QUANTIFICATION OF THE PRODUCT EMISSIONS BY …...2009, GEV testing method, etc… ) and standards on...
Transcript of QUANTIFICATION OF THE PRODUCT EMISSIONS BY …...2009, GEV testing method, etc… ) and standards on...
QUANTIFICATION OF THE PRODUCT
EMISSIONS BY LABORATORY TESTING
WP6
PART I CONSUMER PRODUCT TEST PROTOCOL Marianne Stranger, Frederick Maes, Eddy Goelen (VITO) Asger W. Nørgaard, Peder Wolkoff (NRCWE) Gabriela Ventura, Eduardo de Oliveira Fernandes (IDMEC) Evangelos Tolis, John Bartzis (UOWM) January 2012
This report arises from the project EPHECT which has received funding from the European Union, in the framework of the Health Programme.
“© IDMEC, UMil, UOWM All rights on the materials described in this document rest with IDMEC, UMil and UOWM. 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 Research Comitee, Athens, 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
Table of contents
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TABLE OF CONTENTS
Distribution List _________________________________________________________________ III
Table of contents ________________________________________________________________ V
List of figures ___________________________________________________________________ VI
List of tables ___________________________________________________________________ VII
List of acronyms _______________________________________________________________ VIII
CHAPTER 1 Introduction ________________________________________________________ 1
CHAPTER 2 EPHECT Umbrella for Consumer Product Testing ___________________________ 3
2.1 Consumer product emission testing versus Building product emission testing 3
2.2 Internal versus external diffusion in consumer product testing 5
2.3 EPHECT Umbrella for consumer product testing 8
2.3.1 Start-up conditions: emission test chamber system 10
2.3.2 Initial test conditions 10
2.3.3 Product specific test chamber conditions 11
2.3.3.1 Liquid consumer and personal care products 12
2.3.3.2 Solid consumer and personal care products 14
CHAPTER 3 EPHECT priority compounds ___________________________________________ 16
3.1 Strategy for the identification of key and emerging pollutants 16
3.1.1 Inclusion and exclusion criteria for the selection of key and emerging pollutants 16
3.1.2 Selection of key pollutants 17 3.1.3 Selection of emerging pollutants _______________________________________ 17
3.2 Overview of the key and emerging pollutants per consumer product category 18
CHAPTER 4 EPHECT Analytical Methods ___________________________________________ 20
4.1 Identification of the EPHECT analytical methods 20
CHAPTER 5 EPHECT QA/QC _____________________________________________________ 22
CHAPTER 6 EPHECT plan of work _________________________________________________ 24
6.1 Test chamber experiments of 15 product classes in 4 different labs 24
6.2 Translation into an operational plan of work 25
6.3 Reporting data for BUMAC imputation 26
References_____________________________________________________________________ 31
List of figures
VI
LIST OF FIGURES
Figure 1 Diagram of the kinetic processes involved in the mass transfer model of VOCs from material surfaces (adopted from Sparks et al. 1996). _________________________________________ 6
Figure 2 EPHECT Umbrella for consumer product testing __________________________________ 9 Figure 3 Operational plan of work for spray consumer product testing at VITO ________________ 26 Figure 4 Datasheet for WP6 emission data _____________________________________________ 30
List of tables
VII
LIST OF TABLES
Table 1 Selection of EPHECT consumer products _________________________________________ 3 Table 2 Units of emission test results from EPHECT consumer and personal care products ________ 5 Table 3 Start-up conditions EPHECT consumer product emission testing _____________________ 10 Table 4 Initial conditions for EPHECT consumer product emission testing ____________________ 10 Table 5 The ideal room dimensions and loading factors according to CEN TC 351 WG2 __________ 11 Table 6 Experimental conditions to test liquids, packed in a flask ___________________________ 12 Table 7 Experimental conditions to test liquids, packed in a spray bottle _____________________ 13 Table 8 Experimental conditions to test liquids, packed to be volatilized _____________________ 14 Table 9 Experimental conditions to test solid products; candle emissions ____________________ 15 Table 10. Selected key pollutants. ____________________________________________________ 17 Table 11 Selected emerging pollutants. _______________________________________________ 18 Table 12 Primary and secondary key pollutants, and liq. phase quantification. ________________ 18 Table 13 Specification of selected pollutants. ___________________________________________ 19 Table 14 Overview of the EPHECT analytical methods ____________________________________ 20 Table 15 Test chamber experiments of the EPHECT consumer and personal care products _______ 24 Table 16 EPHECT work division sheet _________________________________________________ 27
List of acronyms
VIII
LIST OF ACRONYMS
WP Work package quats Quaternair amonium salts THC Total Hydrocarbon
Chapter 1 Introduction
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CHAPTER 1 INTRODUCTION
EPHECT work package 6 (WP6) involves 4 different laboratories that will perform lab testing
experiments in product test chambers of different dimensions. The main aim of this document is to
tune the laboratory activities of these research institutes for obtaining meaningful emission data.
Several aspects of the laboratory work are addressed and described in this document. These include:
The formulation of consumer product test protocols (chapter 2)
The assessment of priority compounds, studied in WP6 and further WPs (chapter 3)
The detailed description of analytical methods, used by the different involved laboratories (chapter 4)
The QA/QC strategy, applied in the EPHECT lab testing activities (chapter 5)
The EPHECT plan of work (Chapter 6)
Secondly this document may contribute to the definition and formulation of a general consumer
product test protocol, to assess emissions related to the use and typical use scenarios of consumer
and personal care products in households. It can be considered as a first step to obtain harmonized
lab testing experiments of consumer products. Since different laboratories are involved, using
emission test chambers of various dimensions, attention is also put to analyse products in more than
one lab. The latter experiments will provide valuable information concerning the error of emission
rates from consumer products, which are calculated based on this consumer product test protocol
presented in this document.
This document addresses a strategy to assess product emissions, related to the household use of
consumer products. This is based on available open literature and on pre-screening experiments,
performed by the laboratories involved in WP6. The strategy presented in this document is
optimized, updated and fine-tuned, based on the results of the EPHECT lab experiments that are
organised based on this protocol. The strategy presented here, more specifically applies to the 15
EPHECT product classes that comply with the 6 EPHECT criteria, defined in the EPHECT project
proposal. These selection criteria are the following:
- The product is used in households - The use of the product causes an exposure related to the use - The product emits key or emerging pollutants - The product has a considerable indicative household use frequency - The product mainly causes inhalation exposure - The use causes a health end point
Chapter 2 Ephect umbrella for consumer products testing
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CHAPTER 2 EPHECT UMBRELLA FOR CONSUMER PRODUCT TESTING
2.1 Consumer product emission testing versus Building product emission testing
In the recent decades, research activities on product emissions were mainly focused on building
material emissions. The resulting emission test procedures, evaluation protocols (e.g. AgBB, Afsset
2009, GEV testing method, etc… ) and standards on emission test chamber procedures and sampling
techniques (ISO 16000-3, ISO 16000-6, ISO 16000-9) are well-established. ASTM D6670-01 (2007)
describes a more generic strategy for (VOC) emission testing from materials, products and
equipment (building materials, furniture, consumer products, printers, air cleaners etc.) typically
used in office and residential buildings, in full-scale chambers for VOC emission testing. However,
specifically for the consumer and personal care products studied in EPHECT, dedicated standards for
emission tests are currently not available. Test protocols as well as the results, reported in the open
literature, vary between laboratories and are difficult to compare, mainly due variable test conditions
(Derudi et al. 2012; Salthammer et al. 2009). Therefore, EPHECT aims at a maximal overlap between
the proposed consumer and personal care product test protocols and existing ISO standards and
other relevant emission test/evaluation protocols and standards for building materials.
Table 1 Selection of EPHECT consumer products
1 all purpose cleaner
2 kitchen cleaning agent
3 floor cleaning agent
4 glass and window cleaner
5 bathroom cleaning agent
6 furniture polish
7 floor polish
8 combustible air fresheners
9 air fresheners (spray)
10 passive units
11 electric units
12 coating products
13 hair styling products
14 deodorants (sprays)
15 perfumes
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In building material emission testing, the products are typically installed as a static object in the test
chamber, with respect to relevant ISO standard (ISO 16000-9), test chamber dimensions, and
reported loading factors; the product emissions are assessed respecting valid emission test protocols.
The selection of EPHECT consumer and personal care products (listed in Table 1), consists of products
characterized by exposures which are related to the household uses and use scenarios (resulting
from EPHECT criterion nr. 2). Certain aspects of the emission test protocols proposed in EPHECT may
therefore differ from the well-established building material test protocols, because the emissions will
only occur when a certain interaction between the product and the user takes place: a certain use
scenario should thus be simulated in the test chamber.
An important aspect of an emission test protocol is its repeatability and applicability in emission test
chambers of various dimensions. For building material emission testing, the repeatability will mainly
be function of the product dimensions with respect to the loading factor and the test conditions
(respecting chamber start-up conditions and test conditions). For consumer product testing, the
repeatability of the use scenario can additionally have a considerable impact on the emission test
results.
The list of EPHECT consumer and personal care products, shown in Table 1, implies a variety of use
scenarios. These use scenarios are typically function of the product package (sprays, flasks, etc.) and
of the purpose of the product (floor cleaning agent to be diluted, floor polish to be used undiluted,
etc.). The product package on the other hand is closely related to the aggregation state of the
product (solid, liquid or gaseous). Each package and product purpose combination thus implies a
specific use scenario that should be simulated in the test chamber protocol, in a reproducible way, in
order to assess the emission characteristics and factors of the consumer product.
