literature review on, product composition ... - europa
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LITERATURE REVIEW ON, PRODUCT
COMPOSITION, EMITTED COMPOUNDS
AND EMISSIONS RATES AND HEALTH END
POINTS FROM CONSUMER PRODUCTS
AUTHORS UOWM: DAFNI MISSIA, TASSOS KOPANIDIS, JOHN BARTZIS IDMEC: GABRIELA VENTURA SILVA, EDUARDO DE OLIVEIRA FERNANDES UMIL: PAOLO CARRER NRCWE: PEDER WOLKOFF VITO: MARIANNE STRANGER, EDDY GOELEN WP 4 LEADER: UOWM Kozani September 2010 (rev. Sept 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
EPHECT associated partners
EPHECT collaborative partners
Reviewed by AISE
Table of contents
4
TABLE OF CONTENTS
DISTRIBUTION LIST ......................................................................................................... 3
TABLE OF CONTENTS...................................................................................................... 4
1. INTRODUCTION .......................................................................................................... 7
2. CONSUMER PRODUCTS CLASSIFICATION AND CHARACTERISTICS ............................ 9 2.1. Definition of consumer products ................................................................................................... 9 2.2. Electronic equipment .................................................................................................................. 11
2.2.1. Personal computers ................................................................................... 11
2.2.2. Printers and faxes ...................................................................................... 12
2.2.3. TV sets ........................................................................................................ 12
2.2.4. Mobile phones ........................................................................................... 12
2.2.5. Other (games, converters, etc.) ................................................................. 12 2.3. Appliances ................................................................................................................................... 12
2.3.1. Gas cooking appliances .............................................................................. 12
2.3.2. Washing machines ..................................................................................... 13
2.3.3. Vacuum cleaners ........................................................................................ 13
2.3.4. Air conditioning and humidifying systems................................................. 13 2.4. Fireplaces .................................................................................................................................... 13
2.4.1. Stoves and gas, oil- fired and ethanol furnaces ......................................... 13
2.4.2. Kerosene space heaters ............................................................................. 14 2.5. Household products .................................................................................................................... 15
2.5.1. Laundry detergents .................................................................................... 15
2.5.2. Floor cleaning products ............................................................................. 16
2.5.3. Polishing products ...................................................................................... 17
2.5.4. Carpet cleaners .......................................................................................... 18
2.5.5. Dishwashing products ................................................................................ 19
2.5.6. All purpose hard surface cleaners ............................................................. 20
2.5.7. Sanitary cleaners ........................................................................................ 22
2.5.8. Glass cleaners ............................................................................................. 23
2.5.9. Oven cleaners ............................................................................................ 24
2.5.10. Spot removers .......................................................................................... 24
2.5.11. Metal cleaners ......................................................................................... 24
2.5.12. Drain openers........................................................................................... 25
2.5.13. Shoe polishers .......................................................................................... 25 2.6. Air fresheners .............................................................................................................................. 26 2.7. Pest control ................................................................................................................................. 28 2.8. Clothes and fabrics ...................................................................................................................... 31 2.9. Personal care products ............................................................................................................... 33
2.9.1. Bathing and showering products ............................................................... 34
2.9.2. Hair care products ...................................................................................... 36
2.9.3. Skin care products ...................................................................................... 41
2.9.4. Oral hygiene products ................................................................................ 51
2.9.5. Feet care products ..................................................................................... 52
2.9.6. Baby care products .................................................................................... 52
2.9.7. Fragrances .................................................................................................. 53
Table of contents
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2.9.8. Deodorants ................................................................................................ 54 2.10. Printed material ........................................................................................................................ 56 2.11. Toys ........................................................................................................................................... 57 2.12. Pet care products ...................................................................................................................... 58 2.13. Flowers and plants .................................................................................................................... 59 2.14. Decoration and maintenance ................................................................................................... 59
3. HEALTH RELEVANT EMITTED COMPOUNDS ............................................................ 61 3.1. Criteria for choosing the targeted compounds ........................................................................... 61 3.2. Key emission substances with potential health relevant impact ................................................ 64
3.2.1. Introduction ............................................................................................... 64
3.2.2. Indoor air chemistry ................................................................................... 67 3.3. Brief overview of respiratory effects associated with handling of consumer products within air fresheners, cleaning and maintenance products ............................................................................... 68 3.4. Conclusions ................................................................................................................................. 77 3.5. Brief overview of particle emissions and associated respiratory effects from handling of consumer products within air fresheners, cleaning and maintenance products ............................... 79 4.1. Electronic equipment .................................................................................................................. 89 4.2. Appliances ................................................................................................................................... 93 4.3. Fireplaces .................................................................................................................................... 95 4.4. Household products .................................................................................................................... 97
4.4.1. All purpose cleaners (gel, liquid, tissue, cream) ...................................... 101
4.4.2. Kitchen cleaning agents (liquid, spray, tissues) ....................................... 105
4.4.3. Hard surface (floor) cleaner (powder, spray, gel, disinfectants) ............. 107
4.4.4. Glass and window cleaner (Liquid, spray, tissues) .................................. 109
4.4.5. Bathroom cleaning agents (liquid, sprays, tissues) ................................. 111
4.4.6. Furniture polishes (liquid, spray, tissues) ................................................ 115
4.4.7. Floor polishes (liquid, spray, tissues) ....................................................... 117
4.4.8. Oven cleaners .......................................................................................... 122 4.5. Air fresheners ............................................................................................................................ 122
4.5.1. Combustible air fresheners ...................................................................... 124
4.5.2. Air fresheners (spray) ............................................................................... 132
4.5.3. Passive units (air fresheners) ................................................................... 134
4.5.4. Ethereal oils ............................................................................................. 135
4.5.5. Pluged-in units ......................................................................................... 139 4.6. Pests control ............................................................................................................................. 140
4.6.1. Electric units (insecticide tablets, air fresheners) .................................... 140 4.7. Clothes and fabrics .................................................................................................................... 141
4.7.1. Coating products for (hard surfaces, leather, textiles) ............................ 142
4.7.2. Fabric deodorisers ................................................................................... 143 4.8. Personal care products ............................................................................................................. 143
4.8.1. Hair styling products (spray, gels etc.) ..................................................... 144
4.8.2. Deodorants (sprays) ................................................................................. 147
4.8.3. Perfumes .................................................................................................. 151 4.9. Printed material ........................................................................................................................ 153 4.10. Toys ......................................................................................................................................... 154 4.11. Pet care products .................................................................................................................... 158 4.12. Flowers and plants .................................................................................................................. 158 4.13. Decoration and maintenance ................................................................................................. 158
5. CONSUMER PRODUCTS : EPHECT PRIORITY VERIFICATION .................................. 160
6. CONSUMER PRODUCTS SELECTION FOR EPHECT .................................................. 165
References ................................................................................................................. 167
Table of contents
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APPENDIX I ................................................................................................................. 194
7
1. INTRODUCTION
Each human activity is related to emissions of chemicals into the air. In an
industrialized society, the majority of the population spends more than 90% of the
time indoors. Indoor air pollution may be becoming worse due to certain recent
initiatives to conserve energy. One common method is to make buildings more
energy-efficient to "weatherize" them by sealing them off, as tightly as possible.
Preliminary research suggests that concentrations of at least some indoor air
pollutants vary proportionately with the ventilation rate; thus, decreasing the
ventilation rate by a factor of five may increase concentrations of indoor air
pollutants by the same factor. Given these increased concentrations, the current
trend towards sealing off homes in order to conserve energy, may have serious
health consequences. Even this estimate is subject to significant variations based on
the chosen lifestyle of the population groups, climatologically determined
constrictions, and, most importantly, the age and health status of the individuals.
Elderly with poor health and very young children spend virtually most of their time
indoors. In some cases, a further complicating factor is that they may live in certain
restricted localities within the dwelling more than the healthy persons do.
The sources of indoor contaminants that may affect human health could be divided
into three general categories which, in turn, could be further subdivided. The general
source categories are: (1) infiltration of outdoor air (2) indoor human activities, and
(3) building materials and furnishing. Regarding category (2), contaminants emitted
by human activities, include many classes of consumer products used for personal
care, cleaning, deodorizing, pest management, building maintenance and office
work. Furthermore, devices, such as gas stoves, furnaces and fireplaces, commonly
present in residents, are known as emitters of air pollutants, such as VOCs, CO and
NOx [COSI, 2005].
To assess the population exposure to indoor sources, additional information is
needed, such as duration of daily use of a product, duration of contact-time,
frequency of use, and percentage of prevalence [COSI, 2005]. Generally, exposure
assessment for consumers aims at two groups:
those who use these products and experience the highest exposure and
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those who are exposed after application (e.g. children and especially the
youngest ones may be relatively high exposed, due to their specific time-
activity pattern like crawling on treated surfaces, hand-to-mouth contact, and
relatively low body weight).
The ability of organic chemicals to cause health effects varies greatly, from those
that are highly toxic (e.g. benzene and formaldehyde), to those with no known
health effects. As with other pollutants, the extent and nature of the health effects
will depend on many factors including level of exposure and length of exposure
duration. There are indications that the reaction products of organic pollutants (e.g.
terpenes) may have an impact on comfort and health, but the magnitude of these
effects and their frequency need to be elucidated (ECA, 2007). In addition, a number
of studies in indoor environments suggest that such oxidative reactions may be
associated with adverse health effects (Weschler et al., 2006; Wolkoff et al., 2006).
The sensory irritation (eyes and airways) and inflammation potential of the
ozonolysis products has been studied using a mouse bioassay (Clausen et al., 2001;
Rohr et al., 2002; Wilkins et al., 2001; Wolkoff et al., 1999) and a human eye
exposure model (Nøjgaard et al., 2005).
This report aims at the formulation of an inventory of the necessary scientific basis
on the main consumer product categories, needed to make an estimate of the
exposure risks for the consumer due to using products.
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2. CONSUMER PRODUCTS CLASSIFICATION AND CHARACTERISTICS
2.1. Definition of consumer products
What is a consumer product? This question is essential as for the scope of this
project well defined boundaries have to be set between consumer products and
construction materials/ products.
The Construction Product Directive (CPD), defines as construction product any
product which is produced for incorporation in a permanent manner in construction
works, including both buildings and civil engineering works Additionally, in the
Statements for the Entry into the Minutes, the Council and the Commission stated
that for the purposes of clarification in certain languages, it should be noted that
construction products also include installations and equipment and parts thereof for
heating, air conditioning, ventilation, sanitary purposes, electrical supply, and storage
of substances harmful to the environment, as well as prefabricated construction
works which are marketed as such, for example prefabricated houses, prefabricated
garages and silos. This is a border line in order to exclude some products.
According to the Directive 2001/95/EC, on general product safety, a consumer
product is defined as any product placed on the market, or otherwise supplied or
made available to consumers, intended for consumers, or likely to be used by
consumers under reasonably foreseeable conditions even if not intended for them.
The United States Consumer Product Safety Act gives an extensive definition for the
consumer products: according to them it is any article, or component part thereof,
produced or distributed
(i) for sale to a consumer in order to be used in or around a permanent or
temporary household or residence, a school, in recreation, or otherwise,
or
(ii) for the personal use, consumption or enjoyment of a consumer in or
around a permanent or temporary household or residence, a school, in
recreation, or otherwise.
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Consumer products are an extremely diverse category of products. A definition of
consumer products is limited to expendable products in small containers which are
readily available in retail outlets. In this context, consumer products are items such
as cleaning/ polishing products, insecticides, painting/ finishings/ refinishing
products, personal care products, hobbyists’ products, and deodorizers/disinfectants.
Therefore, a definition that will be used for the EPHECT Project is the following:
Consumer products are defined as any article chemically formulated, used in a
non-permanent way in indoor environments, and intended for housekeeping or
personal care activities or enjoyment. Such products may include: electronic
equipment, appliances, fireplaces, household products like laundry and dish washer
detergents, cleaning products and polishers, air fresheners, pest control products,
clothes and fabrics, personal care products such as showering, perfumes, hair and
skin care products, nail polishers etc., printed material, toys, pet care products,
flowers and plants, decoration and maintenance.
It must however been noted that according to the DG Sanco project call EPHECT
focusses on “…consumer products such as personal care and cleansing products,
…on the user pattern of these products in EU Member States”. Furthermore, in the
approved EPHECT project proposal it was stated that “… the following product
classes might be selected: personal care products, air fresheners, cleaning agents
and sprays”. In spite of the predefined scope, this literature review as well as the
selection procedure of the 15 relevant consumer product classes for EPHECT,
includes and evaluates available data on compositions, emissions and emission
factors of all consumer products enclosed in the EPHECT definition of consumer
products. The information on this wider range of products in the literature review is
included in BUMAC. Therefore, this leads to a more complete and thus more usable
BUMAC database in various current and future studies on consumer product
emissions. To select the 15 EPHECT product classes, the wide range of product
classes in the literature review will be evaluated/verified applying 7 EPHECT product
selection criteria. These criteria have been formulated in such a way, that consumer
product classes within the scope of EPHECT are prioritised. They are scored, based
on available scientific evidence and on expert judgement. The further EPHECT work
packages will then focus on the 15 selected EPHECT product classes.
In the frame of the EPHECT project, consumer product emissions to the indoor air,
as well as, the health effects caused by the emissions of the relevant compounds, is
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investigated. To this direction, consumer products are classified into product
categories, product classes, and after then to product types, as indicated in Table 1
of the Appendix. The aim is to reduce the large number of individual products and
applications to a limited number. Therefore, 13 product categories and then product
classes are divided into product types which are constituted by individual products
(Table 2 of the Appendix). Furthermore, the product classes should cover the whole
area of exposures due to the application of consumer products with emphasis to
inhalation exposure.
The consumer products were classified so that product types with similar uses and
nature are grouped together. Sales data obtained from large companies and super
markets were also evaluated for the selection of the consumer products to be
studied. Also the composition and the use pattern for each type of products within a
category were also examined for every product category.
2.2. Electronic equipment
Electrical and electronic products are highly complex. Part components are produced
at plants all over the world, and suppliers are substituted depending on their prices.
The production process involves a number of chemical products as well as most of
the elemental substances. The products typically have several plastics components to
which various additives have been added in order to ensure the required material
properties, e.g. plasticizers or flame retardants intended to prevent the ignition of
parts exposed to excessive heat.
2.2.1. Personal computers
It is now common for each person’s workspace to contain a desktop computer with a
display unit and more than half of EU households have at least one computer. In
addition, the use of notebook computers spanning both work and nonwork
environments is on the rise. Monitors are used by all age groups and can be found in
many households and in most organisations. According to a Danish Survey
[Malmgren- Hansen et al., 2003], the most popular of the kind are those of 17 and
19΄΄. A typical location of these devices at home is the sitting room and the
children’s room.
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2.2.2. Printers and faxes
Tabletop printers serve individual users in their workspace or home, or clusters of
users in an office suite. Fax machines and photocopiers are prevalent in office
environments.
2.2.3. TV sets
2.2.4. Mobile phones
2.2.5. Other (games, converters, etc.)
Today, several game consoles dominate the world market, which are mainly being
used by children and youths. Power converters for halogen lamps (using traditional
transformers) become very hot and are very often low-cost products manufactured
in the Far East. It is not unusual to use 3-5 converters in each room, because
typically a lamp comes with its own converter [Malmgren-Hansen et al., 2003].
2.3. Appliances
This product category includes:
clothes washers and dryers;
dishwashers;
hair dryers;
vacuum cleaners;
air conditioning and humidifying systems.
Kitchen appliances with high power consumption and consequent heat generation
may be a source of emitted substances, and if the concentration of these substances
is sufficiently high, this may be of importance even though the substances are
released in a relatively short period of time [Malmgren-Hansen et al., 2003].
2.3.1. Gas cooking appliances
The use of solid fuels for cooking and heating is likely to be the largest source of
indoor air pollution on a global scale. Nearly half the world continues to cook with
solid fuels such as dung, wood, agricultural residues and coal.
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Cook stoves commonly used in European countries use two types of biomass fuel. In
developing countries they are individually small, but so numerous that, depending on
emission factors, they could be important influences on global and regional carbon
monoxide (CO) inventories.
2.3.2. Washing machines
2.3.3. Vacuum cleaners
2.3.4. Air conditioning and humidifying systems.
There are several types of HVAC systems used in commercial buildings. The type of
system employed will have a significant influence on air flow patterns within the
building and can have a significant impact on the indoor air quality. The air
distribution systems most commonly used in commercial buildings are: (a)
conventional air distribution systems with ceiling supply and return; (b) conventional
air distribution systems with ceiling supply and return near the floor; (c) underfloor
air distribution systems; (d) displacement systems; and (e) split systems. Indoor air
quality (IAQ) and thermal conditions can be greatly affected by the type of air
distribution system adopted.
2.4. Fireplaces
2.4.1. Stoves and gas, oil- fired and ethanol furnaces
Approximately half the world’s population and up to 90% of rural households in
developing countries still rely on unprocessed biomass fuels in the form of wood,
dung and crop residues. These are typically burnt indoors in open fires or poorly
functioning stoves. As a result there are high levels of air pollution, to which women,
especially those responsible for cooking, and their young children, are most heavily
exposed [WHO, 2000].
Fuel/stove combinations commonly used in developing countries include various
stoves (e.g., traditional, improved, mud, brick, and metal, with and without chimney)
using animal dung, different species of crop residues and wood, root fuel, charcoal,
kerosene, and several types of coals and gases. In general, biomass fuels and coal
have higher CO emission factors than other fossil fuels [Zhang et al., 1999]. In many
circumstances, it is difficult to distinguish the use of solid fuels for cooking from the
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use for heating the home. Biomass fuel is any material derived from plants or
animals which is deliberately burnt by humans. Wood is the most common example,
but the use of animal dung and crop residues is also widespread [WHO, 2000].
Wood combustion for residential heating is an important source of indoor and
outdoor air pollution in many areas of the world. Today, every third Swedish home
can be completely or partially heated by burning firewood. Most wood combustion
occurs in boilers constructed for multiple energy sources (oil, wood and electricity),
and most of the residential furnaces used for wood burning are old installations from
which emissions are several times larger than modern installations. Lately, wood
stoves in Sweden have increasingly come into use as an additional heating device,
often in urban areas. In 1998, there were 38,000 fireplaces (stoves and the like) in
Stockholm.
2.4.2. Kerosene space heaters
15
2.5. Household products
In order to assess the household products contribution to indoor air pollution,
sufficient information about product application and use is also required. The term
“application technique” is used to denote the detailed method employed by the
consumer when using the product. Since consumer products are found in a number
of different forms including aerosols, liquids, semi-pastes or gels, pastes or waxes,
and solids, a broad range of application techniques must be anticipated. To this
direction, source characterization is a primary goal and this characterization can be
done with respect to:
time (in which case the form of the product and the method of application
are important);
temperature (where the form of the product may be important);
ventilation rate (or perhaps with respect to local air flows near the product
and user);
other environmental parameters.
On the other hand, the usage pattern information, although broader in scope,
provides adequate data to assess products’ contribution to indoor air pollution. It
would, ideally, include such data as amount used in various applications, frequency
of use, typical room volumes and air exchange rates where the products are used,
the frequency with which consumers increase ventilation by opening windows and/or
doors, and the size and types of objects to which the products are applied.
