AgBB

AgBB group name Contact allergen

Carcinogen possible identifications, too low match factor

2-Propanol, 1-(2-methoxy-1-methylethoxy)- 020324-32-7 3635 semi-quant.

2-Propanol, 1-(2-methoxypropoxy)- 013429-07-7 2930 semi-quant.

Match factor too low (rt 21.89 ) 1312 semi-quant. Mixture benzene methanol, α,-methyl-, acetate and 3-cyclohexene-1-methanol,α, α 4-trimethyl, and α-terpineol

dihydromyrcenol 18479-58-8 1140 quant.

Linalool 000078-70-6 1109 quant. X

2-propanol,1-(2-(2-methoxy-1-methylethoxdy)-1-methylethoxy)-

20324-33-8 996 semi-quant. X

Phenylethyl Alcohol 000060-12-8 830 semi-quant.

terpineol 98-55-5 652 quant. Other terpene HC

2,6-Octadien-1-ol, 3,7-dimethyl-, (Z)- 032210-23-4 458 semi-quant.

Cyclohexanol, 1-methyl-4-(1-methylethylidene)-

6975-94-6 432 semi-quant.

4-tert-Butylcyclohexyl acetate 000586-81-2 401 semi-quant.

Cyclohexanol, 1-methyl-4-(1-methylethenyl)- 000106-25-2 289 semi-quant.

Geraniol 106-24-1 252 quant. X

Citral 5392-40-5 135 semi-quant. X



1,3,7-octatriene, 3,7-dimethyl- 502-99-8 27,6 semi-quant. Other terpene HC

1,4-cyclohexadiene,1-methyl-4-(1-methylethyl)-



Limonene 138-86-3 14,8 quant. X X

2-butoxyethanol 111-76-2 10,1 semi-quant. X

3-carene 498-15-7 8,4 semi-quant. X

1,4-methanoazulene,decahydro-4,8,8-trimethyl-9-methylene-,(1S-(1alpha,3a.be


1-butoxypropanol 5131-66-8 2,0 semi-quant. X

TVOC 19.636 semi-quant.

* standard deviation of more than 20%

Chapter 6 Conclusion quantification of product emissions by laboratory testing

83

CHAPTER 6 CONCLUSION QUANTIFICATION OF PRODUCT EMISSIONS BY LABORATORY TESTING

The present document reports on the EPHECT consumer product emission tests. It should be

emphasized that the studied products represent only a minor fraction of all the consumer products

available on the European market and cannot be considered as representative for all consumer

products of the studied consumer product classes. Variations in the product composition as well as in

the product emissions between different products of one EPHECT consumer product class (such as

all-purpose cleaners, or electrical air fresheners) were confirmed in this work.

Besides the quantification of the EPHECT key compound emissions of the studied products, this work

package also illustrates the wide variety of other emitted –potentially health relevant- substrates. A

screening on emitted contact allergens, carcinogenic compounds, and AgBB compounds learned that

several other substrates are emitted as well. However, their potential health impact will not be

considered in the subsequent exposure and health risk assessment of EPHECT.

Therefore, the reported data do contribute to the understanding of the indoor use of consumer

products, they illustrate the wide variation of emitted substrates and the respective quantity in

which these are emitted. It also illustrates a QA/QC strategy for product emission testing in different

laboratories. The present data do provide a valuable basis for consumer product exposure studies

and for the respiratory health risk assessment based on the EPHECT priority compounds in the next

work package (WP7). Furthermore, the results contribute to pre-normative work in the

standardisation of consumer product emission testing, as it proposes an EPHECT umbrella for

consumer product testing that is based on the aggregation state, the product package and the use

scenario of the product. It also discusses the repeatability of the proposed consumer product

emission testing strategy more in detail in intercomparison experiments.

In fact, the intercomparison experiment revealed some critical aspects of consumer product emission

testing:

- a use scenario with a low degree of freedom has a positive impact on the repeatability of the

experiment (e.g. perfume testing), leading to a decreased between-laboratory variation

- a use scenario with higher degrees of freedom (e.g. creamy kitchen cleaning agent) makes it

more challenging to obtain repeatable results between different laboratories, leading to a

larger between laboratory variation (affecting the within laboratory variation to a lesser

extend)

- at low loading factors, composing agents occurring at lower concentrations in the product

may not reach detectable test room concentrations (mainly in larger emission test rooms)

- emission test rooms smaller than 0,25m³ are not usable for emission tests of selected

consumer products studied in EPHECT. The more standardized and simplified the preparation

of the test specimen, the better also small chambers can be used by experienced labs for

non-burned and non-sprayed products, taking into consideration that the small chamber


84

volume 0.05 m³ was problematic for emission estimations of terpenes for the tested

products in EPHECT.