When assessing building product emissions in emission test chambers, the emission test result is
typically obtained as specific emission rate per hour and per m² surface (or per kg or per m³ product
or per unit). It is then used to model its concentration in a reference room. For consumer and
personal care product testing, the units of the emission factors are typically related to the amount of
used products. Depending on the product package (spray, flask, ..) this parameter can be expressed
per hour (passive units), and per grams aerosols or product (spray, electric units² ) or product as well
as per square meters surface covered with the product (if used on a surface). They are thus reported
in dimensions of µg/h per unit, in case no dosage is possible, and in µg per hour and per mass aerosol
for a spray product. Emission factors of liquid products applied on a surface are typically reported in
µg per hour and per m2, referring to the reference surface in the test room. An overview hereof is
shown in Table 2.
Chapter 2 Ephect umbrella for consumer products testing
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Table 2 Units of emission test results from EPHECT consumer and personal care products
Use and use scenario Emission Rate units Normalized Emission Rate units
Applied on a surface
all purpose cleaner
µg/h
(dilutions according to
manufacturer or market study)
Area specific emission rate
µg/(h.g.m2)
kitchen cleaning agent
floor cleaning agent
glass and window cleaner
bathroom cleaning agent
furniture polish
floor polish
Combustible, active or passive units
passive units µg/h
Mass specific emission rate
µg/(h.g)
electric units
combustible air fresheners
Sprayed on a surface or in the air
air fresheners (spray)
µg/h
(±0,5 sec or 0.5g automatic spray)
Mass specific emission rate
µg/(h.g aerosol)
(±0,5 sec or 0.5g automatic spray)
hair styling products
deodorants (sprays)
coating products (sprays)
perfumes
glass and window cleaner (spray)
2.2 Internal versus external diffusion in consumer product testing
The important questions about emission testing of building and consumer products are a) what specific pollutants are emitted that may affect occupants; b) how their emission profiles changes over time; and c) are the emission test results meaningful – i.e. are the results independent of test conditions In general, the emission can be characterized by two fundamental physical processes (see Figure 1), partly taken from Salthammer et al. 2009.
a) Gas-phase mass transfer (i.e. external diffusion) b) Source-phase mass transfer (i.e. internal diffusion)
Chapter 2 Ephect umbrella for consumer products testing
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Figure 1 Diagram of the kinetic processes involved in the mass transfer model of VOCs from material surfaces (adopted from Sparks et al. 1996).
The gas-phase mass transfer model (a) is based on molecular diffusion across a laminar boundary layer as described in equation (1), external diffusion.
)CC(k)CC(D
SER iSgiS
(1)
SER is the specific emission rate, D is the diffusion coefficient, is the thickness of the boundary layer, CS is the concentration of the target VOC at the source surface and Ci is the concentration of the target VOC in the air and kg is the gas-phase mass transfer coefficient. Process (b) is limited by internal diffusion from the interior of the source to the surface and can be described by equation (2).
)mm(kSER iSs (2)
Here, ms is the mass of the target VOC in the source, mi is the mass of the target VOC at the surface and ks is the source-phase mass transfer coefficient. Comparing emission test results from different chambers, three different scenarios have to be considered.
For kg >> ks: the emission is controlled by the external diffusion process and the thickness of the boundary
layer is directly related to the air velocity above the surface and turbulence, if it is a point source or activity related emission (e.g. spray). This applies to most wet-applied or liquid building products and certain consumer products during the drying/curing phase. Thus, the external diffusion is significantly affected by both surface air velocity/turbulence and the sample loading factor (m2/m3) (and associated vapour concentration within the chamber). The exact timing of the emissions testing is also critical for wet samples, in particular for temporary point sources. During this phase it is therefore paramount to control both air velocity (and/or turbulence), in order to prevent them from influencing/changing the test result. However, for temporary (activity related) point sources like spray products, the air velocity/turbulence becomes difficult to define and measure (which direction), and no
air
boundary layer
source
Ci
Cs
mi
ms
surface
gas-phase mass transfer(external diffusion)
source-phase mass transfer(internal diffusion)
kg
ks
Figure 3
Chapter 2 Ephect umbrella for consumer products testing
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harmonized practice exists. Thus, any comparison of such temporary sources will by nature be rather difficult to compare between laboratories with quite different chambers without applying rigorous control of all parameters prior to and during testing. However, the extreme sensitivity of the results to such a multitude of variables, does call into the question the validity of testing wet samples and point sources during the curing/drying stage or use. Further, a vapour pressure effect for such wet-like products cannot be ruled out; thus, some agreed upon test condition is helpful, but not a guarantee for obtaining comparable emission data.
For kg << ks: the emission is controlled by the internal diffusion process and the influence of the air flow condition in the chamber should be negligible. This applies to most solid building materials and to wet and liquid products after a surface film have been formed. There will be a transition phase where kG and ks compete together; thus, a more difficult situation arises for
kg ks or if the ratio ks/kg changes over time. For an ageing product, ks/kg will normally reach infinity over time. Thus, VOC emissions controlled by internal diffusion (dry products/materials) are largely independent of surface air velocity and loading, provided the exchange rate is fast enough to prevent a vapour pressure effect.
Thus, for consumer product testing, that is characterized by short-term or temporary activity related emission profiles and dominated by external diffusion any comparison of emission data obtained from different chambers (and even only slightly different test conditions) is by nature encumbered, even if harmonized test conditions are attempted. Two often quoted questions about the outcome of emission testing of building materials in a given chamber are: “does the chamber provide correct” SERs” and “how comparable are the round-robin testing results with other chambers”. These questions lead to the implicit assumption that SER data obtained from that particular chamber may be less reliable. These questions are deceptive, especially in view of round-robin testing, because a successful test requires that the results are independent of test conditions, i.e. the emission data are comparable. This is only the case for emissions where the mass transfer rate within the material is slower than in the boundary layer (i.e. “internal” versus “external” diffusion control). However, many other factors influence the SER, of which the most important ones are material homogeneity and laboratory performance (Oppl, 2008; Wolkoff et al., 2005). For consumer products with short-term emission profiles the issue becomes even more difficult, because of the difficulty of defining and controlling exactly identical test and activity conditions. In theory, under well controlled environmental conditions and satisfactory recovery (minimal sink (wall) effect) and adequate sampling (according to the objective) and analytical performance, comparable SERs should be obtainable for “internal” diffusion controlled emissions from homogeneous materials, independent of type of chamber. Thus, a third frequently asked question is “whether there exists an ideal chamber providing SER data that would be identical in real scenarios”, i.e. a golden chamber standard. One may ask how meaningful is it to predict (model) externally controlled SERs of VOCs and SVOCs from building materials and consumer products in real life indoor scenarios, in view of the inherent difficulties associated with the use of climate chambers. These include all the factors that influence the SERs and external factors. Thus, measured SER in a climate chamber, even with adequate recovery and low wall sink effects, may not be representative of the actual SER from the exact same building material/product in a real indoor setting. Well-knowing that chambers versus chambers may differ, in some cases for reasons outside of the performance of chamber itself, one should consider the objective of the emission test itself. Thus, the sampling strategy should reflect the objective of the testing. This in EPHECT means that the emission data should accommodate requirements set by the risk assessment objective. The important issue here is
Chapter 2 Ephect umbrella for consumer products testing
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that the risk assessment focuses on acute effects, semi-acute effects or longer-term (respiratory) effects. Thus, the sampling strategy should be adopted accordingly, where applicable. With this in mind, one may contemplate the feasibility and meaningfulness of transforming emission data, at least of short-term temporary (point source) emissions to a given model room. Other emission decay models are available simply by use of the known in the product.
2.3 EPHECT Umbrella for consumer product testing
Aiming at an EPHECT test protocol that implies a maximal overlap between the test scenario for the
various selected consumer product classes, as well as a maximal overlap with existing knowledge on
building material emission testing, the consumer product test protocols are presented in the EHPECT
umbrella.
This umbrella, pictured in Figure 2, shows common as well as different steps between the proposed
test scenarios for the different EPHECT product classes. The upper level of Figure 2 indicates the
generic aspects of the test protocol, whilst the lower levels are more specifically dedicated to the
specific consumer product package, use scenario and purpose. The reported test conditions result
from a review of existing open literature on consumer and personal care product emission testing
and from pre-screening experiments, performed in EPHECT. These pre-screening experiments have
addressed several practical issues on test performance, feasibility and repeatability of tests and test
results.
The resulting EPHECT umbrella consists of 3 levels:
- Start-up conditions
- Initial test chamber conditions
- Product specific test chamber conditions
These 3 levels are discussed more in detail in the following paragraphs.
Chapter 2 Ephect umbrella for consumer products testing
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Figure 2 EPHECT Umbrella for consumer product testing
EPHECT umbrella for Consumer Product Emission Testing
- AIR FLOW: deviation of exhaust flow with intake flow < 5%
- TVOC (ISO 16000-9) < 20 µg.m-3
; individual VOC < 2 µg.m-3
(radiello code 130 -min 48h, max 5d)
- collect/sample up to 80% of the intake flow
- AIR EXCHANGE RATE: 0.5/h ± 5% deviation and ±3% accuracy
- RECOVERY AND SINK permeation or diffusion tube - known concentration toluene and n-dodecane in the chamber - conc after 72h in room - recovery > 80%Start-up
conditions
(ISO 16000-9)
Initial test
chamber
conditions
(ISO 16000-9)
- AIR VELOCITY above the sample 0.1-0.3 m/s and accuracy 0.1m/s
- RH 50% ± 5% and ±3% accuracy
- T 23°C ± 2 and accuracy ±1°C
- VOC level (FID)
Liquid
(fluid, cream or gel)Solid
Aggregation
state of the
product?