2.5.1. Laundry detergents
Laundry products are detergents for cleaning textiles. Heavy-duty detergents or all-
purpose detergents are suitable for all washable fabrics; colour detergents are
appropriate for coloured fabrics; light-duty detergents are used for lightly soiled
items and for delicate fabrics.
Laundry detergents and laundry aids are available as liquids, powders / granules,
tablets, gels, sticks, sprays, and as pumps.
16
Besides detergents, there are other laundry products: laundry aids. They contribute
to the effectiveness of laundry detergents and provide specific functioning. The
laundry aids can be categorized in:
pre-treatment aids;
laundry or water conditioners with mainly builders such as polycarboxylates
(5-15 %) and zeolite (> 30 %);
pre-soaking products containing surfactants (10-15 %), builders (80 %),
enzymes (< 5 %);
pre-wash soil and stain removers with surfactants (5-15 %), enzymes,
preservatives;
laundry boosters containing surfactants (< 5 %) and bleaching agents;
after-treatment aids;
fabric conditioners;
starches (corn, potato, rice or wheat starch) and stiffeners (synthetic
polymers);
fabric formers: stiffener based on a copolymer of polyvinylacetate with an
unsaturated organic acid; additives such as polywax;
laundry dryer aids: sheets impregnated with conditioners.
Anti-redeposition agents in laundry products contain anti-redeposition agents aiming
to prevent loosened soil from redepositing onto cleaned fabrics. Examples are
carboxymethylcellulose (CMC) and carboxymethylstarch (CMS).
For treating stains on textile, consumers use laundry liquids/ sprays or detergent
pastes which are applied directly on the garment [RIVM report 320104003/2006].
2.5.2. Floor cleaning products
Floor care products combine cleaning and polishing aspects. Depending on their
application function, these products contain either more cleaning compounds or
more protecting compounds. There are floor-cleaners, floor-polishes, combined
products, floor seal products and floor strip products.
Liquid floor cleaners, which contain soap, are meant for daily or periodically
removing all kinds of grease and dirt from different sorts of floors. By mopping the
floor with a soap solution, a thin layer of the cleaner, which is not wear-resistant, is
17
applied onto the floor that makes afterwards cleaning easier. Therefore, the wiped
surface should not be rinsed with clean water.
Polymers such as polyethylene resins and polyacrylates in floor products form films
and these protect the surface and may provide a shine as well. There are also
siloxane based products.
Combined floor products are designed for cleaning and for preserving the condition
of the existing wax or polymer coating. These products, containing resins and
polyacrylates, provide a protective layer. However, it is difficult to combine these two
functions: either the product cleans reasonably and the protective layer is of minor
quality, or it applies a moderately protective layer and it scarcely cleans.
Floor wet tissues, are ready for use when taken from the package and they are
suitable for single use. After wiping the floor surface, it is not necessary to rinse the
surface and the tissues are thrown away. These tissues with a weight of circa 10 g
contain about 25 g solution.
Mopping products are cleaning pads which must be applied to the mop head; the
area is sprayed with the cleaning solution and then mopped. The solution dries in
moments.
An average frequency of use for the floor cleaning products has been estimated to
be 3 times/week and the cleaning time ranges from 25-30 minutes, depending on
the surface area RIVM report 320104003/2006].
2.5.3. Polishing products
Floor-polishes are meant for keeping the floor in a good state of repair; therefore, a
protective and relative durable wax coating is applied on the floor. The cleaning can
be done easier and less cleaning is necessary. The coating is applied in an undiluted
form by waxing the floor. After drying, a gleaming film is formed.
Floor-polishes contain ingredients such as waxes and polymers. When a product
contains more waxes, the applied wax coating must be polished up and it is not
resistant to alkaline cleaning products. Wax has a ‘natural’ appearance. However, if
18
the floor polish contains more polymers a polymeric film will be formed. This is often
dry self-glossing after wet wiping, making polishing of the deposited films needless.
Furthermore, it is relatively wear resistant and it is difficult to remove. Modifying the
properties of these products means altering the ratio between wax and polymer.
The polishing of a cleaned floor is done twice a year with the undiluted product and
the use duration has been estimated to 90 min [RIVM report 320104003/2006]. The
product is sprinkled on a cloth and is manually rubbed on the floor, which is polished
up.
Furniture polishes include various product forms such as liquids, pastes and aerosols.
They are intended to remove dust and stains from wooden furniture surfaces, to
produce shine and to provide protection against (water) spots. For this reason,
silicone fluids, wax, lemon oil or tung oil are added as ingredient. Lemon oil and tung
oil are used in products without water. Furniture polishing products are applied as
cleaning or as caring products; further, both aims can be combined in one product.
These products are sprinkled on a cloth and are manually rubbed on the wood,
which is polished up [RIVM report 320104003/2006]. Furniture polish usually takes
place once a year.
2.5.4. Carpet cleaners
Carpet cleaners are used for cleaning all kinds of carpets, rugs and upholstery. They
can dissolve and suspend fixated dirt and remove it from the fibre. The cleaning
compounds must adsorb the loosened soil and after drying they must be easily
vacuumed off. When the whole area of the carpet is cleaned, the user leaves the
room. So, the exposure duration is the same as the application duration.
Carpet cleaning can also be done by the use of (wet) powders, which contain water,
solvents and surfactants to emulsify the soil. The soil is absorbed onto the powders;
after drying, the residues together with the bound dirt can be removed by
vacuuming. After scattering a thin layer of powder on the carpet, the brushing is
done with a dry hand brush. The scattering and the brushing are done per square
meter. If the powder is completely dry, that is after about 20 minutes, it must be
thoroughly vacuumed up with a vacuum cleaner. After cleaning with carpet powder
the carpet will be vacuumed.
19
There are no data available about the amount of residues that stays on the carpet. It
is assumed that 10% of the used amount settles on the carpet. The exposure during
post-application is calculated for crawling children, if they are exposed to these
surfaces and its residues. Dermal exposure of children can take place on any
uncovered skin, that is, on the head, the arms and hands, and on the legs and feet.
If dermal exposure of children occurs, they can also be exposed orally via hand–
mouth contact. The hands form about 20 % of the total uncovered skin (see dermal
exposure). It is assumed that 50 % of the product that ends up on the hands is
taken in orally. This means that via hand-mouth contact 10 % of the calculated
external dermal exposure is ingested and that the internal dermal exposure is 90 %
of the calculated external dermal exposure.
Carpet fresheners are for reducing malodours that may be found in carpets and rugs
[RIVM report 320104003/2006]. In this section carpet fresheners are not discussed.
2.5.5. Dishwashing products
The major types of products of this category are hand dishwashing, liquids, machine
dishwashing products and powders.
The cleaning ability of manual dishwashing products is based on surface-active
substances. The pH of these detergents ranges between 5.5 and 8.5. The important
properties of the detergents are:
foaming power: this fulfils an aesthetic function; there is no close relation
between foaming power and cleaning capacity;
cleaning capacity: good wetting of hydrophobic and hydrophilic surfaces;
enhancement of dirt removal;
stable dispersion of removed dirt;
clear drying properties;
easy flow-off on hard surfaces (hydrophilic runoff);
residue free drying, independent of the water composition.
The food residues on the crockery are removed by washing them in water with
dishwashing detergent. Usually, the dirt is removed with a brush. Scourers are used
20
to clear away the heavier food residues. Lastly, the cleaned items are dried either
with a towel or by placing them in a dish drainer.
The results of the dishwashing depend on:
- the temperature of the dishwashing water;
- the water quality: major surfactant combination often performs better in hard
water than in soft water;
- type of soil and adhesive strength of the residue to the surface (condition, material
properties);
- surfactant concentration in relation to the amount of food residue per plate: the
dishwashing performance is not linearly related to the surfactant concentration.
Dishwashing products are also used for other cleaning tasks in the household or for
washing the hands or textiles (non-intended uses).
There are also liquids: rinse aids which reduce the surface tension between the
washed items and water during the final rinse cycle of a dishwashing machine. By
achieving a uniformly draining film, there is a good clear drying effect and there are
no spots, stains and streaks left behind on the tableware.
2.5.6. All purpose hard surface cleaners
All purpose cleaners (liquid and tissues), abrasive liquids, and all kinds of sprays
during the ‘leaving on and cleaning phases’ belong to this sub category. These
products can be used for cleaning hard surfaces like windows, mirrors, wood, floors
and tiled walls. They are used for different purposes in and around the house.
Because the types of soil and the sorts of surfaces differ, there are all kinds of all-
purpose cleaners: regular, concentrated, liquid soft soap and acid cleaners; the last
can remove scale. There is no universal cleaner in particular that can handle all
cleaning objectives and their soil. For manual cleaning surfaces with an all-purpose
cleaner, one uses a sponge, cloth or mop.
The cleaner can be used diluted; if there is localized persistent soil, it can be used in
the undiluted form. In this case, it is necessary to wipe off or to rinse off the
remainder of the cleaning agents. The chemical composition of all-purpose cleaner
21
determines mainly the removal of stains; in scouring agents, abrasives enhance the
mechanical contribution for the cleaning effect. All-purpose cleaners are usually
offered as liquids, but they are also available as trigger sprays or as tissues.
These rinsing agents reduce the surface tension between the washed items and
water during the final rinse cycle. By achieving a uniformly draining film, there is a
good clear drying effect and there are no spots, stains and streaks left behind on the
tableware.
Kitchen cleaners contain more surfactants (5-30 %) and more alkalis (1-35 %), such
as ammonia, caustic soda or caustic potash. However, according to the CleanRigth
website, kitchen cleaners and many household products have alkali content of
maximum 10%. This is necessary for removing all kinds of dirt and grease.
Most people use an all-purpose liquid cleaner for cleaning furniture as well as for
cleaning floors. All-purpose cleaner is most frequently used for cleaning furniture and
cleaning the toilet. Most of the time, an all purpose cleaner is used in bathroom,
toilet and kitchen.
Spray cleaners are suitable for cleaning all washable surfaces and they are designed
for use on smaller washable areas. First, the product is sprayed onto the surface;
then, it is left on the surface to soak in for several minutes; finally, the surface
should be rinsed or taken off with a wet cloth. During spraying, inhalation can take
place. Droplets of the product or the evaporated compound can be inhaled. Sprays
produce an aerosol cloud of very small to small droplets. The speed with which the
droplets fall depends on the size of the droplet. Smaller droplets stay longer in the
air. The phase of leaving the product to soak is independent of the size of the area
to be cleaned; it is more dependent on the cleaning person, on the extent of
filthiness and on the product type. E.g., the time of leaving an oven cleaner on the
surface is much longer than the time of leaving a glass cleaner on the surface. The
exposure duration is the sum of spraying time, time of leaving on, the cleaning time
and the time staying in the specified room after spraying and cleaning (RIVM report
320104003/2006).
22
Tissues can be used for cleaning all washable surfaces. These solid, moist cleaning
tissues are ready for use when taken from the package and they are suitable for
single use. After wiping the surface, it is not necessary to rinse the surface and the
tissues are thrown away. Tissues can be used for cleaning windows, mirrors or other
surfaces; there are also tissues to clean the floor.
Abrasive cleaners are used to remove soil which is firmly attached to the surface. In
these products, small particles of minerals take care for the scouring effect, the
surfactants keep the soil in solution and the added bases can remove greasy dirt.
The surfaces treated by abrasives must be rinsed with water.
Abrasive cleaning products can be divided into abrasive powders, which must be
used with water, abrasive liquids and scouring pads. Mostly, scouring pads are a ball
of fine steel wire which provides the scouring action; further, they can contain a
cleaning mixture, mainly soap.
Relatively softer minerals in abrasives like calcium carbonate are utilized for abrasive
liquids compared with abrasive powders; so, their scouring effect is generally gentler
than powders. Liquids especially for cleaning ceramic cooking rings contain
surfactants and abrasives (metal oxides e.g. Al2O3).
In the RIVM report [2006] is mentioned for surface cleaners a typical use of 2 times
a week and a range from 1 to 7 times a week. According to the same report the
duration of task is 10 to 20 minutes. Weegels gives an average frequency per day of
0.4, which results in a 75 percentile of 0.88 day-1 or 320 year-1 (n=28). This value
included also cleaning the floor, bathroom etc. The frequency of use for a trigger
spray used for cleaning the kitchen working top as well as for wet tissues is
mentioned to be 365 days/year.
2.5.7. Sanitary cleaners
The cleaning of the bathroom presents particular problems. Normal organic and
inorganic soils as well as calcium and rust deposits from the water need to be
removed. Due to the different kinds of soils and of surfaces, various special cleaners
can be used such as bathroom cleaning sprays and liquids.
23
Toilet cleaners are divided in two different products i.e. toilet cleaners containing
acids for removing calcium or metal salts and toilet cleaners containing a bleaching
system which can be hydrogen peroxide or hypochlorite. Hypochlorite bleaches are
used in hard surface cleaning and sanitizing. This can be done in a separate step of
the cleaning task e.g. cleaning the toilet with bleach or the bleach is an incorporated
ingredient in the cleaning product e.g. an abrasive liquid containing bleach. The toilet
cleaner is spout with a squeeze bottle under the rim of the toilet pan. After leaving
the toilet cleaner to soak in the toilet pan, the toilet pan is brushed.
The toilet seat can be cleaned with wet tissues. These contain non-ionic surfactants,
alcohol, perfume, and preservatives. Hygienic wet tissues might contain as well
active hydrogen peroxide.
Boxes containing toilet rim cleaners (auto-active) cling to the inner ring of the toilet
bowl. On each flush of the toilet, they release active ingredients into the bowl. The
toilet rim cleaners or flush/ rinse cleaners should maintain a clean bowl, that smells
fresh. There are solid and liquid toilet rim cleaners. Usually they contain acids like
formic acid, lactic acid, sulphuric acid or phosphoric acid and can dissolve calcium
and metal salts [RIVM report 320104003/2006].
A typical value of 2 times per week is given in the above mentioned report for the
surface cleaners. For cleaning the bathroom or other tiled or ceramic walls, Weststat,
mentioned in the RIVM report gives a 75th percentile of 4 month-1 and a 50th
percentile of 2 month-1. The default value is set at 1 week-1 or 52 year-1. The
amount for surface spray ranges from minimal 5 to maximal 30 gram. The average
mass generation rate is estimated to be 0.39 g/s with a spray duration of 90 sec.
Therefore, the amount for spraying is 0.39 g/s x 90 s = 35.1 g [RIVM report
320104003/2006]. According to the same source, for bathroom cleaning liquids
(containing acids) which are periodically applied as descaling products the frequency
is estimated at 4 times a year.
2.5.8. Glass cleaners
Glass cleaners are being used for removing dirt, smoke deposit and fingerprints from
windows, mirrors, glass cases and glass tables. They clean the area without stripes
and they are generally used undiluted by means of a trigger spray. Based on the
24
general composition, it is assumed that the non-volatile part in glass cleaning sprays
is about 5 % [RIVM report 320104003/2006].
2.5.9. Oven cleaners
Oven cleaners are strong degreasers and they are suitable for removing sticked dirt
of ovens, grills etc. Oven cleaners contain strong alkaline ingredients and therefore,
they can be irritating and caustic. Strong alkali is necessary to remove burned-on
soils. There are trigger sprays and spray cans. When using a spray can, foam is
formed on the target area. The typical use pattern of these products is as follows:
after spraying the oven door is closed and the product has to soak for some minutes.
Then the oven is wiped clean with a wet cloth or sponge and one has to rinse
frequently. Usually, the product information recommends to wear long rubber gloves
and to avoid contact with skin, eyes, mucous membranes and clothing. According to
the RIVM report 320104003/2006 an oven cleaner product is used typically 26 times
a year.
2.5.10. Spot removers
Using a spray spot remover, the user can be exposed to aerosols. To calculate the
exposure of the user during spraying, the ‘spray model’ is used for inhalation
exposure and the model ‘constant rate’ for dermal exposure. When treating the
stains on the garments, there can also be direct skin contact with the product; to
calculate dermal exposure, the model ‘instant application’ is used.
For the scenario ‘removing spots on laundry’, a special liquid spot remover (or
regular laundry liquid) is put on the fabric. Generally, consumers pre-wet the laundry
before applying the detergent or they use the stain remover under running tap
water. When putting on the spot remover and treating the stains on garments, there
can be direct skin contact with the (diluted) product [RIVM report 320104003/2006].
2.5.11. Metal cleaners
Metal cleaners are used for cleaning, polishing, protecting and for restoring all kinds
of metal such as chrome, copper, brass, aluminium and stainless steel. There are
two types of products i.e. water based products and solvent-based products. They
generally contain naphtha, as a solvent, as well as oleic acid, alkalonamine, ammonia
or ammonium chloride [RIVM report 320104003/2006].
25
2.5.12. Drain openers
Drain openers open slow running and obstructed drains by dissolving and by
loosening grease and organic waste. There are different kinds of drain openers,
products containing either sodium hydroxide (caustic soda or caustic liquid) or
sulphuric acid. Both products are corrosive.
There are also drain openers containing beneficial bacteria of the Bacillus species. To
eliminate clogs, pollution and odours these bacteria break down and convert organic
material into its two most basic components i.e. carbon dioxide and water. Free
enzymes are added to the formula to break up complex waste molecules into small,
simple pieces that can be digested directly by the bacteria [RIVM report
320104003/2006].
2.5.13. Shoe polishers
For keeping shoes in good repair, one uses shoe polish. The ingredients such as
waxes (e.g. turpentine oil) are for protecting and for nourishing leather and they
produce a long-lasting glossy shine. Naphtha is a common solvent for these products
[RIVM report 320104003/2006].
26
2.6. Air fresheners
Air fresheners could be: i) solid deodorant disks that are used in the lavatories, ii)
wall-mounted units that emit a fragranced spray and that are used primarily in
lavatories in industrial and institutional environments, and iii) plug-in air fresheners,
used in residential, industrial and institutional environments.
Candles are generally composed of paraffin, mostly solid paraffin, which is made of
heavy straight-chain hydrocarbon from crude oil. There are several different types of
additives used in candles to improve the burning performance and aesthetic
appearance. For example alkanoic acids such as stearic acid are used to improve
hardening characteristics of the wax and increase the melting point. Added colouring
pigments may contain heavy metals. Inorganics such as ammonium phosphates and
borax (a salt mixture containing borates) are added to the wick to act as a flame
retardant to ensure that the wick is consumed at a sufficient rate and to prevent
glowing of the wick upon extinction. In certain types of candles, metals such as zinc,
tin and lead are added to the wick to improve mechanical stability [Pagels et al.,
2009]. More recently fragrance oils have been added to certain types of candles.
Incense has been used since ancient times to produce pleasant fragrances or to
mask odors, and incense burning has been incorporated in many religious
ceremonies and practices. A wide variety of substances used to produce incense
includes resins (such as frankincense and myrrh), spices, aromatic wood and bark,
herbs, seeds, roots, flowers, essential oils, and synthetic substitute chemicals used in
the perfume industry.
Incense is available in various forms including sticks, joss sticks, cones, coils,
powders, rope, rocks, charcoal, and smudge bundles. Incense sticks have a base,
often a slender piece of wood or bamboo, to which incense compounds are attached.
Joss sticks are formed from the incense compound itself, and do not have a base.
Cones taper to a point on top for easy ignition and produce a greater amount of
smoke as they burn down to the larger diameter bottom. Coils are designed to burn
for a long time, and coils containing insecticide are used to repel and kill insects.