- When modelling emission scenario’s, more differences between laboratories are highlighted.

Based on the experimental work presented here, further conclusions regarding emission testing are

provided in the report “Guidance on (consumer products) Emission testing”.


85

REFERENCES

ASTM 5116-10 – Standard Guide for small-scale environmental chamber determinations of organic

emissions from indoor materials/products.

Emissions of air pollutants from scented candles burning in a test chamber. Derudi M., Gelosa S.,

Sliepcevich A., Catteneo A., Rota R., Cavallo D., Nano G. Atmospheric Environment (2012).

Evaluation of VOC Emissions from building products, Sold Flooring material. ECA report 18, 1997.

Influence of Air Fresheners on the Indoor Air Quality. Study ordered by the Federal Public Service of

Helath; Food Chain Savety and Environment. M. Spruyt et al. 2006.

Organic Indoor Air Pollutants; Occurence, Measurement, Evaluation, second edition. Tunga

Salthammer and Erik Uhde. Wiley-VCH, Weinheim 2009.

S.J. Wasson, Z. Guo, J.A. McBrian, L.O. Beach. Lead in candle emissions. The Science of the Total

Environment 296 (2002) 159–174.

Standard ECMA-328 – Determination of chemical emission rates from electronic equipment, 5th

edition 2010.

The use of a house cleaning product in an indoor environment leasing to oxygenated polar

compounds and SOA formation: gas phase chemical characterisation. Rossignol S., Rio C., Ustache A.,

Fable S, Nicolle J., Même A., Anna B.D., Nicolas M., Leoz E. and Chiappini L.. Atmospheric

Environment (2013).

ANNEX

87

ANNEX 1

Source strength determination (NRCWE)

For comparative purposes, an attempt was carried out to determine the source strength normalized

to per gram consumer product (µg/hour per gram) applied for selected key pollutants at different

time intervals and for the entire test period.

The source strength for a given key pollutant was determined as the chamber concentration (Ct) at a

given sampling period (t) multiplied with the air exchange rate (AER) and multiplied with the

chamber volume (Vol) and divided with the amount of product (gram) applied:

Source strength = Ct(µg/m3)xAER(h-1)xVol(m3) per gram product = µg/hour per gram.

Time resolved source strengths for selected key pollutants are shown in Figs. 1a-1c; the time (t) is

taken as the middle of a sampling period. Further, Tables 2a-2c show the average source strength for

the entire test period. Please, that the last time point generally shows the average source strength,

see also Tables 2a-c.

Table 2a. Kitchen cleaning agent: average source strength (µg/h per gram product) for limonene and

dihydromyrcenol.

Laboratory Sampling period, min

NRCWE 0-308

VITO 0-420

UOWM IDMEC 0-420

Key pollutant

-pinene 1.4 - - 0.4

Limonene 161 22 - 38

Dihydromyrcenol 28 10 - 8*

*) Toluene equivalents. - = Not detected.

Table 2b. Electrical air freshener: average source strengths (µg/h per gram product) for selected key pollutants.


NRCWE 0-302

VITO 180-390

UOWM IDMEC 0-378

Key pollutant

Limonene - 34 - 48

Linalool 2874 1571 - 935*

Geraniol - - - 1486

Dihydromyrcenol 2975 - - 935*

*) Toluene equivalents. - = Not detected. # = Sampled between 180-390 min.

ANNEX

88

Table 2c. Perfume: average source strengths (µg/h per gram product) for selected key pollutants.


NRCWE 0-306

VITO 0-420

UOWM

IDMEC 0-424

Key pollutant

Limonene 96 160 - 14

- = Not detected.

Fig. 1a. Kitchen cleaning agent. Source strength of limonene and dihydromyrcenol.