- weigh before and after test
Flask
Spray To
volatilize
To burn
- Chamber < 20L, 20L - 50 m3
- Weigh before and after test
- weigh before and after
test
- ideally: automatic spray
of 0.5 sec
Use
diluted
Use
undiluted
Rinse
after use Don't rinse
after use
Rinse
after use
Don't rinse
after use
- quantity/dilution: function
of real use scenario and
expected (T)VOC levels
- Rinse + wet mop outside
test chamber
- Sample collection:
t0: application (0-1h)
t1: 1h-3h
t2: 3h-5h
t3: 5h-7h
- quantity/dilution: function of
real use scenario and
expected (T)VOC levels
- Wet mop outside test
chamber
- Sample collection:
t0: application (0-1h)
t1: 1h-3h
t2: 3h-5h
t3: 5h-7h
- quantity: function of real
use scenario and expected
(T)VOC levels
- Rinse + wet mop outside
test chamber
- Sample collection:
t0: application (0-1h)
t1: 1h-3h
t2: 3h-5h
t3: 5h-7h
Spray on
a surface
Spray in
the air
- # sprays is function of real use scenario’s and expected (T)VOC levels
- Sample collection:t0: spray (0-1h)t1: 1h-3h t2: 3h-5h t3: 5h-7h
- PM monitoring
- spray at time t0
spray orientation: angle 45°,
upwards to air movement
- sprayed quantity is
approx. 0.5g per 1m3 or 1
automatic spray at max
position if electric device
- Sample collection:t0: spray (0-1h)t1: 1h-3h t2: 3h-5h t3: 5h-7h
- PM monitoring
- weigh before and after test
- light during at least 6h (taken
burning time of candle in
consideration)
- light with a gas lighter
- Sample collection:
t0: 0-3h after installation and lighting
t2: 3h-4h
t2: 4h-5h
t3: 5h-6h (extinguish candle after 5h)
- THC monitoring, PM monitoring,
EC/OC assessment, O2 monitoring at
inlet and outlet
Passive
Active
Electric
unit
To be
heated by
a candle
- electricity supply in room
- run test until at least 3h after
equilibrium
- position max
Sample collection:
t0: 0-3h after installation
t2: 3h-4h
t2: 4h-5h
t3: 5h-6h
- PM Monitoring
- run test until at least 3h
after equilibrium
- dimensions (distance
candle, quantity, dilution)
Sample collection:
t0: 0-3h after installation
t2: 3h-4h
t2: 4h-5h
t3: 5h-6h
- THC monitoring
Product specific
test chamber
conditions
- run test until at least 3h
after equilibrium
Sample collection:
t0: 0-3h after installation
t2: 3h-4h
t2: 4h-5h
t3: 5h-6h
LF ideal room ‘Arrêté sur l’etiquettage (NOR :
DEVL1104875A); CEN TC 351 WG2
if surface = window:LF = 0.07 m
2/m
3
if surface = floor:
LF = 0.4 m2/m
3
if other surface = adapted m2/m
3
- quantity: function of real
use scenario and expected
(T)VOC levels
- Wet mop outside test
chamber
- Sample collection:
t0: application (0-1h)
t1: 1h-3h
t2: 3h-5h
t3: 5h-7h
Test ends when
THC =< 5%
deviation of initial
concentration
Test ends when
THC =< 5%
deviation of initial
concentration
Test ends when
THC =< 5%
deviation of initial
concentration
Test ends when
THC =< 5%
deviation of initial
concentration
Test ends when
THC =< 5%
deviation of initial
concentration
Test ends when
THC =< 5%
deviation of initial
concentration
After 6h
After 6hAfter 6h
After 6h
LF ideal room ‘Arrêté sur l’etiquettage (NOR :
DEVL1104875A); CEN TC 351 WG2
if surface = window:LF = 0.07 m
2/m
3
if surface = floor:
LF = 0.4 m2/m
3
if other surface = suitable
surface m2/m
3
Chamber dimensions in
relation to spray strength
(> 0.5 m3)
Chapter 2 Ephect umbrella for consumer products testing
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2.3.1 Start-up conditions: emission test chamber system
The test chamber start-up conditions in the EPHECT consumer product testing procedures are the
same as those reported in ISO 16000-9 (Indoor Air – Part 9: determination of the emission of volatile
organic compounds from building products and furnishing – emission test chamber method). This
implies the installation settings summarized in Table 1. The listed parameters have been measured or
set before the experiment takes place and will be kept constant during the experiment.
Table 3 Start-up conditions EPHECT consumer product emission testing
Aspect Conditions
Air supply The emission test chamber has facilities capable of continuously controlling the air change rate at a fixed value with an accuracy of ± 5%
Air flow The deviation of the exhaust flow with the intake flow is < 5%
Air Exchange rate 0.5/h ± 5% deviation and ± 3% accuracy
Sample collection limit The sum of sampling air flows can be up to 80% of the intake flow
Recovery and sink Using a permeation of diffusion tube, insert a known concentration of toluene and n-dodecane in the chamber, measure the concentration after 72h in the room. The recovery should be > 80%
2.3.2 Initial test conditions
The initial test conditions are also established in agreement with ISO 16000-9. In consumer product
testing these test conditions are labeled as ‘initial’ conditions, since the emission tests of certain
products might disturb one or more of the initial conditions. This could for instance occur when
assessing the emissions of a diluted floor cleaning agent: applying the product in the chamber will
increase the relative humidity that was initially set at 50%. They are however considered to be less
critical when realistic user scenarios are simulated.
Table 3 summarizes the initial test conditions for EPHECT consumer product testing.
Table 4 Initial conditions for EPHECT consumer product emission testing
Aspect Conditions
Temperature 23°C ± 2°C (accuracy of 1.0°C)
Relative humidity 50% ± 5% (accuracy of 3%)
Air velocity The air velocity above the sample is 0.1-0.3 m/s (accuracy 0.1 m/s) (with an averaging time of 1 minute)
Supply air & background concentrations (TVOC and VOCS)
The concentration of TVOC is below 20 µg.m-3
; Individual VOCs occur at concentrations below 2 µg.m
-3
(radiello code 130 – at least 48h, maximal 5 days)
Chapter 2 Ephect umbrella for consumer products testing
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During the experiments, temperature, relative humidity and air flow rate are monitored
continuously.
2.3.3 Product specific test chamber conditions
This lower level of the EPHECT umbrella describes more specific test conditions for consumer and
personal care product emission testing.
All emission data measured in the test chamber are recalculated to the ideal room dimensions
(CEN/TS 16516 and CEN TC 351 WG2). This implies a room with a total volume of 30 m3, and an air
change rate of 0,5 h-1. This ideal room consists of a floor of 12 m2, a ceiling of 12 m2, one door of 1,6
m2, walls of 31,4 m2 (excluding door and window) and joints (or small surfaces) of 0,2 m2. Table 5
shows an overview of these dimensions. For the windows, reference is made to l’Arrêté sur
l’étiquettage’ NOR : DEVL1104875A and CEN TC 351 WG2, with a surface of one window equal to 2
m2. In case a product can be used on several types of surfaces, the most important surface will be
taken into account (in agreement with NOR: DEVL1104875A). Using the dimensions of this ideal
room in the generation of emission data, will also enable us to refer to EU LCI values. However, a
direct comparison should be carried out with some caution, because LCI values refer to the emission
after 28 days only. Further, it is probable that LCI values in the future will consider multiple-source
contribution.
Whenever applicable, the loading factors, related to the ideal room dimensions, are respected in the
EPHECT test protocols. This implies that e.g. a floor cleaning agent will be tested respecting a loading
factor of 0.4 m2/m3 and a window cleaning agent will be applied respecting a loading factor of 0.07
m2/m3. Products to be applied on surfaces (other than floor, ceiling, door, window or walls) will be
tested respecting the loading factor included in Table 5 as ‘joints or small surfaces’, as far as this is a
representative loading factor for the use of that product in a room.
Table 5 The ideal room dimensions and loading factors according to CEN TC 351 WG2 and CEN/TS 16516
Surface [m
2]
Loading factor [m
2/m
3]
Floor 12 0,4
Ceiling 12 0,4
1 door 1,6 0,05
1 window* 2 0,07
Walls (excl. window & door) 31,4 1
Joints (or small surfaces) 0,2 0,007
* only in CEN TC 351 WG 2
Because the major influence of the aggregation state on the use and use scenario of a product, the
first division is made between liquid and solid consumer and personal care products.
Chapter 2 Ephect umbrella for consumer products testing
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2.3.3.1 Liquid consumer and personal care products
Liquid consumer and personal care products include fluids, creams and gels. Depending of the
product purpose, they can be found in different packages. They can be stored (1) in a flask, (2) in a
spray bottle (pistol spray, continuous spray or automatic spray), or (3) in a format to be volatilized.
The test protocol scenarios, proposed in the EPHECT umbrella depend on this product package. All 3
options are discussed below in detail:
Products packed in a flask
Liquid products, stored in a flask, may involve products to be used in a diluted as well as in an
undiluted concentration. They are typically applied on a surface. The type of surface on which the
product is tested will be of a representative material, typical for the purpose of the product.
Throughout the EPHECT project, similar products tested in more than one lab will be tested on the
same surface material. However, for full scale chambers, a metal surface (steel) may be preferable to
be able to obtain an even surface. After the application, the surface may need to be rinsed. For
practical purposes an additional rinsing process after surface drying will interfere in a full scale
experiment. Thus, data obtained from full scale testing might be considered a worst case scenarion,
because there is no information about the effect of rinsing effect. For small chamber testing both
application and eventually rinsing may have to be carried out outside the chamber. The
interpretation from outside conditioning should be carried out with caution due to lost volatiles.
EPHECT consumer and personal care products on which this section applies are all purpose cleaners,
kitchen cleaning agent, floor cleaning agent, (no spray) window cleaner, (no spray) bathroom
cleaning agent, (no spray) furniture polish and floor polish. Table 6 gives an overview of the
conditions for emission experiments of liquids, stored in a flask.
Table 6 Experimental conditions to test liquids, packed in a flask
Aspect Conditions
Room dimensions No restrictions
Loading factor In agreement with Table 5
Quantity If diluted use: dilution according to the results from the market study on EU uses and use patterns (WP5) and according to expected (T)VOC levels
*.