Smudge bundles are made of bundled herbs and twigs and are typically used to
produce a larger amount of smoke compared to the other types. Rock incense,
27
frequently used for religious practices, is placed on hot charcoal briquettes made
with a small, saucer shape on top to hold the incense [Jetter et al., 2002].
Essential oils are products generally of rather complex composition comprising the
volatile principles contained in the plants and more or less modified during the
preparation process. They are considered to be complex mixtures of various aroma
chemicals. Essential oils and some extracted fragrance compounds are widely
adopted into modern society for their capacity, at least reportedly, in generating
pleasant odours, and providing anti-bioactivity benefits. Many components of
essential oils contain one or more asymmetric carbon atoms that exhibit optical
activity. These chiral compounds of natural (mono- and sesquiterpenes) are
generally found in characteristic enantiomeric distributions. Besides their pleasant
odour, these natural compounds exert significant biological and pharmacological
effects on different experimental models, which are mainly due to their lipophilic
nature [Lahlou, 2004]. Essential oils are strongly smelly liquids that do not mix with
water. They cause the characteristic smell of plants, such as roses and lavender for
example. The oil is obtained using steam distillation or by extraction from various
parts of plants. Essential oils are used as fragrance in various cosmetic products, and
as such are the ‘essence’ of perfume, eau de toilette and aftershave, for example.
Other names for essential oils are aromatic, or ethereal, volatile oils or essences. In
addition to the natural pure oils, there are synthetically prepared essential oils and
essences that are mixed with alcohol or oil.
The most popular and typical essential oils include lavender, lemon, rose, rosemary
and tea tree oils. Depending on the components of the oil, they exhibit antibacterial,
antiviral, antifungal, sedative, antispasmodic and/or anti-inflammatory effects and for
this they have been widely used in medicine, food and cosmetics. Generally, the
major constituents of essential oils are primarily alcohols, aldehydes, oxygenated
monoterpenes, monoterpene hydrocarbons, sesquiterpene hydrocarbons and
oxygenated. Therefore, terpenes could be an important species concerning of
essential oil components [Chiang et al., 2010]. In the same study, the main
composition of essential oils was analyzed by gas chromatograph mass spectrometry.
The essential oil sequence regarding the carbonyl emission factor was found to be
lavender > tea tree > rose > rosemary > lemon oils.
28
When essential oils are used as air fresheners they evaporate with the help of an
aroma lamp. On top of the lamp is a small tray filled with water into which the oil is
dropped. Under this tray is a small candle which warms the water and essential oil.
The aroma of the oil spreads through the room. There should always be sufficient
water in the tray. Six to 12 drops of essential oil is normally enough for an area of
approximately 30 m2. A user said that he used the aroma lamp to evaporate oil 14
times per month. They are usually used in the living room. The size and contents of
the tray into which the essential oil is added depends on the aroma lamp.
2.7. Pest control
Pest control products are used to control invertebrates (insects, arachnids, slugs and
snails), mammals and birds. There is a great diversity in the types of use and
application methods for the products. There are sprays, liquid repellents and strips
from which the active substance can evaporate powders and electrical evaporators.
Some of these products can be used without any preparation, while others have to
be processed (mixed and loaded) before use, for example by diluting or cutting up.
All of these products forms imply a different type of exposure, whereby differences
can occur in the exposure phase (mixing and loading, during or after exposure) and
the route of exposure (inhalation, oral, dermal).
Pest control products are divided into agricultural pesticides and non-agricultural
pesticides, or biocides. Biocides form an extremely diverse group of products, which
are used both by professionals and non-professionals (consumers) to control or
prevent damage by undesired organisms, such as microbial organisms, fungi, flying
and crawling insects, small mammals such as mice and rats, but also mosses, algae
and weeds. Wood preservatives and disinfectants also fall into the biocides category.
Some of the biocides are available to consumers for private use; other products are
only available for professional use [RIVM, 2006b].
Pesticides used in and around the home include products to control insects
(insecticides), termites (termiticides), rodents (rodenticides), fungi (fungicides), and
microbes (disinfectants). They are sold as sprays, liquids, sticks, powders, crystals,
balls, and foggers.
With regard to mixing and loading, there is a distinction between:
29
• liquid concentrate, that is diluted and sprayed using a plant sprayer and
whereby, during the dilution, evaporation can occur
• powders and granules, which are dissolved in water and are sprayed using a
plant sprayer; the powder can produce dust during dissolving
To spray pest control products two types of spraying devices are available: aerosol
spray cans and trigger sprays. Aerosol spray cans are pressure resistant containers
from which a liquid is discharged under the pressure of a propellant; these cans are
ready-to-use spray products. Trigger sprays are dispensers turning a liquid into a
(fine) spray. There are ready-for use pest control product trigger sprays and
formulations, which should be mixed and loaded in a plant sprayer. By turning
around the nozzle of the plant sprayer the spray distribution can be adjusted which
results in a spray with fine or coarse droplets.
With regard to the target, one can distinguish between the following four types of
application:
Targeted spot application refers to the spraying of hiding places of crawling
insects and ant tunnels. It often concerns a relatively small surface to be
sprayed, which is sometimes difficult to reach both for the user and for the
non-user. For example, behind the refrigerator or a radiator, or in/under
kitchen cabinets. When considering the method and extent of exposure, the
spraying of plants against red spider mite and such like can be compared with
the spot application.
Crack and crevice application concerns the spraying of cracks and crevices
to control silver fish, cockroaches and so forth, for example, on baseboards in
living and accommodation areas, and in cracks and holes in wooden floors.
General surface application is the spraying of large surfaces such as a
carpet or couch to control dust mites or fleas, for example.
Air space application is the spraying of living, working or accommodation
areas against flying insects, whereby the user stands in the middle of the
room and sprays all four of its upper corners.
These spray applications differ from each other in the manner and extent to which
the user and the bystanders are exposed. For example, a difference is expected in
exposure during crack and crevice application and during a general surface spray,
30
due to the longer application time of the latter treatment. A difference in the
exposure during application can also occur due to the height at which the spraying
takes place; above the head, as is usual during an air space application, or aimed at
the floor, such as during a general surface spray. After application of these sprays,
there is a difference in the size of the wipe able surface, amongst other things.
The biocides directive (98/8/EC) came into force in the European Union in 1998, and
deals with the authorization of active substances required for biocides which can
occur within 23 categories, summarized as disinfectants, preservatives, pest control
products and other biocidal products. EPA registers pesticides for use and requires
manufacturers to put information on the label about when and how to use the
pesticide. It is important to remember that the "-cide" in pesticides means "to kill."
These products can be dangerous if not used properly.
[http://www.epa.gov/iaq/pubs/insidest.html]
In addition to the active ingredient, pesticides are also made up of ingredients that
are used to carry the active agent. These carrier agents are called "inerts" in
pesticides because they are not toxic to the targeted pest; nevertheless, some inerts
are capable of causing health problems such as: irritation to eye, nose, and throat;
damage to central nervous system and kidney; increased risk of cancer.
Both the active and inert ingredients in pesticides can be organic compounds;
therefore, both could add to the levels of airborne organics inside homes. Both types
of ingredients can cause the effects discussed in this document under "Household
Products," however, as with other household products, there is insufficient
understanding at present about what pesticide concentrations are necessary to cause
these effects.
Exposure to high levels of cyclodiene pesticides, commonly associated with
misapplication, has produced various symptoms, including headaches, dizziness,
muscle twitching, weakness, tingling sensations, and nausea. In addition, EPA is
concerned that cyclodienes might cause long-term damage to the liver and the
central nervous system, as well as an increased risk of cancer.
There is no further sale or commercial use permitted for the following cyclodiene or
related pesticides: chlordane, aldrin, dieldrin, and heptachlor. The only exception is
31
the use of heptachlor by utility companies to control fire ants in underground cable
boxes.
Concerning the frequency of use of pest control products, they are limited to the
actual control of any plague, that is, the product will not be used if there are no
pests. Therefore it is expected that the use of pest control products mainly to take
place in the summer, since it is usually in this period that invertebrates (insects,
arachnids, slugs, snails and such like) appear. For spraying products it has been
estimated that they are used 6 times a year [[RIVM, 2006b].
2.8. Clothes and fabrics
Textiles must not contain a number of chemical substances. The regulations also
include textiles used in toys [DEPA, 2009]:
Brominated flame retardants, penta -and octabromodiphenylethers (penta
and octa-BDE) are banned for any usage, including textiles. (REACH,
Annex XVII, entries 44 and 45) Threshold limit is 0.1% (w/w);
Impregnants tris (2, 3-dibrompropyl) phosphate (TRIS), tris (1-aziridinyl)
phosphineoxide (TEPA), (CAS no. 5455-55-1) and polybrominated
biphenyls (PBB) (CAS no. 59536-65-1) must not be used in textiles which
are intended to come into contact with the skin, e.g. articles of clothing or
linen. The ban covers both import and sale (REACH, Annex XVII, entries
4, 7 and 8);
The sale, import or production of products containing cadmium is banned
if the cadmium is used as a stabiliser in plastic, cadmium coatings or
pigmentation (REACH, Annex XVII, entry 23);
Textiles must not contain certain azo colouring agents. The regulations
also apply for textiles used in toys. It is prohibited to import, sell or use a
specific blue azo colouring agent and azo;
Colouring agents, which can release carcinogenic substances, as well as
certain other products, which contain azo colouring agents (REACH,
Annex XVII, entry 43);
Products which are designed for direct or long-term contact with the skin
must not contain nickel if the nickel emission exceeds 0.5mg/cm²/week
(REACH, Annex XVII, entry 27);
32
In accordance with REACH, Annex XVII, entry 53, PFOS (perfluorooctane
sulfonate and its derivatives) are prohibited in products, including textiles,
from 27 June 2008. Special notice should be taken of the ban on textiles
or other materials with a coating, if the amount of PFOS comprises 1
μg/m2 or more of the coated material.
33
2.9. Personal care products
This wide product category includes a number of products or cosmetics intended to
be used for personal hygiene, care and beauty scopes. According to the EU Cosmetic
Directive 76/768/EEC, a ‘cosmetic product’ shall mean any substance or preparation
intended to be placed in contact with the various external parts of the human body
(epidermis, hair system, nails, lips and external genital organs) or with the teeth and
the mucous membranes of the oral cavity with a view exclusively or mainly to
cleaning them, perfuming them, changing their appearance and/or correcting body
odours and/or protecting them or keeping them in good condition.
Cosmetic products are regulated by the statutory order on Cosmetic Products [BEK
422, 2006] and its amendments. The following special conditions are applicable for
the list of ingredients for cosmetic products:
Impurities present in raw materials are not considered ingredients;
Perfume and aromatic compounds and raw materials for these will be
declared as either “perfume”, or “aroma”. In accordance with Annex 3 of the
statutory order, 26 allergens (which are mainly skin sensitizers) in perfumes
and aromas substances must be indicated in the list of ingredients if their
concentration exceeds 0.001% in leave-on products, and 0.01% in rinse-off
products. This rule on the 26 allergens in perfumes and aromas came into
force in 2005 and applies to all cosmetics produced after 10 March 2005;
Ingredients with a concentration of less than 1% can be declared in any
order following those with a concentration higher than 1%;
Colouring agents can be declared in any order after those with a colour index
number (or name from Annex 4 on colouring agents). Ingredients can be
declared by their common name, in accordance with common nomenclature
(INCI name) for cosmetic ingredients;
With small cosmetic products, or packaging that is so small that it is
impossible to print a list of ingredients of contents, the ingredients must be
printed on an accompanying label, tape, or card that can be attached to the
product. If it is not possible to fasten information of this type onto the
product, the list of ingredients must be clearly displayed close by.
34
In Table 2 of the Appendix and within the main category of “Personal care products”,
secondary categories (shampoos, make-up, lipstick, hair sprays, body lotions,
deodorants etc.) are also defined, which together describe the entire main category.
2.9.1. Bathing and showering products
Showering products. During a shower, some people wash themselves with soap or
gel with the water still streaming over their body. In ‘Notes of guidance for testing
of cosmetics ingredients for their safety evaluation’ by the SCCNFP, a retention
coefficient of 1 % is assumed for shower gel, since shower gel dissolves easily in
water and is used on wet skin. The retention coefficient is the relative amount of gel
that remains on the skin after showering [RIVM report 320104001/2006].
Bathing products. The basic bath products are bath foam, bath salts and bath oil.
Bath salts come in powder, granule and tablet form and are made up of inorganic
salts. The EU’s ‘Technical Guidance Document’ gives 17 g as the amount of bath
foam used. Bath oils can be divided into various categories depending on the
solution, dispersion etc. after the oil has been added to the water:
- floating type: oil droplets float on the water surface
- spreading type: thin film of oil spreads out over the water surface
- dispersal type: oil is dispersed in small particles into the bath water
- milky type: oil gives a white cloudy dispersion in the bath water
The general composition of the basic bathing products is:
Bath foam
- 60-80 % water;
- 20-25 % surface-active agent (cleaning);
- 0.2-2 % surface-active agent (foam stabiliser) ;
- 0.5-5 % lipids: to ‘put back’ the oils;
- 0-3 % thickening agent (to increase the viscosity);
- 0.1 % preservatives;
- 0.3-3 % perfume;
- 0.1-0.2 % colouring.
Bath salts:
35
- 45-50 % sodium sulphate;
- 15-50 % sodium bicarbonate;
- 1 % sodium carboxymethylcellulose (granules);
- 8 % sodium carbonate (tablet);
- 22 % succinic acid (tablet);
other ingredients:
- colouring agent;
- perfume.
Soap is used to cleanse the skin. A bar of ‘normal’ soap usually contains natural fatty
acids such as sodium stearate (C17), sodium palmitate (C15) or sodium oleate (C17).
The term ‘soap’ is protected in many countries. Liquid soap products are therefore
not allowed to be called soap, and are called synthetic detergents. They contain
synthetic active cleaning agents and a lot of water. These surface-active agents
increase the washing power and ensure the formation of foam. These substances
have a hydrophilic and a lipophilic part, and they are divided into anionic, cationic,
amphoteric and non-ionic surface-active agents. These products, such as mousses,
gels and liquid soap are growing in popularity. They are used on the entire body.
The following factors are those that play a role in causing intolerances such as
irritation:
- basic character: watery soap solutions are alkali and have a pH of 9-11.
- water absorption of the skin protein keratin: this makes the epidermis softer and
the uptake of foreign substances through the skin easier (for example the uptake of
preservatives from liquid soap).
-degreasing: the skin is degreased during washing. Particles and micro-organisms
attach themselves to the skin more easily and the uptake of substances also
becomes easier. To solve this problem, oil or fat is added to the soap solution so that
it can put back the oil into the skin. The presence of the surface-active agents means
that the fats remain in the solution and they are rinsed away with the water.
Hand washing products. Hands are washed with ordinary soap or liquid soap. The
latter is usually dosed using a dispenser. The composition of a classical bar of soap
or a liquid soap is [RIVM report 320104001/2006]:
36
Table 2.1. Composition of bar of soap and liquid soap
Classical bar of soap Liquid soap: synthetic detergent
85-95 % sodium salt from fatty acids 60-80 % water
Approximately: Approximately:
0.5 % perfume 15 % surface-active agent (cleaning)
0.1 % antioxidant 1 % surface-active agent (foaming
agent)
0.01 % colouring 2 % lipids: to ‘put back’ the oils
2 % thickening agent
0.3 % preservatives
0.3 % perfume
0.01 % colouring
2.9.2. Hair care products
The general composition of a shampoo is:
- 66 % water;
- 14 % sodium lauryl ether sulphate (surfactant, active cleaning agent);
- 5 % betaines (surfactant, foaming agent; also coconut oil-diethanolamide and
lauric acid diethanolamide);
- 2 % quaternary ammonium compounds (conditioner; also betaines);
- 1 % polyethylene glycol-distearate (hair shining agent);
- 1 % common salt (viscosity regulator);
- 0.5 % fragrance;
- 0.00015 % kathon CG (preservative);
- 10.5 % other ingredients.
A conditioner is used after the hair has been washed with shampoo. After a few
minutes the conditioner is rinsed out, just as with shampoo. As well as being sold
separately as conditioner, they are also often added to the shampoos themselves.
Quaternary ammonium compounds (quats) are often used as conditioners. Other
substances that are used are silicones, fatty acid-protein compounds, panthenol and
37
betaine compounds. The active cleaning agent in shampoos often has a strong
degreasing character; washing with shampoo therefore strips the hair its natural oily
layer. Conditioners have outwardly the same function as the removed oils in that
they adhere to the hair and form a shiny layer [RIVM report 320104001/2006].
According to the California Consumer Products Regulation for hairsprays a
“Hairspray” means a consumer product designed primarily for the purpose of
dispensing droplets of resin on and into a hair coiffure which will impart sufficient
rigidity to the coiffure to establish or retain the style for a period of time.
During spraying the hairspray is atomized; some of the hairspray will end up on the
hair or on the scalp, and some will be sprayed next to the hair. This part will end up
in the room as aerosol particles. It is assumed that 85 % (5.8 g) of the sprayed
hairspray will end up on the hair and the head. With regards the distribution
between the amount that ends up on the hair and the amount on the scalp, the EU’s
‘Technical Guidance Document’ indicates that 10 % of the total amount used (i.e. 10
% of 5.8 g) ends up on the scalp.
The general composition for aerosol can of hairspray is as follows:
- 50 % propellant (butane, dimethylether)
- 45-50 % solvent (ethanol, water)
- 3 % fixative (vinyl polymers including polyvinylpyrrolidone)
- 0.02-0.06 % polymer neutraliser (tri-isopropanolamine)
- % plasticizers (lanoline derivates, phthalates)
- 0-5 % perfume
Corrosion inhibitors may need to be added due to the use of water.
A ‘typical formula’ for hair gel is given below:
- 77.3 % water
- 20 % ethyl alcohol
- 2.7 % polymers
other ingredients:
- perfume
- humectants (moisturizing compounds)
- alkali
38
- surface-active ingredients
- chelates
For a hair mousse the basic substances are:
- 63 % water
- 13.5 % ethyl alcohol
- 6.3 % humectants
- 4.5 % oils
- 2.7 % polymers
- 10 % propane (propellant)
other ingredients:
- perfume
- preservatives
For the hair gel and hair mousse products the exposed area during ‘use’ is the hands
and head, and during ‘contact’ it is only the head.
There are three different types of hair dye:
1. Temporary hair dye, the hair dye is removed by washing the hair.
A) Application: as shampoo (colour rinse), is currently hardly used; 0.5-2 %
active colour ingredients; high molecular water-soluble textile dyes
(monosulphonic, disulfonic and trisulphonic acids of azo, anthraquinone and
triarylmethane).
B) Application in an aerosol can, particularly for special occasions such as
sporting events, carnivals and children’s parties.
2. Semi-permanent hair dye (4 to 5 washes)
- as for permanent dyes, but without an oxidation agent
- dyes with a low molecular weight
(nitrophenylenediamines,nitroaminophenols, aminoanthraquinones and to a lesser
extent azo dyes )
3. Permanent dyes (more than 10 washes)
Permanent hair dyes are produced in two parts (A and B), just before use the two
parts need to be mixed
A) - primary intermediate (a para-compound such as paratoluenediamine)
- a coupler (e.g. resorcinol, couples with the primary intermediate)
B) an oxidiser (usually hydrogen peroxide)
39
The para-compounds are oxidised into benzoquinoneimines using hydrogen peroxide.