Kitchen cleaning agent, source strenght, limonene

0

50

100

150

200

250

0 50 100 150 200 250 300 350 400 450

Time, min

So

urc

e s

tren

gth

, m

icg

/ho

ur

NRCWE

VITO

UOWM

IDMEC

Kitchen cleaning agent, source strenght, dihydromyrcenol

0

5

10

15

20

25

30

35

40

45

50

0 50 100 150 200 250 300 350 400 450

Time, min

So

urc

e s

tren

gth

, m

icg

/m3

NRCWE

VITO

UOWM

IDMEC

ANNEX

89

Fig 1b. Electrical air freshener. Source strength of limonene, linalool and geraniol.

Air freshener, elec.,source strength, limonene

0

5

10

15

20

25

30

35

40

45

50

0 50 100 150 200 250 300 350 400 450

Time, min

So

urc

e s

tre

ng

th,

mic

g/h

ou

r

NRCWE

VITO

UOWM

IDMEC

Air freshener, elec., source strength, linalool

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

0 50 100 150 200 250 300 350 400 450 500

Time, min

So

urc

e s

tre

ng

th,

mic

g/h

ou

r

NRCWE

VITO

UOWM

IDMEC

Air freshener, elec., source strength, geraniol

0

500

1000

1500

2000

2500

0 50 100 150 200 250 300 350 400 450

Time, min

So

urc

e st

ren

gth

, mic

g/h

ou

r

NRCWE

VITO

UOWM

IDMEC

ANNEX

90

Fig. 1c. Perfume. Source strength of limonene.

Results

One laboratory showed generally low source strengths for all three products tested.

In general, certain differences were observed in detecting some of the key pollutants. For instance,

for the kitchen cleaning agent -pinene was absent; for the air freshener -and β-pinene were

absent in the largest chamber, while dihydromyrcenol was undetected in two laboratories and one

laboratory reported camphene that was absent in the other laboratories. For the perfume β-pinene

and linalool were only observed in two laboratories.

In general, the time resolved source strengths, despite normalization, showed large difference

between the laboratories; see Figs. 1a-1c. For the average source strength, the kitchen cleaning

agent a factor of eight for limonene; for the air freshener a factor of four for two of the pollutants

(linalool and dihydromyrcenol); and the perfume about a factor of about twelve was observed for

limonene.

Conclusions

A direct comparison of the emission data is hampered by the large differences in chamber

specifications and possible analytical bias. The major cause of the differences is the air velocity. The

emission rate of this type of point sources is dominated by external diffusion that by nature is

strongly influenced by the air velocity. Furthermore, the user pattern, i.e. amount and application,

will also most likely influence the emission.

Large differences in the source strength are anticipated due to substantial differences in the air

velocity up to a factor of 600. Furthermore, not only different patterns of applying the product, but

Perfume, source strength, limonene

0,00

100,00

200,00

300,00

400,00

500,00

600,00

0 50 100 150 200 250 300 350 400 450

Time (min)

So

urc

e S

tren

gth

, m

icg

/ho

ur

NRCWE

VITO

UOWM

IDMEC

ANNEX

91

also large differences in the amount per chamber volume were apparent that may influence the

outcome.

The data clearly demonstrate great difficulty of carrying comparative emission testing of point

sources with user pattern dependencies. The comparison is hampered by two major obstacles:

different air velocities, the amount of usage and pattern of application.

The experience gained from this comparison of the emission pattern from three different consumer

products opens up for a discussion of proper testing of temporary point sources like consumer

products. The key question is whether it is possible to generate emission data of temporary point

sources in small chambers that allow estimation of realistic exposure concentrations.

ANNEX

92

ANNEX 2

Specific emission rate calculations based on test chamber concentrations (VITO)

Step 1: Mixing correction

The test chamber didn’t always reach full mixing at the sampling times used in this project. This can

be derived from the continuous monitor’s results, and from the test chamber optimisation process

(see also ECA Report no 18 - Evaluation of VOC emissions from building products, Spruyt et al., 2006

Appendix F).

Therefore, a mixing factor specified was taken into account. The quantitative concentrations are

hence corrected with Equation 1, where N is the air exchange rate of the chamber, and t is the

sampling time (centre of the sampling interval).

(eq.1)

The corrected test chamber concentration (Cwell-mixed) is the concentration that should be measured if

the concentration emitted from the source would reach a steady-state condition in the room, as

assumed in ISO 16000-9. Note that Cwell-mixed equalizes Ctest chamber at later sampling times t.