If undiluted use: quantity according to the results from the market study on EU uses and use patterns (WP5) and according to expected (T)VOC levels
*.
Scenario Rinse if use scenario prescribes to do so
Wet mop out room
Sampling t0: during the application (0-1h) t1: 1h – 3h t2: 3h – 5h t3: 5h – 7h
End of the test When THC has less than 5% deviation from the initial concentration
* This implies that the used quantity may be multiplied if a first test leads to values below the detection limits of the used
techniques. After the experiments this multiplication should be taken into account.
Chapter 2 Ephect umbrella for consumer products testing
13
Products packed in a spray bottle
Liquid products packed in a spray bottle will, depending on the product purpose, be sprayed in the
air or on a surface. The type of spraying bottle, and thus the use scenario, will be related to the
product purpose. Products to be sprayed on a surface are packed in a pistol spray bottle; products to
be sprayed in the air will be packed in a bottle to allow continuous or automatic (with electricity
supply) spraying.
In order to avoid spraying on the test chamber walls, the allowed test chamber dimensions to study
these products are restricted to 0.5 m3 or larger.
EPHECT consumer and personal care products, on which this section applies are air freshener sprays
(manual spray or automatic spray), hair styling products (sprays), deodorant sprays, coating product
sprays, and perfumes.
Table 7 gives an overview of the conditions for emission experiments of liquids, packed in a spray
bottle.
Table 7 Experimental conditions to test liquids, packed in a spray bottle
Aspect Conditions
Room dimensions Larger than 0.5 m3
Loading factor If spraying pistol (to be sprayed on a surface) in agreement with Table 5
Quantity If spraying in the air: spray quantity is limited to approximately 0.5g of product ( 0.5s of spraying per m
3 test chamber), or one automatic spray at maximum
capacity) and according to expected (T)VOC levels*.
If spraying on a surface: quantity according to the results from the market study on EU uses and use patterns (WP5) and according to expected (T)VOC levels
*.
The product is weight before and after the experiment.
Scenario If sprayed on a surface: representative selection of the surface material to be sprayed on
Sampling t0: during the application (0-1h) t1: 1h – 3h t2: 3h – 5h t3: 5h – 7h PM monitoring
End of the test When THC has less than 5% deviation from the initial concentration
* This implies that the used quantity may be multiplied if a first test leads to values below the detection limits of the used
techniques. After the experiments this multiplication should be taken into account.
Products packed to be volatilized
Products to be volatilized can be passive units that volatilize without any user interaction, or active
units, that require a source of heating. Both types of products, packed to be volatilized, need time to
Chapter 2 Ephect umbrella for consumer products testing
14
equilibrate with the surrounding air, before any assessment of the product emissions can take place.
In EPHECT, this period to equilibrate is set on 3 hours (equal to 1.5 air changes).
The only restriction on test chamber dimensions is the size of the product to be tested, that should fit
in the test cell.
EPHECT consumer and personal care products, on which this section applies, are passive and electric
units. These units may be air freshener units as well as insect repellent devices.
Table 8 gives an overview of the test conditions for liquid products, packed to be volatilized.
Table 8 Experimental conditions to test liquids, packed to be volatilized
Aspect Conditions
Room dimensions No restrictions (the product should fit)
Loading factor Maximum one unit per full scale chamber
Quantity If passive unit: not applicable If active unit: position max The product is weighed before and after the experiment.
Scenario Passive units should be placed on a board, minimum twice the area of the unit Active units may need electrical supply in the exposure chamber
Sampling t0: 0 h – 3h after installation t1: 3h – 4h t2: 4h – 5h t3: 5h – 6h Full scale chamber: Sample in quadruplicate after establishment of chamber equilibrium (by PID). PM monitoring when active units
End of the test After 6 hours
2.3.3.2 Solid consumer and personal care products
Solid consumer products, considered in EPHECT, are candles. This strategy is based on available open
literature (Derudi et al. 2012), and on the AISE candle emission test protocol (AISE, Development of a
standard methodology for measuring emissions from candles, 2012) that was made available for
EPHECT. The candle should be inserted in the test chamber with the air flow on and should be lighted
with a gas lighter. Then the test chamber must be closed. The candle emissions expected to
equilibrate during 3 hours. Sampling however starts in the period of 0h to 3h after lighting the
candle. The sampling is performed in the following three hours. When the last sampling hour starts,
the candle should be extinguished, and the emissions are monitored during one more hour. For small
test chambers the air flow should be 0.5 m³/h per candle. In case of large test chambers an air
exchange rate of 0.5 h-1 should be used. The air velocity (speed) in the test chamber in the vicinity of
Chapter 2 Ephect umbrella for consumer products testing
15
the candle should be measured without the candle being lighted and should be lower than 0.30 m/s.
The air velocity (speed) with a lighted candle is higher, due to the convection movements caused by
the thermal gradients. The burning rate should be determined after the test, and should be
compared with the burning rate of a duplicate candle burned in a normal room. The two values
should not differ by more than 15%.
The only restriction on test chamber dimensions is the size of the product to be tested.
For candle emissions special attention should be put on relative humidity and oxygen supply. Relative
humidity should be kept below 75%, in order to avoid wall condensation in the room (AISE protocol
for candle emission). The outlet oxygen concentration shouldn’t not decrease more than 2.5%
compared to the inlet oxygen concentration (AISE protocol for candle emission; this number ).
Table 9 shows an overview of the experimental conditions to test candle emissions.
Table 9 Experimental conditions to test solid products; candle emissions
Aspect Conditions
Room dimensions No restrictions – the candle should fit in
Loading factor Small test chambers - air flow of 0.5 m³/h per candle Full scale test chambers - air exchange rate of 0.5 h
-1
Quantity 1 candle; more than one taking into account expected (T)VOC levels*.
The product is weighted before and after the experiment.
Scenario The candle is placed on a preconditioned surface in the test chamber. It is lighted using a gas lighter.
Sampling t0: 0 h – 3h after lighting the candle t1: 3h – 4h t2: 4h – 5h t3: 5h – 6h (with the candle extinguished) PM monitoring EC/OC assessment O2 monitoring at inlet and outlet
End of the test After 6 hours
* This implies that the used quantity may be multiplied if a first test leads to values below the detection limits of the used
techniques. After the experiments this multiplication should be taken into account.
Chapter 3 Ephect priority compounds
16
CHAPTER 3 EPHECT PRIORITY COMPOUNDS
3.1 Strategy for the identification of key and emerging pollutants
3.1.1 Inclusion and exclusion criteria for the selection of key and emerging pollutants
The main focus of EPHECT is the identification and quantification of air pollutants that potentially
may be associated with adverse respiratory effects, i.e. (chemo-) sensory irritation in the airways,
asthma and pulmonary effects.
Although it is well-established that a number of fragrances are known to cause dermal effects by
contact (skin allergy), there is no supporting evidence that such compounds in ozone poor
environments are associated with airway effects (1).
A large number of common industrial chemicals have been assessed for risk of airway effects, like
asthma. In general, except for acid anhydrides and isocyanates, e.g. (2), industrial chemicals have not
been identified to cause asthma (1;3;4). This also goes for chemicals like phthalates (1;5) although
they have received much publicity in the literature. Further, polyethylene glycol ethers are not
considered to be airway sensitizers, e.g. (4;6), in agreement with international scientific guidelines
(7;8); however, recent focus on this type of pollutants (9;10) have prompted the selection of 2-
butoxyethanol as a pollutants of some general interest; further, this common solvent has also been
proposed as a potential proxy for terpene-containing consumer products, cf. (11).
Formaldehyde have previously been associated with asthma in children, however, supporting
evidence has not been identified (12;13) and this is further strengthened by lack of biological
plausibility (14).
A number of reviews argue that increase of airway health effects in cleaning personnel is associated
with the use of cleaning agents, e.g. (15-17). Suspected product categories and pollutants that have
been suggested as important contributors to health effects among cleaning personnel are products
in spray-form, amines (e.g. ethanolamine), chlorine bleach and other disinfectants like quaternary
ammonium compounds and glutaraldehyde (15;17). It has been argued that quaternary ammonium
compounds only have occupational relevance (1), however, the concern may be extended in indoor
environments to new types of quaternary compounds.
Fragrances like pinenes and limonene have also been suggested as airway sensitizers and sensory
irritants; this, however, is judged only to be relevant in ozone-enriched environments, e.g. (18). Thus,
more research into cause-effect relationships is recommended for this group of pollutants, e.g. (13).
In summary, chemically non-reacting VOCs in general are not considered to cause respiratory effects
at indoor concentrations. The ozone-initiated reactions with carbon-carbon unsaturated VOCs
(alkenes), present in a number of fragrances, need to be investigated further, cf. (18); not only
Chapter 3 Ephect priority compounds
17
because of the formation of a host of new oxygenated species (e.g. formaldehyde) of which there is
concern about their airway effects, e.g. (19;20), but also the concern about the formation of ultrafine
particles, see below.
Ultrafine particles have received much focus and concern about respiratory and cardio-pulmonary
effects during the last decade (21). More recently, the focus has been on spray products and
reported respiratory effects, e.g. (22-24) and combustion of e.g. candles and incense. Another
relevant issue of concern is the ultrafine particle formation in the ozone-initiated alkene (e.g.
terpenoids) reactions, e.g. (18).
3.1.2 Selection of key pollutants
The selection procedure for key pollutants has been depending on the Index project (25), WHO
indoor air guidelines (26), WHO air quality guidelines (27), and SCHER (28), see Table 10.
Table 10. Selected key pollutants.