The imines react quickly with the couplers or with non-oxidised para-compounds to
the colour-forming material. The mixture of colour-forming materials are often found
in a shampoo base (pH 9-10, base often ammonia) [RIVM report 320104001/2006].
Home hair bleaching products are usually made up of three parts that are mixed
together just before use. The general composition of hair bleaching products is:
Table 2.2. Composition of bleaching products
Part 1 Part 2 Part3
Decolourant cream Developer Powder
60 % water 80 % water Sodium or ammonium
persulphate
5 % lipids booster 1% foam magnesium carbonate
2 % emulsifier 8 % emulsifier sodium lauryl sulphate
1.5 % stabilisers 1 % alkali
1 % acid 0.01 %
colouring
7% H2O2
The first part contains the actual bleaching agent (H2O2) that in this form can be
stored in a stable state. The second part is the so called ‘bleach base’, and contains
alkali to realize a high pH. The third part contains a substance (often sodium
persulphate: Na2S2O8) to improve the bleaching power.
Concerning the frequency of use of hair bleaching is assumed it is the same as for
hair dye products, since they both depend on the hair growth. One of the directions
for use stated that there should be at least 3 weeks between 2 hair bleaching
sessions, or between a perm and a hair bleaching session. Hair bleaching products
are used by relatively few consumers and are affected by trends.
The various hair-bleaching products on sale for consumer use contain differing
amounts of decolourant cream (40-120 ml), developer (50-120 ml) and powder (12.5
- 48 g). The parts of the hair bleaching products are often given other names such
as, bleaching activator, bleaching powder and decolouration powder. Depending on
40
the product, the total amount varies from 100 g to 228 g per packaging [RIVM report
320104001/2006].
Perm lotion is used to make hair more or less permanently curly. In the perming
process two steps can be distinguished.
1. The hair is washed with shampoo and, after careful rinsing, is curled (with
perming rods: rollers or clips) and is moistened with perm lotion. This liquid contains
an alkaline reducing agent. The reducing agent breaks the sulphur bridges that hold
the elongated creatin chains together. After applying the perm lotion, a plastic cap is
put over the hair and a towel is wrapped around the head. The perm lotion needs 10
to 30 minutes to work, with a maximum of 40 minutes. The directions for use clearly
indicate that this time may not be exceeded. When it has been worked in, the perm
lotion needs to be removed by thoroughly rinsing the hair with lukewarm water.
2. The next step is the neutralising or fixing of the curls. The liquid used for this
purpose is an acid oxidiser. The oxidiser repairs the sulphur bridges, but this time so
that the curls are maintained. Three quarters of the fixing lotion is applied to the hair
in the perming rods. The fixing lotion must be left on for 5 to 10 minutes. The
perming rods are then removed and the hair is thoroughly washed with the
remainder of the fixing lotion. It is left in for 0 to 5 minutes and then rinsed out with
lukewarm water.
The general composition of perm lotion is:
- 92 % water
- 7 % ammonium thioglycolate, for home use 5-8 %, legal maximum 8 %; for
professionals 7-11 %, legal maximum 11 %
- 1 % cloudifier (ensures the distribution of the perm lotion on the hair)
- 0.05 % colouring
- 0.1 % perfume
alkaline compound, ammonium or triethanolamine salts up to pH 9-10.
The general composition of the fixing or neutralising lotion:
- 94 % water
- 4 % H2O2
- 1 % cloudifier
- 0.5 % citric acid
- 0.1 % stabilizer
41
- 0.05 % colouring
In addition to the perm lotions containing ammonia, there are also perm lotions
without ammonia. Perm lotion and neutralising lotion are also available in aerosol
form. The products are then used in the form of a mousse [RIVM report
320104001/2006].
2.9.3. Skin care products
Skin care products include creams, body lotion, face packs, mud baths as well as
products, which beautify the skin, such as facial make-up, eye shadow and lipsticks
[RIVM report 320104001/2006].
Creams. Many different sorts of products are applied to the skin to care for it. In
addition to semi-solid creams, liquids are also applied. There are products for
particular parts of the body such as face creams (day cream, night cream) and hand
cream, and products which can be applied to the whole body, such as body milk.
Reference gives a general formula for creams (cream, salve, body milk, lotion, day
cream, night cream, moisturising cream):
- 20-90 % water
- 10-80 % lipids
- 1-5 % polyol (to hold in the moisture, so that the cream does not dry out)
- 2-5 % surface-active agent (emulsifier)
- 0-5 % special additive
- 0.5 % preservative
- 0.2 % perfume
Suncare products. There are various cosmetic sunscreen products on the market,
such as sunscreen cream, lotion and oil. There are also products that can be used
after sunbathing. Their general composition is like those of creams. Sunscreen
creams contain ± 5-6 % sun filters and ± 5 % titanium dioxide (white pigment).
Sunscreen lotion contains approximately 10% sun filters. Sunscreen oil does not
offer as much protection against sunburn; the oil contains approximately 2-3 % UV
absorbing ingredients which act as the protection factor.
Facial Make-up. Foundation is applied as a layer of make up over the face cream.
This can act as the basis for a layer of powder. There are various types of facial
42
make-up: compact, cream and liquid make-up. In compact make-up the powder
constituents are bonded using oil. Foundations are often emulsions. With the help of
surface-active agents, liquid droplets are dispersed into a different liquid, the
continuous phase. This phase is oil in water/oil emulsions and water in oil/water
emulsions. The water/oil emulsions and oil/water emulsions are for cream and for
liquid foundation.
The powder in foundations contains pigments (iron oxides), silicates (talc, kaolin and
mica), titanium dioxide, zinc stearate, and nylon powder. In dual-use foundation the
powders are treated with silicon. Dual-use foundations can be applied to the face
using a dry or wet pad. The general formulas for compact foundations, water/oil
emulsions and oil/water emulsions are given below:
Table 2.3. Formulas for compact foundations
Ingredients Compact
foundations
Water/oil
emulsions
Oil/water
emulsions
Powder 15-93 % 10-35 % 5-25 %
Oil 2-70 % 15-50 % 10-30 %
Water (only in
emulsions)
5-30 % 20-60 % 40-80 %
Other ingredients
- preservative X x
perfume X x x
Stabiliser x
Antioxidant X
x: ingredient in facial make-up
Make-up removers are used to remove make up; cleansing lotions are also available
which are only used to clean the face. There are various types of facial cleansers on
the market. In addition to make up removers there are cleansing lotions and foams
suitable for cleaning the face and removing any light make up. Cleansing milk,
cream, and gel contain more lipids and can also remove heavier make-up.
Humectants have the ability to absorb a lot of water. They ensure the moisturising
43
effect of the cosmetics product. Most make-up removers are wiped off with a tissue
or rinsed off with water after use.
The general formula of make-up removers is:
- 8-64 % water
- 3-63 % lipids (lotions contain no lipids)
- 10-30 % humectants (moisturizers)
- 1-15 % surface-active agents
- up to 0.1 % alkali
other ingredients:
- preservatives
- colouring
- perfume
- chelates
In addition to the above-mentioned ingredients, foam contains approximately 6 %
alkali and 33 % higher fatty acids. Alcohol-based lotion contains 15 % ethyl alcohol
and 1.5 % detergent. Cleansing milk contains 0.15% polymer.
Eye shadow is applied to the eyelids and to the skin under the eyebrows; it is
creamy. The general formula for eye shadow is:
- 60-80 % lipids (binding agent)
- 10-30 % colour pigments
- 7 % zinc stearate (attachment)
- 5 % titanium dioxide (covering)
- 0.1 % preservative
Mascara is applied to the eyelashes and it is a semi-liquid product. The general
formula for mascara and waterproof mascara is given below:
Table 2.4. Formula for mascara and waterproff mascara
Ingredients Mascara Waterproof mascara
Water 70 % 10 %
Lipids 20 % 50 %
Colour pigments 5-10 % 10 %
44
Surface-active agents 5 %
Polyacrylates 30 %
Preservative 0.05-0.3 % x
Perfume x
x: ingredient in mascara
Eyeliner is applied as a thin line on the eyelid just above or below the eyelashes.
General formula for eyeliner pencil and stick-type eyeliner is as follows:
Table 2.5. Formula for eyeliner pencil and stick-type eyeliner
Ingredients Eyeliner pencil Stick-type eyeliner
Water 83 %
Lipids 50 %
Colour pigments 20 % 5 %
Titanium dioxide 5 %
Silicates (kaolin and talc) 25 %
Humectants (moisturizers) 10 %
Polymer emulsion 2 %
Preservative x
Antioxidant X
Eye make-up remover is used to remove eye shadow and other eye make-up. Both
oil-based and water-based eye make-up removers are available. The oil-based
remover is used for heavy make-up. The water-based remover can be used after
using the oil-based remover, to remove the oiliness and any remaining make-up. The
general formula for oil-based make-up remover is:
- 8 % water
- 62 % lipids
- 15 % humectants (moisturizers)
- 15 % surface-active agents
For the lipsticks the general formula is given below:
- 60 % lipids (wax)
- 30 % lipids (solvent)
- 5-8 % colour pigment (often xanthene dyes)
45
- 0.05 % antioxidant
- 0.1 % perfume
The amount of lipstick used per application has been estimated to be 0.01 g [RIVM
report 320104001/2006].
Shaving soap looks like normal soap, but a lot of glycerine and fatty ingredients have
been added. The soap and cream are applied with a brush onto wetted skin. Foam is
sprayed onto the hands and applied to the face using the hands. A uniform, viscous,
thick foam layer is formed that is long lasting. Glycerine used as a moisturizer and
fatty acids lower the ‘foaming power’ of the soap: a good balance between the
various components is needed.
Aftershave lotions prevent infections in any small wounds that occur during shaving.
The evaporation of ethanol causes the skin to contract and cool off. A formula for
aftershave is:
- 55 % ethanol
- 42 % water
- 2 % humectant (moisturizer)
- 1 % surface-active agent
- 0.1 % allantoin
- perfume
- plant extracts
Nail cosmetics include products such as nail polish, nail polish remover, nail
strengthener and nail hardener. The function of nail strengtheners is to strengthen
weak, brittle nails; nail hardeners make the nails harder. Artificial nails are also
available. These acrylic nails are designed to enhance the natural nails. Hard artificial
nails can be glued onto your own nails for temporary use. Liquid artificial nails are
applied just like nail polish by a professional nail stylist.
Nail polish is available in various forms, such as base coat and topcoat. Base coat
consists of more than 10% synthetic resin. Topcoat contains more cellulose nitrate
and plasticizer but less synthetic resin than normal nail polish. They are used in this
order: base coat, nail polish and then top coat. Nail polish is applied to the nails of
the hands and feet using a very fine brush.
46
The general composition of ordinary nail polish is given in reference:
- 72 % organic solvents
- 10 % cellulose nitrate
- 5 % plasticizer
- 10 % synthetic resin
- 3 % colouring
The composition of the mixture of solvents depends on the ingredients used in the
nail polish. Τhe solvents must be able to dissolve cellulose nitrate, resins and
plasticizers.
Nail polish contains 75 % organic solvents:
- 20 % ethyl acetate
- 15 % butyl acetate
- 5 % ethyl alcohol
- 35 % toluene
Other possible solvents in nail polish are butanol, amyl acetate, and isopropyl
alcohol. Cellulose nitrate is used as a film polymer in nail polish. The addition of
plasticizers gives the film polymer more flexibility and makes it more resistant to
breaking. Nowadays acetyltributyl citrate is usually used as the plasticizer. Camphor
is still used because it is a good plasticizer; phthalates are sometimes used. An
important constituent of nail polish is resins such as alkyd, sulphonamide and acrylic
resins. Used together with cellulose nitrate they increase the bond and the shine of
the nail polish.
The viscosity must be suitable to allow the polish to be applied to the nails easily;
the evaporation speed is also important. The drying time of nail polish should be
between 3 and 5 minutes.
To colour nails, pigments are usually added to nail polish, in the same way as for
blusher and eye shadow. Both organic pigments and inorganic pigments such as
titanium oxide are used. Pigments are coloured, solid substances whose particles
disperse in the solvent; they are physically or chemically inert.
47
Nail polish removers. Nail polish can be removed using organic solvents. The nail
polish remover is applied to a piece of cotton wool or a cotton wool pad, and is then
used to remove the nail polish from the nails. In this way the skin surrounding the
nails can come into contact with the remover, thus degreasing the skin. Some
removers contain moisturisers.
The general composition of nail polish remover is:
- 66 % acetone
- 20 % ethyl acetate
- 5 % butyl acetate
- 1 % lipids (e.g. lanolin derivative)
- 8 % water
- colouring
- perfume
Nail hardener. This product is used to harden weak and breakable nails. Nail
hardener is applied to the nails using a fine brush. These hardeners contain 5 – 10
% potassium aluminium sulphate or 0.2 – 5 % formaldehyde. Nail strengthener is
used to strengthen weak and breakable nails. The product is applied on top of the
nail base coat. There are cream products which some moisturising ingredients and
there are products which are applied using a fine brush, just as with nail polish. The
composition is approximately equal to that of ordinary nail polish, but without
colouring.
They often contain toluene-sulphonamide-formaldehyde co-polymer synthetic resins.
The general composition of nail strengthener is:
- approximately 80 % water
- approximately 5 % formaldehyde
- approximately 1% lactic acid
Hard artificial nails are attached to the fingernails or toenails using glue. These
products are not only used for broken, torn or too short fingernails, but are also used
on a large-scale for decorative purposes on ‘normal’ nails. A typical set contains glue
and artificial nails. The glue for applying the artificial nails contains:
- methyl, ethyl, butyl, cyclohexyl, and allyl esters of α-cyanoacryl acid;
- thickeners;
48
- stabilizers such as hydroquinone, N,N-dimethyl-p-toluidine.
The artificial nail contains acrylic resins, PVC (polyvinylchloride) and phthalate
plasticizer. The real nail underneath can be damaged when the artificial nail is
removed.
Nitromethane is used as a solvent to remove hard artificial nails [RIVM report
320104001/2006; DEPA, 2008].
‘Liquid’ artificial nail. A professional nail stylist can use artificial nails to enhance
broken and/or nails that are too short. To do this, the stylist mixes liquid (monomer)
and polymer powder and applies this to the nails using a fine brush. The liquid nails
harden within 5 minutes due to polymerisation. A set for the application of artificial
nails by a nail stylist contains 1 g of polymer powder and 14 g of monomer-liquid,
combined with mixing palettes and spatulas.
The powder consists of:
- approximately 98 % acrylic-type polymer (e.g. polyalkylmethacrylate)
- approximately 2 % initiator (e.g. benzoyl peroxide)
An often used liquid is:
- approximately 99 % acrylic-type monomer (methyl, ethyl, or butyl
methacrylate)
- approximately 1 % stabiliser (e.g. hydroquinone)
Another possible composition for the liquid is:
- approximately 70-90 % acrylic-type monomer (ethyl methacrylate)
- approximately 5-20 % flow control agent
- < 10 % crosslinker
- < 1% plasticizer (e.g. dibutyl phthalate)
- < 1% UV-protection
- < 1 % activator for the initiator (e.g. N,N-dimethyl-p-toluidine)
- < 1 % stabiliser (methyl ester of hydroquinone)
Another system of achieving artificial nails is that of light-cured nail gels. These UV-
gels contain photo-bonded acrylates that harden on the nails under the influence of
UV-light. This is a viscous solution consisting of various acrylates which is applied
directly onto the nails. The acrylates include methylacrylated and acrylated
urethanes, triethyleneglycol dimethacrylate, methacrylated epoxy resin and hydroxyl
functional methacrylates. Artificial nails are applied by professionals or semi-
professionals. These products are sold directly to the public on a limited scale. They
49
should be applied to healthy nails and may not be used on nails that are infected by
micro-organisms. These ‘liquid’ artificial nails can only be removed using
nitromethane.
Peeling and scrubbing. Peeling creams or gels are used to cleanse the skin of the
face, to stimulate blood circulation and/or to achieve ‘soft’ skin. They remove the
uppermost layer of the epidermis. According to the instructions a peeling gel can be
used once or twice a week. The gel should be applied to the moist facial skin and
then rinsed off with water. A face cream is then applied. Peeling-gel is based on
water with water-soluble polymers, to which ‘abrasives’, humectants, surface-active
ingredients, preservatives, colouring and perfume are added. Plastic granules,
ground nutshells or fruit stones and silicates are used as the abrasives [RIVM report
320104001/2006].
Face packs. In a similar way as for peeling gels, face packs are used to cleanse the
skin of the face, to stimulate blood circulation and to achieve a ‘soft’ skin. Face packs
have a relaxing effect. Ready to use face packs are available, such as gel, mud and
peel-off face packs. They are also sold in powder form. This type of peel-off face
pack is made of 50 % silicates and 50 % gel-forming agents, such as sodium
carbonate, calcium sulphate and sodium alginate. When this powder comes into
contact with water, calcium alginate is formed. This substance ensures that a film
layer is formed on the skin. There are also algae face packs, which contain minerals
and trace elements.
After mixing the powder with water, the mixture can be applied to the face. As the
face pack dries, the skin contracts and cools off due to evaporation. This gives a
refreshing feeling. After approximately 20 minutes, the face pack is removed with
water or is peeled off. Face cream is then applied to the skin.
Sachets of face pack powders are sold, each containing 10 or 15 g of powder. One
tablespoon of water needs to be added to this powder before use. Sachets
containing 15 to 20 ml of gel face pack are also available; these are ready to use
[RIVM report 320104001/2006].
50
Table 2.6. Composition of some personal care products
Ingredients Peel-off face
Packs
Mud packs
Gel packs
Water 40-80 % 40-80 % 40-80 %
Ethanol up to 15 % 5-10 % 5-10 %
Lipids up to 15 %
humectants1) 2-15 % 15-25 % 15-25 %
Film polymers 10-30 % 1.5 %
Powder
- silicates, titanium
dioxide
up to 20 % 20 %
Surface-active
ingredients up to
2 % 1%
Clay minerals 2 %
Alkali 0.5 %
Other ingredients
preservative X x x
perfume X x x
colouring X
buffer X
1) moisturizing compounds
x: ingredient in face packs
Mud bath / clay bath products. During a mud bath or clay bath, a mixture of mud
and cream is rubbed onto the body. There are also products consisting of powder
that need to be mixed with water. Another possibility is that the body is treated with
an algae pack, consisting of a gel-like algae substance. After application, the body is
wrapped in film. It has to be left on for 20 minutes at approximately 35o C, after
which the body is rinsed off with water. This type of mudpack is usually part of a
‘beauty-day’. Those who attend such a day usually do so only a few times a year.
Mud baths contain clay minerals and inorganic salts. For example, Dead Sea mud
contains 28 % salts. Algae packs contain minerals and trace elements, including
iodine.
51
Skin whitening products. Dark-skinned people who want to lighten their skin colour
as much as possible can use bleaching agents or ‘skin whitening creams’. In addition
to the bleaching agent, the cream contains UV-filters.
As of 1 January 2001, bleaching agents with hydroquinone as active ingredient are
no longer permitted in the Netherlands. The use of creams with hydroquinone had
been permitted only on small areas. These creams are intended to bleach skin that
contains excessive amounts of pigment (hyperpigmentation) [RIVM report
320104001/2006].