After correcting the measured test chamber concentration for mixing, 2 different emission profiles

can be identified:

Step 2: The calculation of emission rates, based on test chamber concentrations

From Spruyt et al., 2006 Appendix F and ECA Report no 18 - Evaluation of VOC emissions from

building products

The emission rates are calculated with mass balances. The most general form for emission tests in

test chambers is given in Equation 3 (Kephalopoulos, S., 1999; and Kephalopoulos, S. in Salthammer

et al., 2009).

(eq.2)

Where:

Vchamber: Volume of the test chamber (m³)

ER: Emission Rate (mass units/h)

F: Removal Rate by an air cleaning device in the chamber

Qout : Air flow rate going out of the chamber (m³/h)

C: Concentration in the Chamber

Q in: Air flow rate going in of the chamber (m³/h)

ANNEX

93

C ext Voc concentration of the inlet air (mass unit/m³)

A: Rate of adsorption on surfaces in the chamber (mass units/h)

D: Rate of desorption from surfaces in the chamber (mass units/h)

X: Rate of generation through gas phase reactions in the chamber (mass units/m³/h)

Assuming no sink effects inside the test chamber, and no chemical reactions inside the room, the

equation can be reduced to:

(eq.3)

Re-organised, this mass balance can be formulated as following:

(eq.4)

With a negligible background concentration,

and with

the air change rate, the

equations can be written as:

(eq.5)

(ASTM mass balance)

And thus the emission rate becomes

/L (eq.6)

If the chamber concentrations are constant or if their variations per time unit are negligible

compared to their measured values multiplied by the air exchange rate N (ECA Report no 18 -

Evaluation of VOC emissions from building products):

(eq.7)

So, the emission rate can be calculated as

(eq.8)

Including the well-mixing correction the emission rate becomes:

(eq.9)

Which is in agreement with the ‘9.4.1.1 Direct calculation of Emission factor from individual data

points’ in ASTM D5116-10 as well as standard ECMA-328.

At steady state conditions, which is at longer times t, the exponential factor becomes equal to zero,

and thus less relevant. So at steady state, the equation becomes:

ANNEX

94

at point t in time (eq.10)

Step 3: Emission profile identification

The equation for the computation of emission rates based on test chamber concentrations, depends

on the emission profile of the tested product. For the consumer products tested in EPHECT 3

different emission profiles can be distinguished: (1) a constant emission source, (2) an instantaneous

release with a decaying concentration, and (3) a non-instantaneous release, with a constant decay.

1. The case of a constant emission source

Figure 22 Example, passive air freshener gel tested by VITO

This emission profile (shown in Figure 22) applies to the following EPHECT consumer products:

combustible air fresheners, passive units, electric units

For these products, we assume a constant emission source, meaning that the air fresheners’

emissions did not change over time (dC/dt is negligible). Emission rate of a constant emission source

can be computed using equation 8:

At steady state conditions, which occurs at longer times t (in Figure 22 longer than 3 hours) the

exponential factor becomes equal to zero, and thus less relevant. So the emission rate at time t can

be calculated by:

To enable a better comparability of the measured data, the specific emission rate (SER), independent

of air exchange rate and loadings is to be preferred. SER describes a product-specific emission

behaviour, e.g. mass specific, or area specific, or unit specific.

As a consequence, the SER of a constant emission source, at a point in time t, can be expressed as

follows:

Mass specific SER

0

5

10

15

20

25

30

0 1 2 3 4 5 6 7

con

cen

trat

ion

[pp

m]

time [h]

THC passive air freshener gel

ANNEX

95

expreseed in

Unit specific SER

expreseed in

Where Q= inlet air flow (m³/h) of the chamber

These formulas apply for a situation of online measurements, where the concentration C(t) is

determined at a certain point in time t. However, since most concentration measurements in EPHECT

have been performed offline, the measured concentration applies to a certain time interval, that may

vary between the laboratories.

A first approach would be to set the middle of the measurement time interval equal to t

However, more accurate would be to use a time averaged correction factor in the calculations

(Spruyt et al., 2006). This can be obtained by applying the equation to calculate the average value of

a function in a finite time interval:

This then leads to the following deviation of the time averaged correction factor:

ANNEX

96

With respect to this time averaged correction, the SER(t) equations become:

Mass specific SER

expreseed in

Unit specific SER

expreseed in

2. The case of a decaying concentration in the room

a. During the experiment: Also for these products, the emission rate can be expressed by equation 5:

However, since for these products the test chamber concentration cannot be considered constant,

nor at steady state conditions. In agreement with ASTM-D5116-10 the emission rate cannot be

considered as relatively constant over the test period, reaching and maintaining a constant

equilibrium value. Therefore, the parameter dC/dt cannot be neglected to simplify the formula.