Key pollutants INDEX 2005 WHO 2010 WHO 2000 SCHER
Ammonia x
Benzene x x x
Naphthalene x x x
Formaldehyde x x x
Ultrafine particles x x
-pinene x
Limonene x
Carbon monoxide x x x
Nitrogen dioxide x x x
Ozone (18)
3.1.3 Selection of emerging pollutants
The selection of emerging pollutants has partly been depending on the outcome of the EPHECT WP4
deliverable ‘Literature review on product composition, emitted compounds, emissions rates and
health end points from consumer products’, partly from a compiled selection of relevant emission
literature from the product categories, close to 100 papers (Appendix 1), including recent literature
findings deemed to be of potential interest and concern as a research gap, and identified jointly with
WP7. The selection is further supported by the pre-screening process carried out in winter 2010-
spring 2011. Table 11 shows the selected emerging compounds.
In addition to the above listed compounds others will also be identified during the lab testing
experiments, although they are not assessed to pose respiratory effects, e.g. aromatic compounds,
phthalates, PAH, and chlorinated compounds.
Chapter 3 Ephect priority compounds
18
Table 11 Selected emerging pollutants.
Potential source Odour Sensory irritant
Potential Lung effects
Examples literature
Acrolein Combustion x
Butoxyethanol Common solvent x (x) (10)
Terpenoids Fragrances x (x)* (x)a
(18)
QUATsb
Biocides x (29;30)
Chloramines Disinfectants x x (30)
Perfluorinated siloxanes Coatings x (22-24)
ROSc
Ozone-initiated reactions Particles
x (31)
a) In ozone enriched environments. b) Quaternary ammonium compounds. c) Reactive oxygen species.
3.2 Overview of the key and emerging pollutants per consumer product category
The selection of key and emerging pollutants for the different product categories are briefly listed in
Table 12 and further specified in Table 13. This selection is based on open literature and on pre-
screening experiments, performed in EPHECT. For a complete list, see Appendix 2. Products listed in
column ‘1. Primary Priority key pollutants, gas phase’ must be quantified in gas phase for each
product. Also the major VOCs with a relative intensity above 10% must be quantified. The
compounds listed in the column ‘2. Secondary priority key pollutants’ may be emitted by certain
products, they are detected quantitatively if possible. The 3rd column lists the compounds that will be
detected in the liquid phase of the product. Since up to now little or no literature is available on the
presence of miscellaneous compounds in the various consumer product classes, this set of
compounds is being assessed for any product tested in EPHECT.
Table 12 Primary and secondary key pollutants, and liq. phase quantification.
1. Primary priority key pollutants, gas phase 2. Secondary priority key
pollutants, gas phase
Selected pollutants
(%), liq phase
A1 All purpose cleaner Terpenoids, aldehydes, particles, quats, NH3, disinfectants
Micl. Compounds Terpenoids, aromates, aldehydes
A2 Kitchen cleaning agent Terpenoids, aldehydes, particles, quats, NH3, disinfectants
Micl. Compounds Terpenoids, aromates, aldehydes
A3 Hard surface (floor) cleaner Terpenoids, aldehydes, particles, quats, NH3, disinfectants
Terpenoids, aromates, aldehydes
A4 Glass and window cleaner Terpenoids, aldehydes, particles, quats, NH3, disinfectants
Terpenoids, aromates, aldehydes
A5 Bathroom cleaning agents Terpenoids, aldehydes, particles, quats, NH3, disinfectants
Terpenoids, aromates, aldehydes
A6 Furniture polish Terpenoids, aldehydes, particles Silanes/siloxanes Terpenoids, aromates, aldehydes
A7 Floor polish Terpenoids, aldehydes, particles Terpenoids, aromates, aldehydes
A8 Combustible air freshener Terpenoids, aldehydes, particles, aromates, CO, NO2, EC/OC, oxiPAH
A9 Air freshener (spray) Terpenoids, aldehydes, particles Terpenoids, aromates, aldehydes
Chapter 3 Ephect priority compounds
19
A10 Passive units (air freshener) Terpenoids, aldehydes, particles Terpenoids, aromates, aldehydes
A11 Electric units (air freshener, insecticide)
Terpenoids, aldehydes, particles Terpenoids, aromates, aldehydes
A12 Coating products for (hard surfaces, leather, textiles)
Terpenoids, aldehydes, particles Silanes/siloxanes Terpenoids, aromates, aldehydes
13 Hair styling products (sprays, gel)
Terpenoids, aldehydes, particles Silanes/siloxanes Terpenoids, aromates, aldehydes
A14 Deodorants (sprays) Terpenoids, aldehydes, aromates particles Terpenoids, aromates, aldehydes
15 Perfumes Terpenoids, aldehydes, aromates particles Terpenoids, aromates, aldehydes
A17 Deodorizers Terpenoids, aldehydes, particles Terpenoids, aromates, aldehydes
A18 Toys Terpenoids, aldehydes, aromates Micl. Compounds
A19 Magazines Aldehydes
The consumer product classes written in italics are not compulsory in EPHECT
Table 13 Specification of selected pollutants.
Generic name Compounds
Terpenoids limonene
-pinene
geraniol
a-terpineol linalool Aldehydes: formaldehyde acrolein
glutaraldehyde
acetaldehyde Aromates benzene
toluene
xylenes
Styrene
PAHs (naphthalene and benz-a-pyrene)
Disinfectants chloroamines hypochlorite
H2O2
CO
NO2
Ammonia
Silanes/siloxanes/polymers +/- fluorinated
Quaternary ammonium chlorides
Particles (spray and combustible products only)
Micl. compounds (not associated with respiratory diseases)
PCBs
PCDDs
Phthalates
Chapter 4 Ephect analytical methods
20
CHAPTER 4 EPHECT ANALYTICAL METHODS
4.1 Identification of the EPHECT analytical methods
For each compound to be identified, including the EPHECT priority compounds, details on the
analytical method for compound identification and quantification are established. An overview of the
methods is shown in Table 14.
Table 14 Overview of the EPHECT analytical methods
Terpenoids: Tenax TA tubes C6-C16 ISO 16000-6 limonene alpha-pinene geraniol a-terpineol linalool
TD GC MS sample max. 5 l; 20-200 ml/min column: slightly polar, (5 % phenyl / 95 % methyl poly siloxane capillary column) calibration: methanolic solution of these compounds; spike +/- 5 µl on Tenax tube n
Aldehydes: sampling on DNPH tubes; ISO 16000-3
formaldehyde acrolein glutaraldehyde acetaldehyde
check effective sampling range (Waters booklet): 50 l for 10-1000 ppb calibration with hydrazon standards analysis: HPLC-UV or DAD
Aromates:
Benzene toluene xylenes Styrene PAHs: naphthalene & benz-a-pyrene
See terpenoids ISO 16000-12: not possible for test chamber samples Alternative: PDMS/Tenax 150 ml/min – 60 min; TD-GC-MS with cold trap for high boilers
Disinfectants:
chloroamines hypochlorite (H2O2)
Hery et al. (1995) sampling on filter cassette (Teflon filter and 2 impregnated filters with As2O2 and Na2CO3); 1 l/min; 2 hours; IC; result = sum of chloroamines + ClO
-
Micl. compounds (not associated with respiratory diseases)
PCBs PCDDs Phthalates Isothiazolinones
see PAHs (Alternative: PDMS/Tenax 150 ml/min – 60 min; TD-GC-MS with cold trap for high boilers)
Chapter 4 Ephect analytical methods
21
CO
NDIR monitor method: EN 14626; or continious low cost logger Both methods need calibration
NH3
Sampling on Orbo 554 tubes (conform OSHA method ID-188 Analysis: ion selective electrode
NO2
ISO 16000-15: short term measurements; continuous analytical monitor chemo luminescence ISO7996; alternative manual photometric reference methods with impinger (Saltzman method) ISO 6768
Silanes/siloxanes/polymers +/- fluorinated
1. Sampling on tenax tubes (see terpenoids) and analysis by GC-MS/MS using both EI and CI. 2. Sampling on quartz filters (e.g. Whatman Grade GF/C - 1.2 um retention, Cat No. 1822-025). Extraction of filters by PLE and subsequent analysis of extracts by LC-MS
Quaternary ammonium chlorides (QUATs)
Sampling on quartz filters e.g. (Whatman Grade GF/C - 1.2 um retention, Cat No. 1822-025). Extraction of filters by PLE and subsequent analysis of extracts by LC-MS.
Particles (spray and combustible products only)
Primary aerosols: Optical method (Grimm), aerodynamic and electric mobility (TSI, Dekati). Size distribution, concentration or particle number Secondary aerosol filter sampling
Chapter 5 Ephect QA/QC
22
CHAPTER 5 EPHECT QA/QC
The strategy for quality control of the results obtained under EPHECT focuses on a quality control of the activities performed by laboratories that currently perform chemical analysis of air sampling. It is assumed that all the labs have an internal quality control system; however for EPHECT it is necessary to evidence this control. That will be assured by the following actions:
1) Field blanks should be performed. Before the realization of an emission test experiment a blank of the test chamber should be taken. The concentration values of the blanks should be reported.
2) The analysis of the compounds sampled on adsorbents should be performed in duplicate. For continuous monitoring (such as THC, PMx, NO2 and CO) this concept is not applicable.
It may not be feasible to sample all cartridges in duplicate, since the tests are of short duration, several cartridges should be loaded at the same time and room dimensions, thus intake air flows, may differ. It will for instance be possible to sample two Tenax tubes simultaneously, but it may then be difficult to sample two DNPH cartridges simultaneously as well, because the EPHECT emission test protocol sets a sample collection limit at maximum 80% of the total intake flow (with respect to ISO-16000-9). In such a case the one DNPH cartridge will be analyzed in duplicate. So, whenever possible, sampling and/or the analysis should be performed in duplicate; a maximum deviation of 20% between the results is allowable.
3) To control the VOCs quantification, a blind solution containing terpenes and aromatic
hydrocarbons with a certain concentration will be prepared by IDMEC, and will be sent to the other partners. IDMEC will also participate in this control, but the analysis will be done by a researcher without access to the true values.