2.9.4. Oral hygiene products
Toothpastes. The general composition of a toothpaste is:
- fine abrasive
- cleaning agent: lauryl ether sulphate, alkylpolyglycolethers, alcohol
ethoxy/propoxylates
- fluoride (maximum 0.15 %): the fluoride-level in children’s toothpaste: maximum
0.038 %
The amount of toothpaste that a young child swallows when brushing their teeth is
very different to the amount that an adult swallows. For example, for a 2.5 years old
child which brushes its teeth 1-2 times a day, the amount ingested has been
estimated to 0.53g. On the contrary, for adults the corresponding amount is 0.08g
[RIVM report 320104001/2006].
Toothbrushes are products, which are used approximately two times daily.
Consequently, chemical substances in toothbrushes are substances, to which the
consumers might be exposed, in case the substances are released. Toothbrushes are
put in the mouth, and many times small children also put the wrong end of the
toothbrush in the mouth and bite into and suck the toothbrush for a rather long
time. The expose for chemical substances from toothbrushes takes place by
ingestion through the mouth and at skin contact. The exposure can happen to all
people at all ages.
52
Mouthwash solutions can contain disinfectants such as cetylpyridinium chloride,
benzoate, chlorohexidine, bromochlorophene. These substances are meant to kill
(harmful) micro-organisms.
2.9.5. Feet care products
Antiperspirant creams are applied after cleaning the feet, lightly rubbed in, in the
morning and evening. Aluminium compounds are added as antiperspirants, for
example aluminium capryloyl hydrolyzed collagen.
Anti-fungal products are effective against infections caused by fungus, yeast and
certain bacteria. For fungal infections the infected parts of the feet are washed, dried
carefully and then the cream is applied. The cream is applied in the morning and
evenings until the infected areas have cleared up totally. For fungal infections of the
nails the cream is applied to the affected nails. For the dermal exposure the amount
that is applied to the nail is not important, only the amount that is applied to the skin
[RIVM report 320104001/2006].
2.9.6. Baby care products
Baby salve. Baby salve is used for babies’ sore bottoms. The composition of the salve
is like those for creams. Baby salve can contain 15 % zinc oxide (ZnO). The zinc
oxide salve is used frequently in the first months of life; its use usually tails off
gradually. If the salve is used then the frequency is 2 x/day [RIVM report
320104001/2006].
Baby oil. The most important ingredient of oil is the triglycerides of fatty acids and
glycerine. There are vegetable and animal oils. No European data were found about
the amount used and the frequency of use.
Baby powder. A ‘typical formula’ for baby powder is the following:
- 93 % talcum powder;
- 3 % zinc oxide;
- 4 % magnesium stearate;
other ingredients:
- germicides;
53
- perfume.
2.9.7. Fragrances
Perfume is a composition of fragnances that emit a pleasant odour. A fluid
preparation of natural essences (as from plants or animals) or synthetics and a
fixative is used for scenting. Perfume oils are often diluted with a solvent, though
this is not always the case, and its necessity is disputed. By far the most common
solvent for perfume oil dilution is ethanol or a mixture of ethanol and water. Perfume
oil can also be diluted by means of neutral-smelling oils such as fractionated coconut
oil, or liquid waxes such as jojoba oil. The intensity and longevity of a perfume is
based on the concentration, intensity and longevity of the odorous compounds
(natural essential oils / perfume oils) used: as the percentage of aromatic
compounds increases, so does the intensity and longevity of the scent created.
In perfumes, eau de toilette and eau de cologne the concentration of fragrances
determines the difference between the products. A perfume contains the highest
concentration of a fragrance(s). They are made up of various components such as
aromatic oils, which in turn contain numerous hydrocarbons, fixing agents, modifiers
and usually ethanol as a solvent.
Natural fragrances there are also synthetically prepared fragrances. A perfume is
made up of the individual components of a mixture of fragrances. These are carefully
tuned to each other to produce a new aroma. The various types of perfume also
contain a fixing agent that slows down the evaporation rate of the volatile
ingredients. The fixing agent also refines and extends the ‘heart beat’: the essential
fragrance that is formed after application must remain for between 2 to 4 hours.
Examples of perfume fixative are balsam of Peru, coumarin and musk. Finally there
are modifiers. These fragrances support the main ingredients in the composition or
they create a special effect.
The perfume is sprayed onto the skin at pulse points, such as on the wrist and in the
neck under the ears. To keep the essence of the fragrance, it is best to spray the
eau de toilette on the hand and then to let it evaporate. Consumers apply less eau
54
de toilette when the concentration of fragrance is higher than when the
concentration is lower. This also depends on the composition of the fragrance that is
used. Due to the high concentration of fragrance in perfume, only a small amount
needs to be used.
Perfume can be applied using a pump spray (or a stick). Eau de cologne, with its low
concentration of fragrance, is sprinkled on the body or onto a handkerchief and then
dabbed on the face or neck [RIVM report 320104001/2006].
Table 2.7. Composition of perfumes
Fragrance (%) Ethanol (%)
Perfume
15-20
12-20
10-25
15-30
75-90
Eau de perfume 7-15
Eau de toilette
5-12
2-8
5-10
80-85
Eau de cologne
2-6
2-5
60-80
2.9.8. Deodorants
Deodorants are used in an aerosol can, as a stick (solid) or as a roller (liquid). A
limited number of deodorant sprays contain an antiperspirant as ingredient while
anti-bacterial agents are used to suppress the proliferation of bacteria on the skin
which are responsible for body odour. Some preparations use essential oils
(perfume) as an anti-bacterial agent. Because ethanol degreases the skin, one of the
additives in deodorants acts as an agent to ‘put-back’ lipids to the skin [RIVM report
320104001/2006].
55
Table 2.8. Composition of deodorants
Ingredients
Stick Roller
Spray
Propellant
(iso-butane,
dimethylether)
50-60 %
Solvent (ethanol,
water)
37-47 %
Ethanol 10 %
Water 60-80 %
Carrier liquid 60 %
Lipids 5% 5-15 %
Surface active agent 8% 2-5 %
Polyol 5 %
Antiperspirant 10 % 10 %
Anti-bacterial agent 0.5 % 1-3 %
Perfume 1.5 % 0.3 % 1 %
Additives 2.5 %
56
2.10. Printed material
Paper is historically the most important information carrier. Cellulose, its most
prominent structural component, is a stable polymer in appropriate molecular
environments. While acidity promotes hydrolysis of cellulose and certain transition
metals promote its oxidation, they are both components of iron gall inks, arguably
the most important Western inks [Strlick et al., 2010].
Iron gall ink was in use until the first half of the 20th century and was generally a
mixture of vitriol (FeSO4 with impurities), gallotannins and gum Arabic, but could
contain various additives. Various stabilisation treatments have been proposed
tackling both the problem of acidity and that of transition metals. Treatments
containing various antioxidants, from preventive antioxidants to radical scavengers
and peroxide decomposers have been tested and some have been introduced into
practice.
57
2.11. Toys
An individual toy can cause exposure in different ways. A cuddly toy can be
mouthed, but there will also be intensive dermal contact with the hands and face. A
large number of toys are mouthed (sucked and chewed), including toys which are
not made for that purpose, such as cars, pens and clothes.
Toys can only be placed on the market if they satisfy EU legislation on safety
requirements for toys, or if they are produced in compliance with a prototype that
has been approved by a competent body in an EU country. Toys that meet these
safety conditions must be marked with a CE mark before they can be placed on the
market.
The EU legislation on safety requirements for toys also includes the EN71 series on
safety requirements for toys and the High Voltage Declaration for electrical toys. One
of the points covered by EN71-3 (Section 3: Migration of specific substances)
concerns threshold limits for the migration of metals when children put toys into
their mouths. In addition, toys must not contain dangerous substances or
preparations, as defined in directive 67/548/EEC and 88/379/EEC in amounts that
can harm the health of children.
According to REACH, Annex XVII, entries 51 and 52, it is forbidden to use, import or
sell toys and childcare products for children less than 14 years of age containing the
phthalates DEHP, DBP and BBP in concentrations above 0.1%. DINP, DIDP and
DNOP are forbidden to use, import or sell in concentrations above 0.1% in toys and
childcare products that children are able to put in their mouths.
The REACH regulation 1907/2006 also covers aromatic toys (products which
intentionally have a smell). In these cases, the aroma produced by the toy must be
registered with the Chemicals Agency if the amount equals or exceeds 1 ton per year
(EU regulation no. 1907/2006).
The Association of Toy Manufacturers in Denmark that counts seven of the largest
manufacturers of toys in Denmark, evaluates that less than 1% of the total amount
58
of toys is produced from foam plastic e.g. foam floor puzzles, activity carpets, books
etc. [DEPA, 2006]. The appearance and shape of foam floor puzzles means that they
are often used as a soft playground for children of less than 3 years old. They may
also be used as nursing carpet, which involves full body contact. These puzzles are
usually marked “for children of one year or more”. Activity carpets are recommended
for children from birth. The use of an activity carpet involves full body contact and
children may spend a lot of time on it. Children are also expected to mouth the
product.
In the shops, there are many toys, which are rubbery and slimy, e.g. “slimy balls”
and “sticking animals”. A lot of these types of toys are sold as unique batches, which
are only on the market for a short period. The toys are very popular, not very
expensive and are consequently bought by the children themselves [DEPA, 2005].
Soft toys are typically used extensively by infants. Some children play with them,
others sleep with them, and there are those who are so closely attached to them
that they are carried around most of the time. Most 2-year-olds (the target group of
a survey conducted by the Danish Ministry of Environment, 2009) must however be
presumed to have one or more soft toys which they will cuddle or suck on during the
night. As such, exposure occurs when the child is holding the soft toy, and at
possible release of various chemical substances.
A soft toy may consist of many parts. For example, the fur, the eyes and the nose
may be made from different materials such as textiles and polymers, and it may be
equipped with a bowtie or be clothed. Additionally, there is a kind of soft toys
designed to be heated in the microwave to give off a scent e.g. lavender scent.
According to the above mentioned Danish survey [DEPA, 2009], while soft toys cover
a very wide product area scented soft toys do not represent a large portion, hence
soft toys were surveyed in general.
2.12. Pet care products
To control fleas and their larvae around dogs and cats, the place where the dog
and/or cat sleeps or lies down is treated with a powder pet care product. Cracks,
59
crevices and surfaces can be treated with the insect powder. Up until April 1995 a
flea powder was permitted which was sprinkled over the animals’ fur and rubbed into
the skin. The current thinking is: for the effective control of fleas it is necessary to
treat both the area around your cat or dog and the animal itself with a registered
product designed for this purpose. Active substances in dusting powders to control
fleas and their larva are deltamethrin, permethrin and propoxur [RIVM report
320005002/2006]. Pets are usually treated outside and it would be expected that the
residues disappear quickly outside, but no specific research has been found.
Residences, feeding and drink troughs for aviary birds, pigeons and chickens, but
also for dogs and cats are disinfected when the animals have contracted a fungal,
viral or bacterial disease. Disinfectant for fumigation with active ingredient
paraformaldehyde is permitted as a disinfectant for bird residences. However, not
only dry disinfection takes place. Both disinfectants for fumigation and Halamid with
active ingredient sodium-p-toluenesulphonchloramide are regularly mentioned on the
internet for consumer application [RIVM report 320005003/2006].
Not adequate research has been carried out about emissions from pet care products.
2.13. Flowers and plants
Houseplants are usually treated outside and someone would expect that residues
would disappear quickly outside but no relevant research has been found. Most of
the products used for the treatment of flowers and plants fall in the category of pest
control products. However, no relevant studies were found in the literature review.
2.14. Decoration and maintenance
During the decoration and maintenance activities of a building or any indoor
environment many of the products used might contribute to significant emissions of
indoor pollutants. In the frame of these activities, many elements of the indoor
environment may be changed, such as floorings, carpets, wall papers, furnishing,
painting, gypsum board constructions, ceilings, kitchen cabinets etc.
In the frame of the BUMA project [2009], the materials that might be used during
the construction, decoration and maintenance activities of an indoor environment
60
were studied and prioritized for their emissions of specific compounds (Table 4 of the
Appendix).
61
3. HEALTH RELEVANT EMITTED COMPOUNDS
3.1. Criteria for choosing the targeted compounds
The selection of the target compounds was based on knowledge of the consumer
product composition, derived from the literature review and the knowledge of
substances hazardous to humans. More specifically, the following criteria were set in
order of the target compounds to choose:
Gaps on the emissions of chemicals and particles identified from the market
survey and the BUMA database, associated with the use of 20 products from
the consumer product classes
Priority compounds under INDEX, SCHER, WHO;
Other compounds of known health effects and considered relevant for
indoor air exposure;
Compounds of special interest indoors i.e.;
◦ Compounds emitted in “significant” amounts;
◦ Compounds that may cause other health effects apart from
respiratory (i.e. irritations)
In the Appendix - Table 6 are presented the target compounds as they have been
chosen from the priority compounds of INDEX, SCHER and WHO. In the same table,
compounds of special interest for investigation under the EPHECT project are also
presented.
The following table summarizes the key pollutant compounds regarding the EPHECT
project.
Table 3.1.
EPHECT - LIST
OF KEY AND EMERGING
POLLUTANTS
Listed
in WHO
INDEX
IAQ
Model
BAMA Sensory
irritation (eyes/
up.
airways) Estimated
LOAEL mg/m3
Odour thresholds
mg/m3
Notes
62
ACROLEIN x LOAEL:
0.21 mg/m3
(Weber-
Tschopp et al., 1977)
0.008
(Nagata, 2003)
Sensory
Irritant
FORMALDEHYDE x x x x NOAEL: 0.63
mg/m3
(Lang et al., 2008)
at or below 0.1 mg/m3 without
interfering
background(Wolkoff and Nielsen, 2010)
110 ppb (Berglund et al., 2012)
Sensory irritant
IARC 1
According to WHO 2010 it
is not assessed as a
sensitizing
compound
BENZENE x x x x 8.7 (Nagata, 2003) IARC 1
Naphthalene x x (x) 0.44 (Amoore and
Hautala, 1983)
Lung
inflammation
Not a sensitizer
(WHO 2010)
TERPENOIDES: Limonene
-Pinene
linalool, geraniol, a-terpineol
X
X
x LOAEL (a-pinene):
450 mg/m3 (Falk et al.,
1990)
0.045 (Cain et al., 2007)
0.10 (Nagata, 2003)
Not known
Odorous compounds.
Not sensory irritants – very
high thresholds for
sensory
irritation, see (Wolkoff,
2010, 2012). No indication
that these
compounds are airway
sensitizers, however,
some concern
that some of their oxidation
products may have
sensitizing properties
(see Radical
products).
AMMONIA x (x) 1.0
(Nagata, 2003)
Odorous
compound
Sensory irritant
(Nielsen et al., 2007)
QUATERNARY
AMMONIUM CHLORIDES
Benzalkonium
salt Emerging
Potential lung effects,
however,
63
chloride exposure
expected to be low
CHLORAMINE x - Emerging
SILOXANES x/-
perfluorinated
- Emerging
A number of
lung injury cases have
been reported about use of
spray coating
products. Severe lung
effects, if per-fluorinated
(Nørgaard et
al., 2010; Pauluhn et al.,
2008).
RADICAL
PRODUCTS FROM
OZONE CHEMISTRY
ROS or OH radical as metric (Borm et al., 2007)
x (x) - Emerging
SHER
One of the key VOC is
formaldehyde. However,
there is some
concern about some of the
poly-functional
oxygenates may have
sensitizing
effects (Anderson et
al., 2010; Forester and
Wells, 2009)
(to be investigated in
OFFICAIR; (Wolkoff et
al., 2012)).
There is also some concern
about the radical
formation may have oxidative
properties.
ULTRAFINE PARTICLES
(x) - Emerging
2-BUTOXYETHANOL
0.21
(Nagata, 2003)
Odorous
compound Review on
health effects
64
(Multigner et
al., 2005; Louisse et al.,
2010), not
relevant, see SCOEL 2007
and IARC 2006
documents
3.2. Key emission substances with potential health relevant impact
3.2.1. Introduction
Millions of Europeans spend more than 90% of their time indoors: at home, in the
office, factory, school, restaurants, theatres, etc. The combination of the generally
higher indoor concentrations and the overwhelming fraction of time spent indoors
results in the overall domination of indoor air pollution exposures. Indoor air
pollution may cause or exacerbate illnesses, increase mortality, and have a major
economic and social impact (Mendell et al., 2002). Air pollution in indoor
environments has been linked to a number of reported adverse health effects,
including the so-called ‘Sick Building Syndrome’, SBS (where the symptoms include
eyes, nose, throat, skin irritation, headache and tiredness), irritative effects, allergic
responses that trigger asthma episodes, oxidative stress, inflammation and
neurogenic effects, aggravation of chronic obstructive pulmonary disease (COPD)
and cardiovascular diseases (CVD). Large-scale European surveys have reported a
general increase of the prevalence of allergies, asthma and other respiratory
diseases. Among other factors, this trend was associated with adverse health effects
of indoor as well as outdoor air pollution that includes particles; however, so far, few
chemical compounds (acid anhydrides and isocyanates) have been directly identified.
Adverse effects of particle origin are particularly exerted towards susceptibles
subjects, namely children, the elderly and people affected by diseases (SCHER
report, 2007).
Consumer products represent a source of ubiquitous pollutants in indoor
environment that influences indoor air quality in dwellings. Certain consumer
products, such as personal care products, cleaning agents, air fresheners etc, may
emit hazardous and other health relevant air pollutants. Despite hygienic or aesthetic
65
benefits, some consumer products may increase the risk of health effects by the
inhalation of particulate matter, volatile and semivolatile compounds, and secondary
pollutants formed by reactive chemistry and degradation (ECA report, 2006).
Particulate matter (PM)
Results from experimental toxicity studies and epidemiological studies demonstrate
the negative effect of indoor PM on health. The majority of observed health effects
related to indoor PM are in the respiratory tract, in terms of chronic obstructive
pulmonary disease (COPD), asthma, wheezing and cough. Indoor sources include
combustion of wood burning (any combustion), incense burning, cooking processes
and candle burning. Other important source of combustion products is traffic.
Volatile and semi-volatile compounds
The concern about exposure to SVOCs is also linked to their occurrence in home
dust, which could lead to non-negligible exposure through ingestion, in particular for
infants. The contribution of settled dust to human exposure could represent a large
part of the total exposure for some phthalates and PBDEs. Further, skin sorbtion is
an important source of exposure to SVOCs.
Formaldehyde - Predominant symptoms and signs of formaldehyde exposure in
humans are irritation of the eyes, nose and throat, together with concentration-
dependent discomfort, lacrimation, sneezing, coughing, nausea and dyspnoea.
Repeated exposures are not associated with more severe effects and/or lowering of
the threshold concentration, though indication on the opposite still exist (Wolkoff and
Nielsen, 2010); consequently, short-term concentrations are predictive of these
effects also after long-term exposure.
Benzene - It is readily absorbed from oral and inhalation exposures. Less than 1% is
absorbed through the skin. The acute toxicity of benzene is low. Major concerns of
systemic benzene toxicity include myelogenous leukaemia. This disease has been
typically seen in chronic and subchronic occupational exposures, but may be of
concern following indoor exposures as well (World Health Organization Statistics IAG,
2010).