According to (Salthammer et al., 2009) as well as ASTM D5116-10, the specific emission rate can be

expressed as:

With

As a consequence, based on n+1 experimental data, n-1 emission rate values can be obtained, using

this method.

According to Salthammer et al., 2009 the most simple model is the one where a compound is

emitted from a sample into the chamber, and then it is removed with the exhaust air. This ‘dilution-

model’ has been introduced by Dunn and Trichenor, 1988, for a source with a constant and

exponentially decaying emission rate respectively. However, the emission rates presented in this

document are computed by applying the equation presented by Salthammer et al. 2009.

Since most concentration measurements in EPHECT have been performed offline, the measured

concentration applies to a certain time interval that may vary between the laboratories. For emission

rate computation of products with a decaying emission rate, the more simple approach to set the

middle of the measurement time interval equal to t will be applied over the time averages

correction.

ANNEX

97

Mass specific SER

expressed in

With

Unit specific SER

expressed in

With

When comparing the outcomes of the different test room, a correction for well-mixing is applied on

the room concentrations. This is particularly influencing on the first sampling points, and then has a

decreasing influence when correcting concentrations at later point t in time. The correction is applied

in the calculation of ϪC/Ϫt.

b. For the full emission test measurement Using the above formulae, dC/dt cannot be computed for the full emission test measurement (which

measures the average concentrations over the total duration of the experiment).

Therefore, we assume that for this measurement, that generally takes 7 hours, dC/dt is negligible. In

such situation, the formula that was deviated for a time averaged correction factor is applied for this

full emission test duration measurement. The equations listed below are thus applied for the total

emission test measurements:

With respect to this time averaged correction the SER(t) equations become:

Mass specific SER

expreseed in

Unit specific SER

expreseed in

ANNEX

98

This applies for two types of emission profiles:

Instantaneous release

Figure 23 Example of the THC profile of a perfume, tested at VITO

This applies for all sprayed EPHECT products: air fresheners (spray), coating products, hair styling

products, deodorants (sprays), perfumes

No instantaneous release

This applies for the following EPHECT products: glass and window cleaner, all purpose cleaner,

kitchen cleaning agent, floor cleaning agent, bathroom cleaning agent, furniture polish, floor polish

References:

ASTM 5116-10 – Standard Guide for small-scale environmental chamber determinations of organic

emissions from indoor materials/products.

Evaluation of VOC Emissions from building products, Sold Flooring material. ECA report 18, 1997.

Influence of Air Fresheners on the Indoor Air Quality. Study ordered by the Federal Public Service of

Helath; Food Chain Savety and Environment. M. Spruyt et al. 2006.

Organic Indoor Air Pollutants; Occurence, Measurement, Evaluation, second edition. Tunga

Salthammer and Erik Uhde. Wiley-VCH, Weinheim 2009.

Standard ECMA-328 – Determination of chemical emission rates from electronic equipment, 5th

edition 2010.

0

1

2

3

4

5

6

-1 0 1 2 3 4 5 6 7

con

cen

tra

tio

n [

pp

m]

time [h]

THC perfume spray

-0,02

0

0,02

0,04

0,06

0,08

0,1

0,12

0,14

0,16

0,18

-1 0 1 2 3 4 5 6 7

con

cen

trat

ion

[p

pm

]

time [h]

THC kitchen cleaning agent

ANNEX

99

ANNEX 3

Specific emission rate calculations of EPHECT consumer products, based on test chamber concentrations

ANNEX

100

DECAYING EMISSION SOURCES



Perfume VITO 0,916 0,5 0,06 0,1 5.168 221 1.561 66 8.196 526

NRCWE 20,24 0,5 0,20 0,01 5.776 153 - - - -

IDMEC 0,255 0,86 0,07 0,3 5.042 157 1.728 55 14.719 476

UOWM 0,051 0,5 0,16 3,1 1,4 1,4 4,2 3,6 - -

room size AER mass L SER(tpeak) SER (average) SER(tpeak) SER (average)

[m³] [/h] [g] [g/m³] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g]