4) To control aldehyde quantification, a blind solution containing formaldehyde, acetaldehyde,
acrolein and glutaraldehyde will be prepared by IDMEC and sent to all partners. IDMEC will also participate in this control, but the analysis will be done by a researcher without access to the true values.
For the calculation of the total uncertainty of the analysis procedure, the following formula is
proposed:
Chapter 5 Ephect QA/QC
23
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)
5) The compounds listed in Table 16b as ‘2nd level: complex’ (ammonia / Silanes / siloxanes / polymers / fluorinated and Quaternary ammonium chlorides (QUATs) / phthalates) will be sampled by the respective labs who perform the emission tests, but the analysis will be performed centrally by one selected lab (which is part of WP6). This lab is selected based on the experience and equipment of the laboratories.
For these compounds only one sample will be collected at the peak concentration. QA/QC will be performed using (C)RM if available (external).
6) Whenever applicable calibration records should be presented.
7) The heterogeneity of a products is an aspect that should be considered. Where possible, a
product test is performed in duplicate. This implies that two different product packages should be bought, and each should be subjected to an independent test. The results should be presented individually.
8) The product to be tested should be ‘new’ (the package cannot be opened, the product cannot be
used before).
9) The activities of preparation of the products to be tested shall have no or as little as possible,
impact on the integrity of the sampled product. This relates to minimising:
a) evaporation of volatile substances
b) deterioration of the product due to heat production during sampling or sub-sampling;
c) contamination of the sample(s) by the sampling devices, the other sample(s);
To control these potential influences of the preparation activities of the product, all preparatory
steps should be taken in a short period of time.
Chapter 6 Ephect Plan of work
24
CHAPTER 6 EPHECT PLAN OF WORK
The previous chapters have described (1) EPHECT protocols for test chamber experiments per
product type/package, (2) EPHECT priority compounds per product class focussing on respiratory
health, (3) EPHECT methods for sampling and analysis and (4) EPHECT methods for quality control
and assurance. This chapter combines the previous sections in one overall plan of work, distributing
the lab testing experiments and the sample analysis amongst WP6 associated partners.
6.1 Test chamber experiments of 15 product classes in 4 different labs
Table 15 shows the EPHECT consumer product classes that are analysed in the different involved
laboratories in WP6.
Table 15 Test chamber experiments of the EPHECT consumer and personal care products
NRCWE (10)
VITO (6)
UOWM (5)
IDMEC (5)
Analysed in more than 1 lab
all purpose cleaner
X X X
kitchen cleaning agent X X
floor cleaning agent X
X
X
glass and window cleaner
X
bathroom cleaning agent X
furniture polish X
X X
floor polish X
X X
combustible air fresheners
X
X
air fresheners (spray) X X
X
passive units X X
X
electric units X X
coating products X
hair styling products
X
deodorants (sprays)
x
X X
perfumes X X X
this product class is tested in all laboratories (same brand) X this product class is tested by one or a few laboratories (may be different brands)
The brand and product type selection for EPHECT lab testing experiments is based on the IPSOS
market study. This market study was part of EPHECT and took place in 4 EU regions. It led to the
identification of the most used product brand and type in all 4 regions, as well as to the identification
of the EU most used brand per product class. The following strategy will be followed:
Chapter 6 Ephect Plan of work
25
Selection of product 1: EU most used
For each EPHECT product class, the EU most used brand (according to the EPHECT IPSOS market
study) is tested applying the above specified emission test protocol, in at least one of the
involved labs.
Selection of product 2
For the majority of the products (11 out of 15; excluding glass and window cleaner, bathroom
cleaning agent, coating products, hair styling spray), a second product brand is tested, applying
the above specified emission test protocol. This second product is then the brand, which
according to the IPSOS market study, is most used in the region of the analysing lab.
Inter-lab study
For 3 product classes (kitchen cleaning agent, electric air freshener, and perfume), the same
product brand and type is exchanged and tested in all 4 involved laboratories, allowing a
comparison of the emission test results within the participating labs.
Complementary to the lab testing experiment to assess the product emissions, TUM is responsible
for quantification of selected compounds (terpenoids, aromates and aldehydes) in 15 of the tested
liquid products.
In agreement with the available techniques in the 4 involved laboratories, the analysis of the
compounds that have to be identified and/or quantified is distributed between the different involved
laboratories. Table 16 shows this work division sheet, which clarifies whether samples are analysed in
the laboratory where the experiment took place, or is sent to another laboratory that is responsible
for the analysis of the samples from the whole team.
6.2 Translation into an operational plan of work
Combining Tables 12 and 13 on key and emerging pollutants expected to be present in the tested
consumer products, together with the work division and QA/QC (table 16) as well as the EPHECT
emission test umbrella, a detailed operational plan of work for consumer product emission testing
can be formulated for each product class.
This plan of work then schedules the successive sampling phases during each emission test
experiment and specifies the different samples to be collected in each phase; adapted to the
preconditions of each laboratory (test chamber dimensions and related total intake flow). An
example of the operational plan for the VITO lab testing experiments on spray type consumer
products (types A9, A13 and A14) is shown in Figure 4. Each lab has developed an operational plan of
work, adapted to their emission test chamber dimensions (with respect to the EPHECT umbrella
start-up condition on a sample collection limit smaller than 80% of the intake flow) and their
chamber facilities to collect samples.
Chapter 6 Ephect Plan of work
26
Figure 3 Operational plan of work for spray consumer product testing at VITO
6.3 Reporting data for BUMAC imputation
Data generated in WP6 are not only used in WP7 for details exposure and health risk assessment. All
emission data, generated in this work package, are included in BUMAC. Therefore, the emission data
and experimental details are collected in datasheets, per product class tested. An example of the
datasheet is shown in Table 16.
Chapter 6 Ephect Plan of work
27
Table 16 EPHECT work division sheet
Complexity of the analysis
QA/QC EPHECT key, gap and emerging pollutants
# samples per
product
NCRWE (1) VITO (2) UOWM (3) IDMEC (4)
Sampling Analysis Sampling Analysis Sampling Analysis Sampling Analysis
Basic Terpenoids:
limonene 4 (1) (1) (2) (2) (3) (3) (4) (4)
level 1 duplicate collection - max 20% deviation
alpha-pinene 4 (1) (1) (2) (2) (3) (3) (4) (4)
level 2 (C)RM (external) geraniol 4 (1) (1) (2) (2) (3) (3) (4) (4)
a-terpineol 4 (1) (1) (2) (2) (3) (3) (4) (4)
linalool 4 (1) (1) (2) (2) (3) (3) (4) (4)
Aldehydes:
formaldehyde 4 (1) (1) (2) (2) (3) (3) (4) (4)
acrolein 4 (1) (1) (2) (2) (3) (3) (4) (4)
glutaraldehyde 4 (1) (1) (2) (2) (3) (3) (4) (4)
acetaldehyde 4 (1) (1) (2) (2) (3) (3) (4) (4)
Aromates:
benzene 4 (1) (1) (2) (2) (3) (3) (4) (4)
toluene 4 (1) (1) (2) (2) (3) (3) (4) (4)
xylenes 4 (1) (1) (2) (2) (3) (3) (4) (4)
styrene 4 (1) (1) (2) (2) (3) (3) (4) (4)
PAHs: naphthalene 4 (1) (1) (2) (2) (3) (3) (4) (4)
Chapter 6 Ephect Plan of work
28
Complexity of the analysis
QA/QC EPHECT key, gap and emerging pollutants
# samples per product
NCRWE (1) VITO (2)
UOWM (3) IDMEC (4)
Particles (spray and combustible products only)
Primary aerosols (analysed in real time by FMPS,
SMPS, dust monitors etc.)
(1) (1) (2) (2) (3) (3) (4) (4)
Secondary aerosols (filter sampling)
(1) (1) (2) (2) (3) (3) (4) (4)
Complex 1 lab for analysis Disinfectants: chloroamines 1 (@peak) (1) (2) (2) (2) (3) (2) (4) (2) level 1 (C)RM if available
(external) hypochlorite 1(@peak) (1) (2) (2) (2) (3) (2) (4) (2)
(H2O2) 1
Micl. compounds (not respiratory health)
(PCBs) 1
(PCDDs) 1
on PDMS tenax Phthalates benz-a-pyrene
1 (1) (1) identification
(2) quantification
(2) (2) (3) (2) (4) (2)
Isothiazolinones 1
CO - - - - - - (4) (4)
CRM NO2 - - - - - - (4) (4)
Ammonia (1) (4) (2) (4) (3) (4) (4) (4)
Silanes/siloxanes/polymers +/- fluorinated
(1) (1) (2) (1) (3) (1) (4) (1)
Quat. ammonium chlorides (QUATs) (1) (1) (2) (1) (3) (1) (4) (1)
VOC Identification&analysis
1 (3/4 samples)
(1) (1) (2) (1) (3) (1) (4) (1)
Chapter 6 Ephect Plan of work
29
Chapter 6 Ephect Plan of work
30
Figure 4 Datasheet for WP6 emission data
References
31
REFERENCES
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(2) Thrasher JD, Madison R, Broughton A, Gard Z. Building-related illness and antibodies to albumin conjugates of formaldehyde, toluene diisocyanates, and trimellitic anhydride. American Journal of Industrial Medicine 1989;15:187-95.
(3) Dales R, Raizenne M. Residential exposure to volatile organic compounds and asthma. Journal of Asthma 2004;41:259-70.
(4) van Kampen V, Merget R, Baur X. Occupational air sensitizers: an overview on the respective literature. Am J Ind Med 2000;38:164-218.
(5) Jaakkola JJK, Knight TL. The role of exposure to phthalates from polyvinyl chloride products in the development of asthma and allergies: A systematic review and meta-analysis. Environ Health Perspec 2008;116:845-53.
(6) Multigner L, Catala M, Cordier S, Delaforge M, Fenaux P, Garnier R, et al. The INSERM expert review on glycol ethers: findings and recommendations. Toxicol Lett 2005;156:29-37.