66
Naphthalene - Respiratory epithelium is the main target of chronic naphthalene
exposure. Adverse health effects include the onset of hyperplasia, atrophy, chronic
inflammation, hyaline de generation of olfactory epithelium. Reports have established
associations between naphthalene exposure and haemolytic anaemia or cataracts
following acute exposure or occupational exposure to naphthalene. A relationship
appears to exist between an inherited deficiency in the enzyme, glucose 6-
phosphate dehydrogenase (G6PD), and susceptibility to naphthalene-induced
haemolysis. Overall, the balance of evidence indicates that naphthalene is not
genotoxic (IAG 2010).
Acetaldehyde - The critical health effects arising from exposure to airborne
acetaldehyde are eye and upper respiratory tract irritation, with the possibility of
chronic tissue damage and inflammation in the respiratory tract following long-term
exposure. The threshold for sensory irritation, however, is too high to be relevant in
indoor air (Wolkoff, 2010).
Toluene - Toluene has low acute toxicity. Human effects on the central nervous
system are considered as the most sensitive effects in both short- and long-term
inhalatory exposure to toluene. There has been no indication that toluene is
carcinogenic in bioassays conducted to date and the weight of available evidence
indicates that it is not genotoxic [IAG 2010].
Xylene - Despite its structural similarity to benzene, xylene does not influence
haematopoiesis. Acute controlled exposure studies have identified self-reported
symptoms of irritation (e.g., watering eyes and sore throat) or neurological
impairment (e.g., mild nausea, headache, altered reaction time and altered balance)
as potential effects of xylene following inhalation exposure in humans, mostly
observed on industrial sites.
Limonene - In general, limonene is a chemical with low acute toxicity, with the
exception of its irritative (skin, eyes) and sensitizing properties [WHO, 1998].
Potential hazard to the general population are skin irritancy and sensitisation from
use of consumer products, varying with the concentration of limonene in the product
and, for sensitisation, with its oxidation status (addition of oxidised limonene to the
list of substances used in allergy testing has been recommended). No information is
67
available on the chronic health effects of inhalation exposure to d-limonene in
humans, and no long term inhalation studies have been conducted in laboratory
animals (Andersson et al., 1997; Wolkoff and Nielsen, 2001).
3.2.2. Indoor air chemistry
There is increased concern about the potential health impact of indoor air chemistry,
in particular of products resulting from ozonolysis of terpenes that include ultra-fine
particles (UFP) and fine particles. However, it is clear that more research is required
before definite conclusions can be reached (ECA report ,No 26).
A few epidemiological studies have indicated that reactive chemistry may have been
responsible for reported sensory irritation symptoms (eye, skin etc.). Specifically, a
number of studies related to cleaning activities, both professional and domestic,
indicate an increased prevalence of asthmatic symptoms among the personnel
[Medina et al, 2005].
Based on bioassay studies, human exposure studies and epidemiological studies, the
respiratory tract seems to be the principal target site for both acute and chronic
effects of terpene/ozone reaction products, including UFP.
The formation of unidentified strong upper airway irritants in reaction mixtures of
terpenes and ozone has been recently reported. Identified products included
formaldehyde (major key irritant along with polyoxygenated VOCs, Wolkoff et al.,
2008) and other aldehydes, carboxylic acids, and peroxides. Their potential to cause
irritation at low concentrations is unclear; however, odour annoyance due to their
usually low odour thresholds could cause subjective reactions.
Maximum irritation of reaction mixtures of limonene and ozone, measured in mice,
was observed at low humidity (<2% RH) and short time (16-30 s) reaction mixtures.
Moderate humidity (approximately 32% RH) and longer reaction times (60-90 s)
resulted in significantly less irritation, suggesting that some unidentified
intermediates react with water vapor to give less irritating products; alternatively,
the mucous membranes are more robust at high relative humidity. Irritation
measured at four ozone concentrations (1, 2, 4 and 7 mg/m3) using low
humidity/short time reaction conditions for limonene (280 mg/m3) and isoprene
68
(1400 mg/m3) revealed that at 1 mg/m3, irritation was at the same level as that for
the pure terpenes, indicating that at 1 mg/m3 ozone the combined irritant effect was
near the no effect level for the product mixture.
Findings of both animal and human exposure studies indicate that gaseous
limonene/ozone and pinene/ozone reaction products may cause sensory irritation of
the eyes and upper airways at ozone and terpene concentrations that are close to
high-end values measured in indoor settings. However, full scale studies are
necessary for further substantiation.
Further research is needed to better define the role of UFP generated by ozone
(mainly from outdoor but sometimes also from indoor sources such as laser printers
and copiers and terpene (s-limonene and -pinene) reactions in the observed
effects, given that whether UFPs or the gaseous oxidation products of
terpenes/ozone reactions are responsible for the biological observed response
remains controversial. Moreover, no specific literature is available on potential long-
term health effects. Still, (McDonald et al., 2010; Wolkoff et al., 2008) and (Delfino
et al., 2008) indicate that gaseous products may be more important, and that indoor
generated SOA are less important.
However, the relationship observed in epidemiological studies between ozone
exposure and health effects could be hypothesized to be partially due to the action of
products of ozone-initiated indoor chemistry, including particles, given that people
usually spend most of their time indoors.
3.3. Brief overview of respiratory effects associated with handling of consumer products within air fresheners, cleaning and maintenance products
Background
The purpose of this part is to provide a brief overview of studies within epidemiology
and exposure studies in context of cleaning, consumer products, and personal care
products and associated respiratory diseases, excluding cancer. Respiratory diseases
in children are also excluded from this overview. In addition to already compiled
literature, a brief literature search in the PubMed database was carried out with
69
defined search profiles, see Table 3.2 for results. The search was screened and
papers deemed relevant for indoor air were selected on the basis of abstract and
title. The overview will only select some of the identified studies for further
discussion.
Table 3.2. Results of literature search in PubMed (2012-2002).
Search profile in PubMed (medio
February 2012)
Papers deemed relevant; *
= review paper
Total
Air freshener and asthma 0 3
Air freshener and lung effects 0 0
Air freshener and respiratory effects 0 0
Consumer products and asthma (Zock et al., 2007)* 39
Consumer products and lung effects (Pauluhn et al., 2008) 59
Consumer products and cardiovascular
effects
0 47
Consumer products and airway effects (Elberling et al., 2004) 8
Cleaning and asthma (Corradi et al., 2011)
(Arif and Delclos, 2012)
(Vizcaya et al., 2011)
(Choi et al., 2010a; Choi et
al., 2010b)
(Quirce and Barranco,
2010)*
(Mäkelä et al., 2011)
(Bello et al., 2010)
(Sastre et al., 2011)
(Hoy et al., 2011)
(Heinrich, 2011)*
(Zock et al., 2010)*
(Obadia et al., 2009)
(Bernstein et al., 2009)*
(Delclos et al., 2009)
(Arif et al., 2009)
(Barnes et al., 2008)
(Delclos et al., 2007)
148
70
(Nielsen et al., 2007)*
(Mirabelli et al., 2007)
(de Maçãira et al., 2007)
(Nickmilder et al., 2007)
(Jaakkola and Jaakkola,
2006)*
(Medina-Ramón et al., 2006;
Medina-Ramón et al., 2005;
Medina-Ramón et al., 2003)
(Rosenman, 2006)*
(Zock et al., 2002)
Cleaning and airway effects (Sastre et al., 2011)
(Quirce and Barranco,
2010)*
(Choi et al., 2010b)
(Gorguner et al., 2004)
(Hoy et al., 2011)
(Nielsen et al., 2007)*
(Jaakkola and Jaakkola,
2006)*
(Rohr et al., 2002)
49
Cleaning and lung effects (Mäkelä et al., 2011)
(Sastre et al., 2011)
(Hoy et al., 2011)
(Petrova et al., 2008)
(Sunil et al., 2007)
(Medina-Ramón et al., 2006)
47
Cleaning and respiratory diseases (Arif and Delclos, 2012)
(Vizcaya et al., 2011)
(Quirce and Barranco,
2010)*
(Mäkelä et al., 2011)
(Sastre et al., 2011)
(Hoy et al., 2011)
(Tonini et al., 2009)
130
71
(Charles et al., 2009)
(Zock et al., 2009)
(Bello et al., 2009)*
(Arif et al., 2009)
(Mirabelli et al., 2007)
(de Maçãira et al., 2007)
(Nickmilder et al., 2007)
(Delclos et al., 2007)
(Orriols et al., 2006)
(Medina-Ramón et al., 2006;
Medina-Ramón et al., 2005)
(Gorguner et al., 2004)
(Medina-Ramón et al., 2003)
(Rosenman et al., 2003)*
(Zock et al., 2002)
Fragrances and asthma (Quirce and Barranco,
2010)*
(Hoy et al., 2011)
(Holst et al., 2010)
(Caress and Steinemann,
2009)
(Millqvist et al., 2008)
(Elberling et al., 2007)
(Harth et al., 2007)
(Elberling et al., 2005a)
19
Fragrances and respiratory effects (Quirce and Barranco,
2010)*
(Hoy et al., 2011)
(Schnabel et al., 2010)
(Schnuch et al., 2010)
(Millqvist et al., 2008)
(Elberling et al., 2007)
(Elberling et al., 2006b)
(Elberling et al., 2006a)
19
72
(Elberling et al., 2005b)
(Dayawansa et al., 2003)
Personal care products and asthma (Arif et al., 2009; Delclos et
al., 2009)
37
Personal care products and airway
effects
0 2
Personal care products and respiratory
effects
(Arif et al., 2009) 16
Airway effects and cleaning (epidemiology)
Several reviews on the basis of epidemiological studies have discussed associations
between work-related airway effects (asthma) and exposure to cleaning, in particular
among cleaning personnel (Bernstein et al., 2009; Jaakkola and Jaakkola, 2006;
Quirce and Barranco, 2010; Rosenman, 2006; Zock et al., 2010), biocides in
consumer products (Hahn et al., 2010), and personal care products (Bondi, 2011).
Recent studies continue to identify associations between use of cleaning agents and
respiratory diseases, e.g. bronchial hyperresponsiveness (Arif and Delclos, 2012),
and use of detergents in hospitals (Corradi et al., 2011),
The key conclusion from these studies is the potential association between use of the
agents and respiratory effects, although no specific chemical has been identified, yet.
Table 3.3. Compounds tentatively associated with respiratory diseases among
cleaning personal.
Sensitizers:
Amines, e.g. (e.g. ethanolamine)
Disinfectants
Quaternary ammonium compounds
Fragrances containing terpenes
Isothiazolinones (formaldehyde
releasers)
Chlorine bleach (hypochlorite)
Glutaraldehyde
Sensory irritants:
Chlorine (bleach) (hypochlorite)
Ammonia
Hydrochloric acid
Monochloramine
Mixing bleach and acid or ammonia
Sodium hydroxide (caustic soda)
Quaternary ammonium compounds
Monoethanolamine
73
However, several compounds of concern have been suggested. Among these are the
following cleaning related agents (sensitizers or sensory irritants) believed to cause
work-related airway symptoms, see Table 3.3, but not fragrances (Quirce and
Barranco, 2010). (Zock et al., 2010) summarized that “the most important products
that have been repeatedly reported include products in spray-form, chlorine bleach
and other disinfectants”. Zock and colleagues further concluded that “many cleaning
agents are respiratory irritants and have some sensitizing properties”. A statement
that is also used by the research group to explain reported symptoms, e.g. (Vizcaya
et al., 2011). However, except for chlorine (chloramines), formaldehyde and
glutaraldehyde, thresholds for sensory irritation (chemesthesis) of organic volatiles,
that include fragrances, in cleaning agents are by far too high to be causative of
sensory irritation in eyes and the upper airways (Wolkoff, 2010; Wolkoff, 2012).
Further to the above, “we should not be so naïve as to transfer these findings from
occupational settings to our daily cleaning activity in our homes” as stated by
(Heinrich, 2011).
(Caress and Steinemann, 2009) carried out random national telephone interviews
and determined the prevalence of individuals in the US population reporting adverse
effects from exposure to fragranced consumer products. The outcome of the study
indicated 19 % of the population reporting adverse health effects from air fresheners
and 11 % reported sensory irritation from scented laundry products. Telephone
interviews and the questions therein may be strongly biased as pointed out by
(Wasserman and Keith, 2009). The entire discussion about the impact of olfaction
from fragrances is very complex due to a number of factors as partly presented by
(Wolkoff, 2012).
Elberling and colleagues have reported in a number of questionnaire studies that, in
general, adult people (mainly adult women) already with perceived or recognized
skin atopy (contact allergy) also self-report symptoms (bronchial hyperreactivity)
related to inhalation of airborne chemicals, e.g. fragrances, e.g. (Elberling et al.,
2005a; Elberling et al., 2005b; Elberling et al., 2004) and (Schnabel et al., 2010).
However, human exposure studies as shown below are not in support of a direct
relationship.
74
Special group of chemicals in consumer products
Chemicals of some concern are quaternary ammonium chlorides (QUATs). They are
used e.g. as disinfectants and antistatics (Quirce and Barranco, 2010). The main
exposure route would be inhalation of aerosols from QUAT-containing spray
products; thus, the airborne exposure is limited to the occupational setting rendering
this type of compounds perhaps less relevant for airway allergy symptoms among
office workers with existing QUATs, cf. (Nielsen et al., 2007). A few respiratory cases
have been reported among cleaning personnel (Houtappel et al., 2008; Purohit et al.,
2000; Villar-Gómez et al., 2009; Quirce and Barranco, 2010); thus, the effect of new
QUATs could be of some concern, but primarily in occupational settings. Asthmatics
may be more susceptible towards bronchoconstriction; for instance, inhalation up to
1.8 mg of benzalkonium chloride caused severe reduction in FEV1, while controls
were unaffected (Lee and Kim, 2007). In a recent in vivo study with mice inhaling
common QUATs benzalkonium chloride was found to be the most potent causing
lung effects (Larsen et al., 2012).
One group of consumer products in particular those emitted as aerosols from spray
products may be of concern, cf. (Vernez et al., 2006).There are number of reported
cases about the use of spray products, e.g. (Pauluhn et al., 2008; Weibrecht and
Rhyee, 2011; Nørgaard et al., 2009) and references therein. For instance, it was
recently concluded that no safe threshold for acute respiratory symptoms could be
identified for spray products (Vernez et al., 2006). Silicon-containing chemicals, like
siloxanes, in particular fluorinated siloxanes are common chemicals in surface-
coating products used in spray can products. A few studies have indicated that
fluorinated siloxanes may be associated with severe lung effects, cf. (Nørgaard et al.,
2010), while non-fluorinated siloxanes are harmless, as also inferred from a human
exposure study of 10 ppm octamethylcyclotetrasiloxane showing no lung effects
(Utell et al., 1998).
Some key human exposure studies with cleaning related chemicals
To our knowledge few controlled human exposure studies with consumer products or
pure fragrances have been reported. In general, the studies were carried out to
discover differences between asthmatics and non-asthmatics. Further, a number of
studies have compared normal subjects (low negative affectivity) with subjects with
75
high negative affectivity exposed to fragrances, cf. (Chen and Dalton, 2005; Dalton,
2003; Dalton and Jaén, 2010).
It should be noted that a number of single-blind studies have reported lung function
effects. For instance, one study indicated that exposure only to the yes elicited lower
respiratory symptoms among non-asthmatics (Millqvist et al., 1998). This, however,
is in discordance with later studies, see below.
Patients (n), skin sensitive to two fragrance allergens, either ISO (isoeugenol) (11) or
HICC (hydroxyisohexyl-3-carboxaldehyde) (10), respectively, were exposed for one
hour to a level of 1 mg/m3 in a controlled climate chamber; geraniol was used as
control at the same concentration level (Schnuch et al., 2010). Patients, who also
had a history of allergic asthma, six out of eleven and four out of ten, respectively,
to ISO and HICC, were protected against dermal exposure during the exposure
period. The values for lung function (FEV1) and exhaled nitrogen oxide (FeNO) were
statistically unaffected between baseline before and after the exposures for any of
the compounds. Other measures of inflammation (eosinophils, CRP and mast cell
tryptase) also remained unchanged, but a tendency towards an increase of hyper-
responsiveness was observed after exposure to any of the compounds. Despite the
protection of dermal contact, two ISO subjects reported skin symptoms post the
exposure, and indication of bronchial hyper-responsiveness was observed among five
patients all together. Apparently, this is an independent risk factor as also found in
population-based studies on allergic diseases, e.g. (Elberling et al., 2005a). For
instance, contact sensitization to a fragrance mixture in women did not influence
predicted FEV1 and FVC values; however, an increased risk of association with
bronchial hyper-responsiveness was identified, but not in men (Schnabel et al.,
2010).The exposure study illustrates that high concentrations of fragrance allergens
may pose a risk of developing skin symptoms among patients sensitized to specific
fragrances, but otherwise changes in the respiratory system may occur, but without
objective changes.
In a controlled human exposure study 217 non-asthmatics and 164 asthmatics (89
mild and 75 moderate) were exposed for 30 min to two fragranced aerosol products
(TVOC = 15-31 mg/m3), an air freshener, an air sanitizer, and sham air, respectively
(Opiekun et al., 2003). The moderate asthmatics reported more nasal congestion
76
following the exposure than the non-asthmatics; otherwise, exposure-related
changes were absent in ocular redness and nasal swelling among all groups.
Likewise, no effects on the lung function were observed.
In a double-blind eye exposure study of 21 eczema patients with respiratory
symptoms and 21 healthy subjects, the former did not report symptoms when the
eyes were exposed to a common perfume for 15 min (Elberling et al., 2006b). Thus,
the authors concluded that eye chemesthesis failed to elicit lower respiratory
symptoms.
A large number of controlled human exposure studies with either single VOCs,
mixture of VOCs, or emissions from construction products have been reported during
the last three decades, for details, see (Wolkoff, 2012). Several of the exposure
scenarios contain some key fragrances, in particular limonene and -pinene, and
solvents, and several aldehydes. The total exposure concentrations were two to
three orders of magnitude higher than generally encountered in indoor
environments. Apart from increased odour intensity (i.e. poorer IAQ), chemosensory
irritation in eyes and airways and lung effects were unobservable in the subjects in
comparison with sham exposure, except for one study that indicated nasal irritation
at 24 mg/m3 total VOC. However, both the odour intensity and nasal irritation
declined to 40 % from the initial values during the exposure. It is possible that
severe asthmatics exposed to high VOC concentrations may have decreased lung
function; results are partly contradictory, but the general picture is that effects on
the lungs at VOC concentrations less than ~ 10 mg/m3 is negligible or absent. It is
speculated that other mechanisms may have an effect.
Exposure of asthmatics to high concentrations of formaldehyde did not result in
observable effects of the lung function formaldehyde, cf. (Wolkoff and Nielsen,
2010). Still, sensory irritation in eyes, nose and throat is commonly reported in
asthmatic patients; it has been speculated that trigeminal stimulation could be one
route (Schnuch et al., 2010). However, this would require concentrations unlikely to
be found indoors; thus, other hypotheses have been put forward, e.g. learned
aversion related mechanisms and previous exposure experiences may play a role,
e.g. (De Peuter et al., 2005; Eberlein-König et al., 2002; Van Diest et al., 2005;
Winters et al., 2003; Österberg et al., 2007); individual factors, e.g. negative
77
affectivity may play a role, cf. (Lang et al., 2008) and (Runeson et al., 2003;
Runeson et al., 2007), see also (Dalton, 2003; Dalton and Jaén, 2010). Thus, irritant-
induced asthma is less likely to occur and should be used with caution as a plausible
mechanism of asthma development.