Glass and window cleaner VITO 0,916 0,5 0,58 0,6 239 8 - 21 no comparison possible

NRCWE

IDMEC

UOWM

room size AER mass L SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average)

[m³] [/h] [g] [g/m³] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g]

Air freshener spray VITO 0,916 0,5 0,75 0,8 1.240 19 5.167 71 240 3,8 609,0 8,1 - - - - - -

DIFFERENT PRODUCT NRCWE 20,24 0,5 5,10 0,3 1.564 10 - - - - - - 827 - 363 - 371 -

IDMEC

UOWM



Deodorant VITO 0,916 0,5 0,34 0,4 - - 530 24 - - - - 593 44 364 - 637 -

DIFFERENT PRODUCT VITO 0,916 0,5 0,42 0,5 3.538 73 134 9 137 3 346 15 824 52 283 - 335 -

IDMEC

UOWM

room size AER mass L SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average)

[m³] [/h] [g] [g/m³] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g]

coating product VITO

NRCWE 20,24 0,5 11,80 0,6 23.904 23 530.455 730 899.949 - - 7.804

IDMEC

UOWM

room size AER mass L SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average)

[m³] [/h] [g] [g/m³] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g]

Furniture polish VITO

DIFFERENT PRODUCT NRCWE 0,916 0,5 12,60 13,8 1.213.642 60.252 3.380 55 - 6 - - - - - - - - - - - - - - - - - -

IDMEC 0,255 0,84 1,84 7,2 - - - - - - 28.425 31 126.687 104 94.420 116 165.757 137 15.340 17 5.002 7 202 - 2.271 3 22 -

UOWM



bathroom cleaning agent VITO

NRCWE 20,24 0,5 7,80 0,4 178 4 31 6 9.680 -

IDMEC

UOWM



Floor cleaning agent VITO

DIFFERENT PRODUCT NRCWE 20,24 0,5 1,50 0,1 523 5 808 28 428 - 2.213 - - - - - - -

IDMEC

UOWM 0,051 0,5 0,07 1,3 - - - - - - - - 470 - 470 - 869 -

room size AER mass L SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average) SER(tpeak) SER (average)

[m³] [/h] [g] [g/m³] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g]

All purpose cleaner VITO

DIFFERENT PRODUCT NRCWE

IDMEC 0,255 0,87 1,37 5,4 564.836 829 81 - 118 - 92 - - - - - - - - - - - - - - - - - - -

UOWM 0,051 0,5 30,18 593,0 - - - - - - 112 - 99 - 52 - 2 - 1 - 384 - 59.775 - 5.769 - 372 - 536 -

CONSTANT EMISSION SOURCES

room size AER mass L SER(teq) SER (average) SER(teq) SER (average) SER(teq) SER (average) SER(teq) SER (average) SER(teq) SER (average)

[m³] [/h] [g] [g/m³] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g]

Electrical air freshener VITO 0,916 0,5 0,27 0,3 28 31 32 44 59 80 2.059 1.588 - -

NRCWE 20,24 0,5 0,40 0,02 56 159 265 0 - - 4.394 5.645 - -

IDMEC 0,255 0,86 0,64 2,5 - 57 68 9 82 63 2.090 1.127 4.951 1.792

UOWM 0,051 0,5 0,48 9,4 0,2 0,4 4,1 3,9 2,1 1,6 0,5 0,7 - -

room size AER mass L SER(teq) SER (average) SER(teq) SER (average) SER(teq) SER (average) SER(teq) SER (average) SER(teq) SER (average) SER(teq) SER (average) SER(teq) SER (average) SER(teq) SER (average)

[m³] [/h] [g] [g/m³] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g]

Passive air freshener VITO 0,916 0,5 0,40 0,4 642 427 321 282 504 454 467 743 209 200 53 34 661 476 476 0

DIFFERENT PRODUCT NRCWE 20,24 0,5 0,27 0,01 42 26 - - - - 2.194 1.155 - - - - - - 1.933 1.279

IDMEC

UOWM

room size AER mass L SER(teq) SER (average) SER(teq) SER (average) SER(teq) SER (average) SER(teq) SER (average) SER(teq) SER (average) SER(teq) SER (average) SER(teq) SER (average) SER(teq) SER (average)

[m³] [/h] [g] [g/m³] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g] [µg/h.g]