(7) SCOEL. Recommendation from the Scientific Committee on Occupational Exposure Limits for 2-Ethoxyethanol and 2-Ethoxyethyl acetate. 2007. Report No.: SCOEL/SUM/116.
(8) International Agency for Research on Cancer (IARC). Formaldehyde, 2-Butoxyethanol and 1-tert-Butoxypropanol-2-ol. [88], 1-325. 2006. Lyon, World Health Organization. Monographs on the Evaluation of Carcinogenic Risks to Humans. Ref Type: Serial (Book,Monograph)
(9) Choi H, Schmidbauer N, Spengler J, Bornehag C-G. Sources of propylene glycol and glycol ethers in air at home. Int J Environ Res Public Health 2010;7:4213-37.
(10) Nazaroff WW, Weschler CJ. Cleaning products and air fresheners. Exposure to primary and secondary pollutants. Atmospheric Environment 2004;38:2841-65.
(11) Wolkoff P, Wilkins CK, Clausen PA, Nielsen GD. Organic compounds in office environments - Sensory irritation, odor, measurements, and the role of reactive chemistry. Indoor Air 2006;16:7-19.
(12) golden R. Identifying an indoor air exposure limit for formaldehyde considering both irritation and cancer hazards. Critical Reviews in Toxicology 2011;41:672-721.
(13) Heinrich J. Influence of indoor factors in dwellings on the development of childhood asthma. Int J Hyg Environ Health 2011;214:1-25.
(14) Wolkoff P, Nielsen GD. Non-cancer effects of formaldehyde and relevance for setting an indoor air guideline. Environ Int 2010;36:788-99.
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(15) Quirce S, Barranco P. Cleaning agents and asthma. J Invest Allergol Clin Immunol 2010;20:542-50.
(16) Mapp CE, Boschetto P, Maestrelli P, Fabbri LM. Occupational asthma. Am J Respir Crit Care Med 2005;172:280-305.
(17) Zock JP, Vizcaya D, Le Moual N. Update on asthma and cleaners. Curr Opin Allergy and Clin Immunol 2010;10:114-20.
(18) Kephalopoulos S, Kotzias D, Koistinen K, Carslaw N, Carrer P, Fossati S, et al. Impact of ozone-initiated terpene chemistry on indoor air quality and human health. EUR 23052 EN ed. Luxembourg: Office for official publications of the European Communities; 2007.
(19) Forester CD, Wells JR. Yields of carbonyl products from gas-phase reactions of fragrance compounds with OH radical and ozone. Environ Sci Technol 2009;43:3561-8.
(20) Wolkoff P, Clausen PA, Wilkins CK, Nielsen GD. Formation of strong airway irritants in terpene/ozone mixtures. Indoor Air 2000;10:82-91.
(21) Oberdörster G, Oberdörster E, Oberdörster J. Nanotoxicology: An emerging discipline evolving from studies of ultrafine particles. Environ Health Perspec 2005;113:823-39.
(22) Nørgaard AW, larsen ST, Hammer M, Poulsen.S.S., Jensen KA, Nielsen GD, et al. Lung damage in mice after inhalation of nanofilm spray products: The role of perfluorination and free hydroxyl groups. Toxicological Sciences 2010;116:216-24.
(23) Pauluhn J, Hahn A, Spielmann H. Assessment of early acute lung injury in rats exposed to aerosols of consumer products: Attempt to disentangle the "magic nano" conundrum. Inhalation Toxicology 2008;20:1245-62.
(24) Vernez D, Bruzzi R, Kupferschmidt H, De-Batz A, Droz P, Lazor R. Acute respiratory syndrome after inhalation of waterproofing sprays: A posteriori exposure-response assessment in 102 cases. Journal of Occupational and Environmental Hygiene 2006;3:250-61.
(25) Kotzias D. The INDEX project - Critical appraisal of the setting and implementation of indoor exposure limits in the EU. Ispra (VA), Italy: European Commission, Directorate General, Joint Research Centre; 2005.
(26) World Health Organization. Selected pollutants. WHO indoor air quality guidelines. Copenhagen: WHO Regional Office for Europe; 2010.
(27) World Health Organization. Air Quality Guidelines for Europe. 2 ed. Copenhagen: World Health Organization, Regional Office for Europe; 2000.
(28) Scientific Committee on Health and Environmental Risks (SCHER). Opinion on risk assessment on indoor air quality. Brussels: European Commission: Health & Consumer Protection Directorate-General; 2007 May 29.
(29) Hahn S, Schneider K, Gartiser S, Heger W, Mangelsdorf I. Consumer exposure to biocides - identification of relevant sources and evaluation of possible health effects. Environ Health 2010;9:7.
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(30) Bondi CAM. Applying the precautionary principle to consumer household cleaning product development. J Clean Prod 2011;19:429-37.
(31) Borm PJA, Kelly FJ, Künzli N, Schins RPF, Donaldson K. Oxidant generation by particulate matter: from biologically effective dose to a promising, novel metric. Occup Environ Med 2007;64:73-4.
(32) Salthammer T. Environmental Test Chambers and Cells. Part 1 - Chapter 5 in Organic Indoor Air Pollutants. Uhde E. and Salthammer T., Wiley-VCH, 2009, sec. edition.
Derudi M., Gelosa S., Sliepcevich A., CattaneoA. Rota R., Cavallo D., Nano G. Emissions of air pollutants from scented candles burning in a test chamber. Atmos Environ 55; 257-262: 2012
ASTM D6670-01 (2007) Standard practice for full-scale chamber determination of volatile organic emissions from indoor materials/products
Hery et al (1995) "Exposure to Chloramines in the Atmosphere of Indoor Swimming Pools" Annals of Occupational Hygiene 39(4), 427-439
Appendix 1 Literature compilation Appendix 2 Complete list of key and emerging compounds
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
This report arises from the project EPHECT which has received funding from the European Union, in the framework of the Health Programme.
“© IDMEC, UMil, UOWM All rights on the materials described in this document rest with IDMEC, UMil and UOWM. 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
Chapter 2 Description
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.
Chapter 2 Description
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
Detailed substance classes and allergenic compounds Detailed substance classes and allergenic compounds
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
Detailed substance classes and allergenic compounds
IL and MSDS available online IL contains allergenic comp.
n.a.
(23) Deodorant spray 2
Detailed substance classes and allergenic compounds
MSDS online available n.a.
Perfumes (24)
(25)
Perfume 1 Perfume 2
Detailed substance classes and allergenic compounds Detailed substance classes and allergenic compounds
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
Chapter 2 Description
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
Chapter 2 Description
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”.
Chapter 2 Description
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.
Chapter 2 Description
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.
Chapter 2 Description
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).
Chapter 2 Description
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..
Chapter 2 Description
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
Chapter 2 Description
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
Chapter 2 Description
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
Chapter 3 Consumer product emission testing
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
Chapter 3 Consumer product emission testing
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.
Chapter 3 Consumer product emission testing
18
3.2 Emission testing at NRCWE
3.2.1 Laboratory facilities
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.
Chapter 3 Consumer product emission testing
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.
Chapter 3 Consumer product emission testing
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.
3.2.2 Use scenario simulations
Used quantities
All tested products have been weighted before and after the experiments, outside the test chamber.
The amount applied was in accordance with the recommended prescription for the product.
Bringing the product in the test room
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.
Chapter 3 Consumer product emission testing
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
3.3.1 Laboratory facilities
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)
Chapter 3 Consumer product emission testing
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.
Chapter 3 Consumer product emission testing
23
3.3.3 Use scenario simulations
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.
Bringing the product in the test room
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.
Chapter 3 Consumer product emission testing
24
3.4 Emission testing at UOWM
3.4.1 Laboratory facilities
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.
Chapter 3 Consumer product emission testing
25
3.4.3 Use scenario simulations
Used quantities
All tested products have been weighted before and after the experiments, outside the test chamber.
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.
Bringing the product in the test room
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
Chapter 4 Intercomparison experiment and QA/QC in Ephect
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
Air exchange rate, h-1
0.5 0.5 0.5 0.87
Temperature, C 23 23 23 23
Rel Humidity, % 18 50 50 55 Air velocity, cm/s 0.05 30 9 16 Amount used, g 0.4 0.266 0.479 0.64 Amount per vol, g/m
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
Air exchange rate, h-1
0.5 0.5 0.5 0.84
Temperature, C 23 23 23 22
Rel Humidity, % 18 50 50 51 Air velocity, cm/s 0.05 30 9 13 Amount used, g 0.2 0.063 0.156 0.1 Amount per vol, g/m
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:
Chapter 4 Intercomparison experiment and QA/QC in Ephect
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
Chapter 4 Intercomparison experiment and QA/QC in Ephect
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%.
Chapter 4 Intercomparison experiment and QA/QC in Ephect
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
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 1,9 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
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 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
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 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
Chapter 4 Intercomparison experiment and QA/QC in Ephect
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
Chapter 4 Intercomparison experiment and QA/QC in Ephect
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.
Chapter 4 Intercomparison experiment and QA/QC in Ephect
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
Chapter 4 Intercomparison experiment and QA/QC in Ephect
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.
Chapter 4 Intercomparison experiment and QA/QC in Ephect
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).