Although it is well-established that a number of fragrances cause dermal effects by
contact (skin allergy), there is no supporting evidence that such compounds in ozone
poor environments also are associated with airway effects (Nielsen et al., 2007). Skin
allergy and airway allergy have different routes of action, TH2 versus TH1 (Durham,
1998).
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. (Thrasher et al., 1989), industrial chemicals have not been identified to cause
asthma (Dales and Raizenne, 2004; van Kampen et al., 2000; Nielsen et al., 2007).
This also goes for chemicals like phthalates (Jaakkola and Knight, 2008; Nielsen et
al., 2007). Further, polyethylene glycol ethers, that are common solvents in
numerous products, are not considered to be airway sensitizers, e.g. (Multigner et
al., 2005; van Kampen et al., 2000), in agreement with international scientific
guidelines (SCOEL, 2007; International Agency for Research on Cancer (IARC),
2006); however, recent focus on this type of VOCs (Choi et al., 2010a; Nazaroff and
Weschler, 2004) has prompted the selection of 2-butoxyethanol as an indoor
pollutant of general interest; further, this common solvent has also been proposed as
a potential proxy for terpene-containing consumer products, cf. (Wolkoff et al.,
2006).
3.4. Conclusions
People spend more than 90% of their time indoors. Exposure to indoor air pollutants
may result in adverse respiratory health effects. Consumer products, after building
materials and indoor combustion sources represent a significant source of pollutants
in the indoor environment, which may influence the indoor air quality in dwellings.
Current scientific knowledge on the use of consumer products and resulting
emissions in indoor air, although limited, indicates that they are a source of indoor
PM, VOCs and SVOCs. There is increased concern about the potential health impact
78
of indoor air chemistry, in particular of products resulting from ozonolysis of terpenes
(e.g. limonene and pinenes).
In more detail it can be stated that:
Epidemiological studies among cleaning personal indicate associations between occupational exposure to cleaning agents and respiratory effects. A number of oxidants have been proposed as potentially “causative”.
The exposure of aerosols from the use of spray products appears to be an important risk factor for respiratory effects.
Human exposure to VOCs at indoor concentration levels (< 10 mg/m3) may cause odour problems, but chemosensory irritation and lung effects have not been found after 2-4 hours of testing.
Severe asthmatics may react to odours, otherwise no effects have been substantiated in exposure studies.
Exposure of “chemical intolerant” patients to fragrances do not elicit clear sensory irritation symptoms.
In general, industrial chemicals, e.g. solvents, are not considered to be airway allergens.
There is no association between exposure to a skin allergen and asthma; however, hyper-responsiveness may occur in women.
Current knowledge about the actual exposure of the residents in the long term (in
quantitative terms) is as yet unknown. It depends on a number of factors, including
the product used, the frequency of use, residential characteristics, ventilation rate,
time spent in the environment, etc.; moreover, exposure to emissions is highly
variable and poorly predictable. In general, all indoor air contains some background
pollution, the composition of which depends on the materials and activities (e.g.
smoking) in the building. Because outdoor air also contributes significantly to the
quality of indoor air, the “base-line” from other sources is highly variable and strictly
local.
Many studies indicate (see paragraphs 3.2 and 3.3) that elevated inhalation exposure
to air pollutants occurs during the use of common cleaning products and air
fresheners. Further quantification of emissions from consumers products linked to
the use pattern is needed. New studies would need to identify compounds in the
emissions, especially from the combustion/pyrolysis processes (candles and incense).
In addition fine and ultra fine particles should also be measured.
79
Further research is also needed to study potential adverse health effects associated
with consumer products exposure. It is necessary to determine how indoor air
pollutants may contribute to sensory irritation, inflammation, respiratory and
cardiovascular effects.
There is also a need to investigate the toxicity and health effects of exposures to
combined pollutants, as well as to study the potential health impact of indoor air
chemistry. The role of UFP generated by ozone (mainly from outdoor but sometimes
also from indoor sources such as laser printers and copiers and terpenes (s-limonene
and -pinene) needs to be studied further, whether UFPs or the gaseous oxidation
products of terpenes/ozone reactions are responsible for the biological observed
response. Adverse health effects need to be clarified both in terms of acute and
chronic effects.
3.5. Brief overview of particle emissions and associated respiratory effects from handling of consumer products within air fresheners, cleaning and maintenance products
Introduction
Epidemiological studies of cleaning work have shown associations with respiratory
effects, i.a. asthma or exacerbation thereof (Bondi, 2011; Quirce and Barranco,
2010;Zock et al., 2010); however, unambiguous risk factors have not been identified.
Furthermore, a risk assessment of gaseous versus particle phase pollutants has not
been attempted.
The objective of this chapter is to provide a brief overview about the emission of
fine/ultrafine particles emitted from consumer products within the EPHECT regime,
and associated health effects. The overview is based on ongoing literature search
during the last decade about particle emissions and health effects associated with
consumer products within the EPHECT regime.
Zock et al. (2010) summarized that “the most important products [associated with
respiratory effects in the cleaning industry] that have been repeatedly reported
include products in spray-form, chlorine bleach, and other disinfectants”. Further, it
80
was recently concluded that no safe threshold for acute respiratory symptoms could
be identified for spray products (Vernez et al., 2006). Zock and colleagues
furthermore concluded that “many cleaning agents are respiratory irritants and have
some sensitizing properties”. We have no knowledge about these agents occur in the
gas or the particle phase. To our knowledge, it appears improbable that organic
solvents and fragrances will reach high enough gas-phase concentrations to cause
irritating and sensitizing effects in the airways, cf (Wolkoff, 2013).
At present, groups of compounds, that are suspected to be associated with adverse
health effects, are shown in Table 1, cf. (Quirce and Barranco, 2010), but see also
(Arif and Delclos, 2012). Some of these are present in wet products to be applied,
e.g. by mobbing or washing, while others may be contained in spray products and
associated with risk of inhalation. Within EPHECT the following product categories
may form aerosols during the spraying and by combustion (candle), see Table 2.
Table 3.4. Compounds associated with respiratory diseases among cleaning personnel. Sensitizers: Amines (e.g. ethanolamine)
Disinfectants *
Quaternary ammonium compounds
(QUATs) *
Fragrances containing terpenes
Isothiazolinones (formaldehyde
releasers) Chlorine bleach (hypochlorite)
Glutaraldehyde
Sensory irritants: Chlorine bleach (hypochlorite)
Ammonia
Hydrochloric acid
Monochloramine
Mixing bleach and acid or ammonia
Sodium hydroxide (caustic soda) *
Quaternary ammonium compounds *
Mono-ethanolamine
*) To be aerosolized during spraying and possibly remain in the solid state after evaporation
of solvents.
Particle (aerosol) formation
Aerosols may derive from: First) the spray process itself as solvent droplets; second)
the droplets may contain compounds of which some have sufficiently low vapor
pressure to be present in solid state (e.g. QUATs), i.e. after the spraying activity and
evaporation of solvents (primary aerosols); and, third, products that contain terpenes
(fragrances) form polyoxygenated compounds of which some have low vapor
pressure leading to self-nucleation, condensation, etc., i.e. formation of secondary
organic aerosols (SOA), initiated by reactions with ozone (Coleman et al.,
2008;Destaillats et al., 2006). Finally, candles emit a number of combustion
81
products, i.e. inorganic, organic compounds,and some of these as particles, e.g.
(Bothe and Donahue, 2010;Pagels et al., 2009).
Table 3.5. Products, source type and potential aerosolizer within EPHECT.
Products Source type Aerosolized as particle during
use
1 All purpose cleaners (sprays) T +
2 Kitchen cleaning agents (sprays) T +
3 Floor cleaning agents T
4 Glass and window cleaners (sprays) T +
5 Bathroom cleaning agents (sprays) T +
6 Furniture polish T
7 Floor polish T
8 Combustible air fresheners (candle) T +
9 Air fresheners (sprays) T +
10 Passive units C
11 Electric units C +
12 Coating products (sprays) T +
13 Hair styling products (sprays) T +
14 Deodorants (sprays) T +
15 Perfumes T +
16 Ethereal oils T
17 Deodorizers T +
19 Magazines T
T = Temporary source – activity dependent.C = Building up to constantemission rate – “stable” exposure concentration.
Knowledge about the dynamic behavior (time profile and particle size distribution)
and the chemical properties of the particles are important for a risk assessment.
Briefly, for acute effects, in particular, alkalinity, siccative, surfactant properties may
be relevant.Just as important is the source of the particles, i.e. indoor versus outdoor
generated. For instance, the content of transition metals and oxidative stress
potential in ambient (outdoor) particles may be relevant for longer-term effects
(Kelly and Fussel, 2012; Rohr and Wyzga, 2012), but probably less relevant for
EPHECT generated aerosols indoors.
Activity related measurements
The particle emission and characterization of some air freshener sprays and candles
have been reported, e.g. (Afshari et al., 2005;Chen et al., 2010;Géhin et al.,
2008;Glytsos et al., 2010;Pagels et al., 2009), and nano-coating products (Nørgaard
et al., 2009). It is self-evident that the particle size distribution in spray products
depends upon nozzle diameter and pressure, cf. (Hagendorfer et al., 2010).
82
Furthermore, a number of studies have characterized the formation of SOA from
ozone-initiated reactions with terpenes in a number of consumer products, e.g.
(Sarwar et al., 2004).
Candles
Candle combustion showed complex particle-size profiles that were time dependent.
Generally, GMD (geometric mean diameter) was less than 20 nm and sometimes less
than 10 nm, and with a shift towards larger diameter particles greater than 100 nm
(Géhin et al., 2008;Glytsos et al., 2010;Pagels et al., 2009). The chemical
composition of the particles is dominated by inorganic compounds from unscented
(uncoloured) candles (Pagels et al., 2009), which do not appear to be a health
concern. In a double-blind study candle emission (907000 particles/cm3; 200 µg/m3)
exposure for three hours showed no health effects among healthy women (n=22);
the effects included change in heart rate, lung functions (spirometry), oxidative
stress, and inflammation in the airways (rhinometry) (Bohgard et al., 2011);
however, some minor changes in the heart rate variability were observed.
In a cross-sectional study (3471 persons) the prevalence of rhinitis symptoms or
atopy or increased levels of FeNO was not found to be associated with self-reported
use of candles, gas kitchen cookers and wood stoves (Hersoug et al., 2010).
Elevated risk of oxidative stress in the airways have been inferred from in vitro
studies of epithelial lung cells (A549) exposed to emissions from candles and
incense, in particular incense more than candles, see for example (Bluyssen et al.,
2013;Chuang et al., 2012;Matsumura et al., 2010). A risk assessment of such
observations, however, is hampered without detailed knowledge of the exact
exposure dose and procedures to translate to human exposure, cf. (Gerde, 2008).
Spray products
Use of hairspray showed particle size GMD from > 1 m to 2.5 m (Glytsos et al.,
2010). (Afshari et al., 2005) reported fine particles with GMD less than 1 m, while
GMD from less than 10 to ≤ 1000 nm was reported by (Géhin et al., 2008). A
majority of the particles (60-70 %) were less than 1 m from a water-based air
freshener (Rogers et al., 2005).
83
Nano coating products for tiles
Nørgaard et al. (2009) reported nano-spray coating products with and without
fluorinated siloxanes for tiles with GMD from less than 10 nm to about 200 nm with
the majority below 100 nm.
Reported cases of consumer spray products
Disinfectants
Few cases have been reported about spray products that contain QUATs(Houtappel
et al., 2008;Purohit et al., 2000;Villar-Gómez et al., 2009); thus, the effect of new
QUATs could be of some concern, but this is expected to be primarily in occupational
settings, cf. (Nielsen et al., 2007).
Coatings
To our knowledge a number of spray coating products have been reported to cause
severe lung damage, although, generally, recovery occurred within 48 hours, e.g.
(Pauluhn et al., 2008;Vernez et al., 2006). Although, also severe and even lethal
cases have been reported, e.g. (Malik and Chappell, 2003;Testud and Lambert-
Chhum, 2004).The causative agent(s) and associated mechanisms still need to be
clarified. In general, spray products for surface coating are composed of surface
active coating substances, solvents and propellants. In many cases of pulmonary
toxicity, the exposure was to a fluorinated acrylate or siloxane, e.g. (Rigler et al.,
2011). The outbreaks have at some occasions been associated with changes in the
formulation, i.e. change in active components or composition of the solvent, e.g.
(Yamashita and Tanaka, 1995).
Mice exposed to a commercial spray product containing perfluorinated siloxane
polymersshowed lethal pulmonary toxicity at concentrations only 10% higher than
the no-observed adverse effect level (Nørgaard et al., 2010). It was suggested that
the toxicological mechanism included reactions with lung surfactants causing alveolar
collapse, interstitial inflammation and edema. Hydrocarbon toxicity has also been
proposed, e.g. (Weibrecht and Rhyee, 2011), however, non-declared siloxane
materials or the like could be another plausible explanation.
84
Ultrafine particles formation from consumer products and ozone-initiated
reactions
As mentioned above, terpenes, common compounds in fragrances, easily undergo
ozone-initiated reactions to produce both gaseous (Calogirou et al., 1999) and
ultrafine particle phase (SOA) products, e.g. (Wainman et al., 2000). The ultrafine
particles are structurally poly-oxygenated compounds (low vapor pressure) with both
carbonyl, carboxylic, and hydroxy entities, e.g. (Glasius et al., 2000;Koch et al.,
2000).
It is relevant to envisage that the morphology of ozone-terpene initiated SOA differs
substantially from ambient and traffic-related (combustion) particles; thus, a direct
parallel to the well-established adverse health effects of ambient particles is not
applicable to this type of SOA. On that basis, it is concluded with regard to
respiratory effects, that the gaseous products are relevant for risk assessment,
rather than the SOA, from ozone-initiated terpene reactions.
Indoor measurements
Long et al. (2000) characterized ultrafine particle formation during (short-term)
mopping events using an α-pinene oil based cleaner; the particle formation was
ascribed to ozone-initiated reactions. Other cleaning and maintenance product use
have also shown ultrafine particle formation in the presence of ozone and with GMD
around 100 nm to 1000 nm, e.g. (Destaillats et al., 2006;Huang et al., 2011;Sarwar
et al., 2004;Singer et al., 2006). Further, a number of studies have demonstrated
ultrafine particle formation from ozone exposure of air fresheners and perfume in
climate chambers with GMD peaking around 100 nm (Coleman et al., 2008;Liu et al.,
2004;Sarwar et al., 2004;Singer et al., 2006).
Epidemiological studies
One epidemiological study of US office buildings showed a positive association with
both upper airway effects and late afternoon outdoor ozone concentration, although
no causality has been identified (Apte et al., 2008;Erdmann and Apte, 2004); the
authors suggested ozone-initiated terpene reaction products as a possible source
without distinguishing between gaseous and particle phase products. Other
epidemiological studies have suggested terpene oxidation products to be associated
with reported respiratory effects; however, these studies should be interpreted
85
cautiously due to uncontrolled multiple-exposure (Buchdahl et al., 2000;Höppe et al.,
1995;Soutar et al., 1994), and furthermore, gaseous and particle were separated.
Positive associations with indoor generated SOA in epidemiological studies of 29
elderly subjects with cardiovascular diseases have not been found for multiple
plasma biomarkers (Delfino et al., 2008). In another study with 60 elderly subjects
plasma inflammatory biomarkers were not associated with SOA (Delfino et al., 2010).
Finally, ST-segment depression in 38 subjects indicated significant positive
associations with markers of combustion-related particles and gases, but not SOA or
ozone (Delfino et al., 2011).
Bioassay studies (in vivo)
Acute airway effects of ultrafine particles from ozone-initiated limonene were
investigated in a mouse bioassay by denuding the reaction mixture, i.e. separation of
the gaseous products from the particle phase, thus entering the exposure chamber.
It was shown that the denuding process only changed the size distribution slightly
towards smaller particle sizes, but without a biological response (Wolkoff et al.,
2008). The result indicates that denuded SOA from an ozone-initiated limonene
reaction mixtureare without respiratory effects at concentrations up to 10 mg/m3 in
mice.
Denuded α-pinene SOA (200 g/m3), derived from UV radiation of a mixture of
nitrogen dioxide (+/- sulfur dioxide) and α-pinene, was exposed to F344 rats and
ApoE-/- mice for seven days (McDonald et al., 2010). Pulmonary inflammation was
not observed in either mice or rats; rather, the authors suggested the gaseous
products to be of concern. Furthermore, the biological response was mild, also about
cardiovascular effects. In general, the α-pinene generated SOA did not cause
pulmonary or systemic responses in rats (Godleski et al., 2011) or in vivo oxidative
stress (Lemos et al., 2011).
Overall, respiratory effects, that included pulmonary inflammation,of SOA in rodents
from ozone-initiated terpene reactions was not observed and cardiovascular effects
were mild.
86
Human exposure studies
In women (n=130), 2½ hours’ exposure of a typical indoor mixture with 23 VOCs
with limonene and α-pinene (TVOC = 26 mg/m3) showed no effect on nasal lavage
fluid (polymorphonuclear cells, total protein, IL-6 and IL-8)with or without the
presence of ozone (Laumbach et al., 2005).In a parallel study, symptom rating and
objective health effects, that included lung functions, were marginal and non-
significant (Fiedler et al., 2005).A double-blind exposure study with healthy women
(n=22) to an ozone-initiated lime oil reaction mixture (30000 particles/cm3, 0.07
mg/m3) for three hours did not show sign of adverse health effects; these included
change in HR and HRV, lung functions (spirometry), oxidative stress, and
inflammation in the airways (rhinometry) (Bohgard et al., 2011).
Overall, clinically relevant airway inflammatory effects from ozone-initiated terpene
generated SOA is not supported from the controlled human exposures.
In vitro studies
Pulmonary epithelial cells (A549) were exposed to a reaction mixture of ozone (4
ppm) and limonene (20 ppm) for 1-4 hours (Anderson et al., 2013). It was
concluded on the basis of a number of inter alia proliferation and inflammatory
cytokine measures in the cells that the exposure may produce more severe effects
than the parent compounds, especially IL-8, but not ozone. Long-term exposure
(weeks) of differentiated epithelial tissue samples (MucilAir), to limonene and the
mixture of limonene and ozone both increased cytokine production, and some
reduction in MCP-1 after one-two weeks, while IL-6, Il-8, MCP-1, and GM-CSF
remained unaltered compared to clean air after one week of exposure; and, no
changes in proliferation. No cytotoxicity, but subtle changes in cellular functions were
observed by exposure of A549 cells to SOA generated by UV radiation of a mixture α-
pinene, nitrogen oxide, nitrogen dioxide, and sulfur dioxide (Gaschen et al., 2010),
while exposure of A549 cells to a mixture of UV radiated ambient hydrocarbons (2
ppm), that included α-pinene and isoprene, and nitrogen dioxide increased IL-8
(Sexton et al., 2004).
BEAS-2b cells showed only some elevation of IL-8, among several inflammatory
markers, to the exposure of magnetic nanoparticles coated with α-pinene or
87
terpinolene SOA, but not to SOA or the particles alone, or clean air (Jang et al.,
2006).