Candle VITO 0,916 0,5 21,80 23,8 7,80 0,27 0,84 1,49 0,30 0,61 0,42 0,62 0,24 0,41 0,16 0,31 0,00 0,08 0,09 0,05

NRCWE

IDMEC 0,050 7,43 26,01 520,2 7,49 5 0,44 0,62 0,31 0,23 14 9 0,15 0,19 0,85 0,26 0,16 0,27 0,14 0,07

UOWM

toluene m+p-xylene

Limonene linalole

Limonene linalole eucaliptol alpha - Terpeniol formaldehyde acetaldehyde acrolein

3-carene eucaliptol

Limonene α-pinene β-pinene linalole benzene

Limonene β-pinene linalool

Limonene α-pinene β-pinene geraniol

Limonene α-pinene β-pinene linalole toluene

toluene m/p-xylene

dihydromyrcenol

Limonene linalole alpha-pinene beta-pinene

Butyl acetate Aliphatic Solvents C6-C10* Decamethylcyclopentasiloxane acroleine

Aliphatic solvents (C8-C13) m-xylene naphthalene octane

linalool

propilcyclohexane decane limonene linalole

geraniol PM1 PM2,5

a-terpeniol Linalyl anthranilate formaldehyde

styrene

limonene toluene dihydromyrcenol

limonene linalole a-pinene α-Terpineol acetone propionaldehyde 2-butanone

1-metoxy-2-propanol

nonane

limonene camphene a-pinene propionaldehyde butanoneβ-pinene carene formaldehyde acetaldehyde acetone

ANNEX

101

ANNEX 4

Comparison of the A.I.S.E. candle emission test protocol (in 0.913 m³) with the EPHECT candle emission test at VITO (0.913 m³), at IDMEC (0.05 m³)

Comparison of room concentrations

Sample after extinction EPHECT (VITO)

Sample without extinction AISE (VITO)

Sample after extinction EPHECT (IDMEC)

timing steady state sample collection 300-330 min 180-240 min 316-355 min

TEST ROOM CONCENTRATIONS (per candle) [µg/m³]

formaldehyde [50-00-0] 350 218 962

benzene [71-43-2] 11 74 66

IDEAL ROOM CONCENTRATIONS (30 m³) (per candle) [µg/m³]

formaldehyde [50-00-0] 11.501 7.178 577.020

benzene [71-43-2] 345 1.213 39.603

Comparison of emission factors and rates

Sample before extinction EPHECT (VITO)

Sample without extinction AISE (VITO)

Sample before extinction EPHECT (IDMEC)

timing steady state sample collection 240-270 min 180-240 min 316-355 min room volume [m³] 0,913 0,913 0,05 quantity [# candles] 1 2 1 total weight loss [g] 22 26 26 AER [/h] 0,5 1 7,43 T [°C] 22 ± 0,8 (20,7 - 23,13) 23 ± ? 25,0±1.9 RH [%] 54 ± 18 (34 - 84) 51,9±3,7 O2 deviation [%] 2% 1,67%

sampling collection time [h] 4-4,5 h 3-4 h 5,3-5,9 h sample collected after # air changes [ACH] 2,5 4 44 burn rate [g/h] 3,1 3,2 (2,7-3,8) 3,7 weight loss until the end of this sampling 14,0 12,8 21,8

AISE FORMULAE

ER = emission rate = C.n.V/a RSD VITO(EPHECT)-VITO(AISE)-

IDMEC(EPHECT) RSD VITO (EPHECT)- IDMEC (EPHECT)

ER (formadehyde) [µg/h] 210 200 357,3 34% 37%

ER (benzene) [µg/h] 5,6 33,8 19,8 72% 79%

ENR/Ϫm

ENR/Ϫm (formaldehyde) [µg/h.g] 15,0 15,6 16,4 5% 7%

ENR/Ϫm (benzene) [µg/h.g] 0,4 2,6 0,9 89% 55%

ENR = normalized emission rate = ER/BR

ERN (formadehyde) [µg/g] 67,4 62,3 96,8 25% 25%

ERN (benzene) [µg/g] 1,8 10,5 5,4 75% 71%

EPHECT FORMULAE

Specific emission rate

SER (formaldehyde) [µg/g.h] 17,7 16,1 16,4 5% 5%

SER (benzene) [µg/g.h] 0,5 2,7 0,9 85% 39%

ANNEX

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