Chapter 4 Intercomparison experiment and QA/QC in Ephect
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
IDMEC – 1 0.26 0.12 0.06 0.88 0.86 130.32 - 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 - - - -
VITO – 2 0.92 0.4 0.3 0.5 1.73 393.34 - Nearly instantaneous (k > 4 [h-1]) - < 0.5
IDMEC – 2 0.26 0.06 0.06 0.88 0.91 151.76 - Nearly instantaneous (k > 4 [h-1]) - < 0.5
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
IDMEC – 3 0.26 0.12 0.06 0.88 1.45 239.05 - Nearly instantaneous (k > 4 [h-1]) - < 0.5
NRCWE – 3 20.24 2 0.0005 0.6 42.04 125.26 - Nearly instantaneous (k > 4 [h-1]) - < 0.5
NRCWE – 4 20.24 1 0.0005 0.6 20.3 135.87 - 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
IDMEC – 0 0.26 0.12 0.12 0.86 0.81 337.04 - Nearly instantaneous (k > 4 [h-1]) - < 0.5
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
VITO – 0 0.92 0.37 0.3 0.5 0.43 193.52 - Nearly instantaneous (k > 4 [h-1]) - < 0.5
IDMEC – 1 0.26 0.12 0.06 0.88 0.86 496.65 - Nearly instantaneous (k > 4 [h-1]) - < 0.5
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 - - - -
VITO – 1 0.92 0.3 0.3 0.5 1.33 737.57 - Nearly instantaneous (k > 4 [h-1]) - < 0.5
IDMEC – 2 0.26 0.06 0.06 0.88 0.91 539.59 - Nearly instantaneous (k > 4 [h-1]) - < 0.5
NRCWE – 2 20.24 1 0.0005 0.6 39.8 368.35 - Nearly instantaneous (k > 4 [h-1]) - < 0.5
UOWM – 2 0.05 0.01 0.09 0.56 0.2288 8.52 7.7 - 1.19 (7.17) > 7.17
VITO – 2 0.92 0.4 0.3 0.5 1.73 707.69 - Nearly instantaneous (k > 4 [h-1]) - < 0.5
Chapter 4 Intercomparison experiment and QA/QC in Ephect
38
IDMEC – 3 0.26 0.12 0.06 0.88 1.45 585.31 - Nearly instantaneous (k > 4 [h-1]) - < 0.5
NRCWE – 3 20.24 2 0.0005 0.6 42.04 320.88 - Nearly instantaneous (k > 4 [h-1]) - < 0.5
UOWM – 3 0.05 0.015 0.09 0.56 0.07 5.34 1.67 1.67*exp(-0.31t) - ~6.5
VITO – 3 0.92 0.3 0.3 0.5 1.94 578.85 - Nearly instantaneous (k > 4 [h-1]) - < 0.5
NRCWE – 4 20.24 1 0.0005 0.6 20.3 380.79 - Nearly instantaneous (k > 4 [h-1]) - < 0.5
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
Chapter 4 Intercomparison experiment and QA/QC in Ephect
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.
Chapter 4 Intercomparison experiment and QA/QC in Ephect
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
A synopsis of the experimental setup parameterization and the emission results are given in
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
IDMEC – 1 0.26 0.13 0.84 0.1 29.3 - 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
IDMEC – 0 0.26 0.13 0.91 0.07 1082.95 - Nearly instantaneous (k > 4 [h-1]) - < 0.5
IDMEC – 1 0.26 0.13 0.84 0.1 826.44 - Nearly instantaneous (k > 4 [h-1]) - < 0.5
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 – 0 0.26 0.13 0.91 0.07 3150.24 - Nearly instantaneous (k > 4 [h-1]) - < 0.5
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
A synopsis of the experimental setup parameterization and the emission results are given in
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%
* calculated with response factor of toluene
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%
* calculated with response factor of toluene
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%
* calculated with response factor of toluene
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
partner A partner B partner C partner D
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
partner A partner B partner C partner D
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
partner A partner B partner C partner D
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 (%)
Acrolein Result (g/g) Reference
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 (%)
Acrolein Result (g/g) Reference
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 (%)
Acrolein Result (g/g) Reference
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.
Chapter 5 Ephect consumer product emission tests
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
Chapter 5 Ephect consumer product emission tests
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).
Chapter 5 Ephect consumer product emission tests
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
Chapter 5 Ephect consumer product emission tests
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)-
99-85-4 0,03 semi-quant. Other terpene HC
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
Limonene 138-86-3 81,6 quant. X
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
beta-phellandrene 555-10-2 0,03 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
CAS-number Concentration [µg/m³]
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
Chapter 5 Ephect consumer product emission tests
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
Concentration [µg/m³]
Explicitly in AgBB
Group named in AgBB
Limonene 138-86-3 145 quant. X
β-Pinene 127-91-3 14,1* quant. X
α-pinene 80-56-8 5,66 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
alpha-phellandrene 99-83-2 0,17 semi-quant. Other terpene HC
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
Concentration [µg/m³]
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
CAS-number Concentration [µg/m³]
Explicitly in AgBB
Group named in AgBB
Limonene 138-86-3 10,9 quant. X
cyclotetrasiloxane, octamethyl- 556-67-2 3,6 semi-quant. X
Chapter 5 Ephect consumer product emission tests
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
CAS-number Concentration [µg/m³]
Explicitly in AgBB
Group named in AgBB
Limonene 138-86-3 61,3 quant. X
propylene glycol 57-55-6 2,0 semi-quant. X
benzene,1-methyl-3-
(1methylethyl)- 535-77-3 1,9 semi-quant.
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
1,3,7-octatriene,3,7-dimethyl- 502-99-8 0,4 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
camphene 79-92-5 0,0 semi-quant. Other terpene HC
Table 42 AgBB compounds in the emission test room when testing perfume (in a 0,913 m³ room) ; sample 0-30 min.
Perfume compound
CAS-number Concentration [µg/m³]
Explicitly in AgBB
Group named in AgBB
Limonene 138-86-3 67,2 quant. X
β-Pinene 127-91-3 20,3 quant. X
1,4-cyclohexadiene,1-methyl-4-(1-
methylethyl)- 99-85-4 1,02 semi-quant.
Other terpene HC
benzene,1-methyl-3-
(1methylethyl)- 535-77-3 0,60 semi-quant.
X
1-hexanol,2-ethyl- 104-76-7 0,51 semi-quant. X
1,3,7-octatriene,3,7-dimethyl- 502-99-8 0,48 semi-quant. Other terpene HC
camphene 79-92-5 0,02 semi-quant. Other terpene HC
Chapter 5 Ephect consumer product emission tests
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
CAS-number Concentration [µg/m³]
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
1,4-cyclohexadiene,1-methyl-4-(1-
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
camphene 79-92-5 67,9 semi-quant. Other terpene HC
beta-phellandrene 555-10-2 64,0 semi-quant. Other terpene HC
hexanal 66-25-1 46,8 semi-quant. X
3-carene 498-15-7 29,1 quant. X
alpha-phellandrene 99-83-2 16,7 semi-quant. Other terpene HC
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
Concentration [µg/m³]
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
1,3,7-octatriene,3,7-dimethyl- 502-99-8 167 semi-quant. Other terpene HC
β-Pinene 127-91-3 132 quant. X
1,4-cyclohexadiene,1-methyl-4-(1-methylethyl)- 99-85-4 129 semi-quant.
Other terpene HC
α-pinene 80-56-8 75,0 quant. X
beta-phellandrene 555-10-2 72,7 semi-quant. Other terpene HC
benzylalcohol 100-51-6 45,9 semi-quant. X
3-carene 498-15-7 21,8* quant. X
alpha-phellandrene 99-83-2 16,2 semi-quant. Other terpene HC
benzaldehyde 100-52-7 12,2 semi-quant. X
camphene 79-92-5 7,5 semi-quant. Other terpene HC
Isobutylacetate 110-19-0 5,0 semi-quant. X
Chapter 5 Ephect consumer product emission tests
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
Concentration [µg/m³]
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
camphene 79-92-5 80,8 semi-quant. Other terpene HC
β-Pinene 127-91-3 31,9 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)- 99-85-4 21,5 semi-quant.
Other terpene HC
α-pinene 80-56-8 17,2 quant. X
Limonene 138-86-3 14,8 quant. 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 475-20-7 5,7 semi-quant.
Other terpene HC
1-butoxypropanol 5131-66-8 2,0 semi-quant. X
Chapter 5 Ephect consumer product emission tests
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.
Chapter 5 Ephect consumer product emission tests
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
β-Pinene 127-91-3 276 quant. 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
1,3,7-octatriene,3,7-dimethyl- 502-99-8 107 semi-quant. Other terpene HC
camphene 79-92-5 67,9 semi-quant. Other terpene HC
beta-phellandrene 555-10-2 64,0 semi-quant. Other terpene HC
hexanal 66-25-1 46,8 semi-quant. X
3 - Carene 498-15-7 29,1 quant. X
alpha-phellandrene 99-83-2 16,7 semi-quant. Other terpene HC
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.
Chapter 5 Ephect consumer product emission tests
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
1,3,7-octatriene,3,7-dimethyl- 502-99-8 167 semi-quant. Other terpene HC
β-Pinene 127-91-3 132 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.
beta-phellandrene 555-10-2 72,7 semi-quant. Other terpene HC
benzylalcohol 100-51-6 45,9 semi-quant. X
3-carene 498-15-7 21,8 quant.* X
alpha-phellandrene 99-83-2 16,2 semi-quant. Other terpene HC
benzaldehyde 100-52-7 12,2 semi-quant. X
camphene 79-92-5 7,5 semi-quant. Other terpene HC
Isobutylacetate 110-19-0 5,0 semi-quant. X
TVOC 28.859 semi-quant.
* standard deviation of more than 20%
Chapter 5 Ephect consumer product emission tests
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
camphene 79-92-5 80,8 semi-quant. Other terpene HC
β-Pinene 127-91-3 31,9 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)-
99-85-4 21,5 semi-quant. Other terpene HC
α-pinene 80-56-8 17,2 quant. X
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
475-20-7 5,7 semi-quant. Other terpene HC
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
Chapter 6 Conclusion quantification of product emissions by laboratory testing
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”.
Chapter 6 Conclusion quantification of product emissions by laboratory 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.
Laboratory Sampling period, min
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.
Laboratory Sampling period, min
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
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]
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
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]
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
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]
bathroom cleaning agent VITO
NRCWE 20,24 0,5 7,80 0,4 178 4 31 6 9.680 -
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]
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
102