In summary, there are severe limitations and interpretational difficulties of the in
vitro data for risk assessment, cf. (Gerde, 2008); in particular, a translation of the
high concentrations to realistic indoor levels. Furthermore, if an effect, the study
generally does not allow for a separation of the gaseous versus the particle phases;
another problem is the pronounced effect of limonene alone to be separated in the
mixture. Another impediment is lack of use of a reference control for comparative
purposes, e.g. nitrogen dioxide (Aufderheide et al., 2002), a well-known lung irritant.
Conclusion
In view of the overall objective of EPHECT regarding risk assessment of aerosolized
fine and ultrafine particles, they are recognized in the use of spraying processes;
further, secondary organic aerosols in ozone-initiated terpene reactions. It is also
recognized that certain chemical groups from the cleaning industry are suspected to
be associated with adverse respiratory effects. It is further recognized that ultrafine
particles generated from ozone-initiated terpene reactions are not considered to be
of concern regarding respiratory effects.
Except for a limited number of cases that are specifically associated with the use of
quaternary ammonium compounds and surface coating products that contain inter
alia fluorinated (acrylate or siloxane) polymers. Experimental respiratory toxicology,
in general, of consumer product aerosols is scarce. Finally, it is well-established that
ambient fine and ultrafine particles are associated with adverse respiratory and
cardiovascular effects; however, it is also recognized, due to different morphology
(and chemistry, e.g. transition metals), that EPHECT consumer product generated
organic aerosols do not possess similar properties. It is also recognized that there is
no convincing evidence to support that ozone-initiated terpene generated ultrafine
particles possess adverse respiratory effects at typical indoor scenarios. Whether
such secondary generated organic aerosols, that become a component of ambient air
particles, may have potentiating effects is an important research gap.
In view of the above (a number of experimental research gaps), risk assessment of
particles generated from EPHECT products has not been carried out.
88
4. EMISSIONS OF CONCERNED CONSUMER PRODUCTS
Even though household products provide substantial benefits to human life, such as
the promotion of hygiene and aesthetics, the emission composition from such
products are potentially associated with an elevated exposure risk for building
occupants. Several studies have implicated these consumer products as sources of
indoor pollutants. Actually, the use of cleaning products can lead to emissions of
primary or secondary pollutants indoors.
The emissions composition for household products is likely different among
manufacturers in different countries. Moreover, the chemical composition and
concentrations of total VOCs were substantially different between products even
within the same product category.
A few laboratory studies have been carried out, in particular emission testing of
cleaning agents under controlled conditions in climate chambers. Quantitative
analyses of different cleaning agents have shown many different VOC classes. About
100 different VOCs have been identified (Table 4.).
Table 4.1. Typical volatile organic compounds found in cleaning agents [Wolkoff et
al., 1998]
VOC class Examples
Alkanes Hexane, decane and tetradecane
Halogenated alkanes Seldom: 1,2-dichlorpropane, methylene chloride (abandoned)
Alkenes Terpenes: α-pinene, limonene, and many other isomers Sesquiterpenes: longifolene, and many other isomers
Aromatics Toluene, ethylbenzene, styrene
Alcohols Ethanol, 2-propanol, butanol, hexanol, 2-phenylethanol
Glycols/glycol ethers Dipropylene glycol, 2-ethoxyethanol, 2-methoxyethanol, 2-(2-ethoxyethoxy)ethanol, 2-(butoxyethoxy)ethanol, 2-(dodecyloxy)ethanol
Ethers Dioxane
Aldehydes Formaldehyde, acetaldehyde, glutaraldehyde
Ketones Acetone, butanone, 2- and 3-octanone, acetophenone
Acids Acetic acid
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Esters Acetates (butyl, citronellyl, hexyl, 1-phenylethyl), phthalates, certain acrylates
4.1. Electronic equipment
In contrast to other sources of emissions indoors, such as building materials and
furnishings, electronic devices are ‘active’ emission sources. Firstly, they consume
electrical power which results in the creation of hot areas inside the device. This
favours VOC and SVOC emissions from the various components and materials when
the unit is in operation. Secondly, in the case of hardcopy devices, the volatile
ingredients of consumables (paper, toner and ink) also contribute to the total organic
emissions [Destaillats et al., 2008]. This may lead to users being exposed to different
types of emitted pollutants.
In a survey conducted in Denmark in order to estimate emissions from electrical and
electronic appliances, measurements were made to detect substance emissions -
among which acetaldehyde, benzene, and formaldehyde- from appliances after 7
hours of use and after 9 days of use in test chambers with a controlled atmosphere.
Products under investigation were categorized as following:
1. Computers, game consoles, and equipment for computers
2. Electrical equipment used in the kitchen/utility room
3. Audio and video systems
4. Communications equipment (telephones and related equipment)
5. Electrical equipment used in connection with personal care
There is growing concern about the levels of potentially harmful pollutants that may
be emitted from office equipment and for which either toxicological effects or
potentially significant exposures have been described in the literature. Office
equipment has been found to be a source of ozone, particulate matter, volatile
organic compounds (VOCs) and semivolatile organic compounds (SVOCs).
In Table 3 of the Appendix, VOC emission rates reported in the literature from
desktop and notebook computers are summarized. When available, chamber
concentration data are also reported. Emission rates are reported separately for
90
computers operating with cathode-ray tube (CRT) monitors and with thinfilm
transistor (TFT) monitors. When reported in the original article, the sum of VOC
concentrations determined as ∑VOC is included. Typically, the ∑VOC emissions have
been higher for computers with CRT than with TFT monitors. Reported VOC
emissions include aromatic hydrocarbons, alkanes, alcohols, ketones and volatile
carbonyls, particularly formaldehyde. Reported VOC emission rates for notebook
computers have been significantly lower, both for idle and operating conditions. For
notebooks, the chemical composition of emissions has included alcohols,
carboxylates and ketones. The number of studies is limited but generally the results
indicate that ∑VOC emissions are in the range of 100–200 mgh-1 unit-1 [Destailats et
al., 2008].
In Table 3, are also reported the SVOC emission rates from studies of desktop
computers in operation, together with chamber concentrations corresponding to the
desktop studies and for a single notebook study. Organophosphorous flame
retardants have been measured during computer operation, but brominated flame
retardants (BFRs) sorb to the chamber walls so they have only been detected after
computer operation by heating the chamber to 120 0C and collecting air samples
during the heating period. The plastic covers of video-display units (VDUs) have been
shown to contain and emit triphenylphosphate (TPP) flame retardants. In that study,
reported time-dependent emission rates of TPP over a 193-day period showed a
significant reduction in air concentrations of this pollutant after the first 50 days.
Printed circuit boards held at elevated temperature (60 0C ) have been shown to emit
several PBDEs. Reported calculations of the emission rates for the SVOCs are in the
low ng h-1 per computer range [Destailats et al., 2008].
Various types of printers are widely used in both office environments and homes,
and are known to be potential sources of gaseous and particulate impurities. A
number of studies have addressed the role of modern laser printers as a significant
emission source of ultrafine aerosol particle indoors as well as formaldehyde and
nitrogen dioxide [COSI, 2005]. Ultrafine particles from laser printers are secondary
particles produced by the nucleation of volatile organic compounds originating from
paper and toner. Fuser roller temperature is a key parameter in particle generation
and the initial precursors are volatile organic compounds which are vaporized by the
fuser. Koivisto et. al. [2010] mention that at the start of the print job, the particle
91
concentration increased rapidly and started to decay immediately. They also found
that in print phase volumetric particle emissions were roughly 200 times larger than
in the activation phase.
Malmgren-Hansen et al. [2003] mention that the highest emission of VOCs resulting
from TV sets consists of phenol and toluene. The same authors indicated that the
emissions of most of the substances decreased to 5-20 % of the initial emission after
approx. 4 months. However, the formaldehyde emission appeared to decrease at a
lower rate. In the same study is shown that over time, the concentration of
phosphate-based flame retardants in the air samples increased slowly. The
concentration of TBP, TCEP, and TCPP flame retardants increased very slowly,
reaching approx. 75 % of the concentration at 600 hours (25 days) after 100 hours.
It can be assumed that the concentration levels will begin to decrease again at some
point, but when decrease will start is not known. The measured constant
concentrations indicate that the emission of flame retardants will continue for many
months (years). Photocopiers contribute with high concentration of ozone which
occurs during the copying process.
In a survey conducted from Danish Ministry of the Environment two types of mobile
phones for their indoor emissions were tested. It was found that one of the phones
(excluding the charger) emitted small quantities of toluene and siloxanes. The
second type of mobile phone (including the charger) emitted toluene, siloxanes,
butylated, hydroxytoluene, xylene, hexanal, acetaldehyde and formaldehyde. Neither
with nor without charger a mobile phone of the tested types was found to pose any
risk of negative health impacts when used in the indoor climate [DEPA, 2005].In a
survey conducted for electronic equipment emissions, by the Danish Technoloical
Institute (2003), TVOC, Toluene, Suspected teratogenic, 2-ethylhexanol, n-
pentadecane, Ethylmethylbenzene, n-tetradecane, Naphtalene, Tetrachlorethene, 2,6
di-tert-butyl-4- methylphenol (BHT) were the main emitted compounds. Mobile
phones were switched on 3 hours before measurement.
However, limited data were found about mobile phone emissions in the indoor
environment in the literature review.
92
Game consoles. Today, several game consoles dominate the world market and they
are mostly used by children and youths. Styrene, phenol, 2-ethylhexanol,
formaldehyde, acetone, acetophenone, o-xylene, trimethylbenzene, α-pinene,
toluene, acetaldehyde, hexanal, 2-methyl-1-propanol, 3-carene, benzaldehyde,
nonanal, propanal, pentanal and octanal were identified in game console emissions
[Danish Technological Institute, 2003]. The largest emissions from the game console
are C11-C18 compounds, followed by styrene and phenol.
Voltage converters. Power converters for halogen lamps (using traditional
transformers) become very hot during use resulting in high concentrations of the
emitted compounds. Additionally, they are often low-cost products manufactured in
the Far East. It is not unusual, in a typical home, to use 3-5 converters because
normally a lamp comes with its own converter. Converters tested from the Danish
Technological Institute [2003] were found to emit trimethylbenzene, m-,p-xylene,
ethylbenzene, 2-methyl-1-propanol, formaldehyde, o-xylene, 2-pentylfurane, 2-
ethylhexanol, 2-buthoxyethanol, phenol, hexanal, tetramethylbenzene, acetaldehyde,
decanal/alcohol, BHT – butylhydroxytoluene, cyclohexanone, formic acid, butylester,
butanal 2-ethylhexanoic acid, pentanal, formic acid, 2-methylester, alcohol,
acetophenone, acetone, 2-hydroxybenzenethanol, α-pinene, propanal, butylacetate,
3-methylbutanal/pentanal, chlorobenzene, octanal and benzaldehyde. Unexpectedly
large emissions were measured, in the same study, for toluene, C11-C18
compounds, trimethylbenzene and xylene. Moreover, emissions of toluene from a
voltage converter reach the same level as emissions from a monitor, although it is
much smaller in size. Formaldehyde emissions, from a single voltage converter, are
larger than all other emissions of this substance as established through literature
surveys on all types of electronic devices.
Hairdryers tested in the above mentioned study were found to emit basically n-
tetradecane, n-pentadecane, n-hexadecane, n-ethylhexanol, naphthalene and 2,6 di-
tert-butyl-4- methylphenol (BHT).
Electric shavers tested in the same survey of the Danish Technological Institute,
emitted TVOC, 1-ethoxy-2-propanol, cyclohexanone, 2,6 di-tert-butyl-4-methylphenol
(BHT), 2-ethylhexanol, several n-alkanes, cyclohexanone, naphthalene,
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methylnaphthalenes, mange alkylbenzenes, mange n-alkanes, cyclohexanone and
benzene.
4.2. Appliances
Cooking fumes from heating of cooking oils contain potentially harmful chemicals
such as aldehydes, ketones, hydrocarbons, fatty acids, alcohols, aromatic compounds
and heterocyclic compounds. Acetaldehyde, formaldehyde, CO, and NO2 are the
major pollutants emitted during cooking. In COSI report [2005] is mentioned that the
lowest CO and NO2 emissions have been measured during electrical backing of
bacon and preparing lasagne using the microwave. Lowest acetaldehyde and
formaldehyde emissions were measured during pork roasting preparation by gas
cooking. Highest CO and NO2 emissions were reported during gas cooking while
preparing broil fish. Highest acetaldehyde and formaldehyde emissions were also
measured during broil fish preparation, however, by electrical cooking. When used in
simple cooking stoves, these fuels emit substantial amounts of toxic pollutants.
These pollutants include respirable particles, carbon monoxide, oxides of nitrogen
and sulphur, benzene, formaldehyde, 1,3-butadiene, and polyaromatic compounds,
such as benzo(a)pyrene. From these cookstoves, highest mean formaldehyde
emission have been identified for natural gas while highest CO emissions have been
measured for brush wood as fuel, while the use of using natural gas has the lowest
CO emissions [COSI, 2005].
Charging the washing machine with laundry powder may lead to generation of dust
particles. Similarly, for dish washers, the main emissions to the indoor air derive from
the detergent/ cleaning product used rather than the washing machine itself. The
main emissions of these kinds of products are described in detail later on in this
document.
Relatively little prior work has investigated the range of VOCs emitted from dish and
clothes washers, hair dryers and vacuum cleaners. The most common VOCs, with
confirmed identification in more than one-third of the products used for dish wash
and laundry, were ethanol, limonene, linalool, β-phenethyl alcohol, chloromethane,
1,4-dioxane, β-myrcene, benzyl acetate, benzyl alcohol, benzaldehyde, α-terpineol,
β-citronellol, 2-butanone and α-pinene. Of these, the most common VOCs, in more
94
than one-third of the products, were limonene, linalool, citronellol, eucalyptol,
geraniol, and α-pinene [Steinmann, 2009]. Caress and Steinemann [2004, 2005]
found that 10.9% (second study only) of people who participated in their study,
reported irritation from the scent of laundry products, fabric softeners, or dryer
sheets that are vented outside. Among asthmatics 21.2% reported irritation from the
scent of laundry products, fabric softeners, or dryer sheets that are vented outside.
Vacuum cleaners tend to increase the concentrations of the coarse particulate matter
[Yu et al. 2009].
The quality of the air passing through systems from air conditioning can be altered
by four classes of processes: (1) primary emission of compounds, particularly volatile
organic compounds (VOCs) from materials; (2) sorption and desorption processes
between pollutants and surfaces; (3) pollutant removal by deposition or chemical
reaction at surfaces; and (4) reaction between air pollutants and surface materials
that lead to the release of chemically transformed compounds. Of particular interest
for (3) and (4) are ozone-surface interactions, which tend to reduce the ozone
concentration in the supply air, but may generate carbonyls or organic acids that can
be released into the air [Morrison et al, 1998].
The HVAC duct distribution system can spread pollutants from one portion of the
office to another. Regular maintenance and duct sealing can help minimize these
problems [http://www.afhh.org/dah/dah_ventilation.htm]. Generally, an HVAC
system can affect the indoor air quality in the following ways.
[http://www.iaqtest.com/pubs/Basics%20of%20Indoor%20Air%20Quality.pdf]:
dust or dirt in ductwork or other components
microbiological growth in drip pans, humidifiers, ductwork, coils
improper use of biocides, sealants, and/or cleaning compounds
improper venting of combustion products
refrigerant leakage
The most prominent pollutants of HVACs are the occurrence of biological growth in
the presence of moisture provided by air washers and other recirculating water
systems. These problems appear to be exacerbated by dust accumulation and
infiltration of outdoor air contaminants that are distributed to occupied spaces by the
HVAC system [EPA, 1995]. Although the HVAC system can help to remove and/or
95
dilute more than 80% of aerosols from outdoors, they can also provide favourable
breeding grounds for bioaerosol to colonize [Law et al., 2001]. Bioaerosols consist of
all airborne particles of biological origin, i.e., bacteria, fungi, fungal spores, viruses,
and pollen and their fragments, including various antigens. Particle sizes may range
from aerodynamic diameters of ca. 0.5 to 100 μm. Furthermore, non-biological
particles may serve as carriers of fungal allergen molecules into the lung
independently of the whole fungal spore. In the case of combustion particles such as
tobacco, smoke or cooking-generated particles, such an interaction could have
serious implications. Law et al [2001] mention that elevated concentrations of
bacteria and fungi would occur in the morning HVAC system startup and decrease
afterwards. The overnight shut-off of the ventilation systems could lead to the
accumulation of micro-organisms during these periods.
Man made mineral fibres (MMMFs) that can cause irritation in upper respiratory tract,
and skin, can also be emitted to indoor air from the HVAC system. The present limit
for the fibres presented in the Finnish Classification of Indoor Climate 2000 reaches
up to 0.01 fibres/cm3 or 10000 fibres/m3. This limit value originated from the
clearance value of asbestos fibre measurement after asbestos removal and it
contains all respirable fibres [Kovanen et al., 2007].
EUROVEN, a multidisciplinary group of scientists, reviewed many studies and
concluded that occupants in buildings with air-conditioning may have increased risk
of SBS symptoms as compared with occupants in buildings with natural ventilation or
a mechanical ventilation system without cooling. The group also suggested that
improper design, operation, and maintenance of HVAC systems could have
contributed to the increased prevalence of SBS symptoms [Humelgaard et al, 2007].
4.3. Fireplaces
Household combustion is mainly responsible for elevated indoor levels of CO, SO2
and NO2. If properly operated and maintained, appliances that burn gaseous fossil
fuels have high combustion efficiencies and thus generate insignificant amounts of
CO. However, the high combustion temperature associated with gas combustion
favours the formation of NO2.
96
In households with limited ventilation (as is common in many developing countries),
exposure experienced by household members, particularly women and young
children who spend a large proportion of their time indoors, have been measured to
be many times higher than World Health Organization (WHO) guidelines and national
standards.
Emitted pollutants from wood combustion in wood stoves and fireplaces include
PM2.5, acetaldehyde, benzene, formaldehyde, toluene, xylenes and carbon
monoxide, resin acids/terpenoids, levoglucosan, phenol, alcohols, butanone, 3-
butene-2-one 3-methyl-3-butene-2-one, glyoxal, acetone, acrolein, 2-methylfuran,
2,5-dimethylfuran, 2-furaldehyde, arbon monoxide and halogenated compounds
[COSI, 2005; Hedberg et al., 2002; Mc Donald et al., 2000; Schauer et al. 2001].
Additionally, wood combustion products include polycyclic aromatic hydrocarbons
(PAHs), such as benzo[a]-pyrene, which contribute to the ambient air mutagenicity.
Wood combustion has been estimated to account for more emissions of PAHs than
any other source [Mc Donald et al., 2000]. Schauer et al. [2001] found that guaiacol
(2-methoxyphenol), and guaiacols with additional substituents at position 4 on the
molecule, and resin acids are emitted in significant quantities from pine wood
combustion. Syringol (2,6-dimethoxyphenol) and syringols with additional
substituents at position 4 on the molecule are emitted in large amounts from oak
and eucalyptus firewood combustion.
Several studies were performed to quantify and characterize the emission from
conventional wood stoves and fireplaces. Non-mineral potassium is widely used as a
tracer for wood smoke but nonmineral is contributed by several other major air
pollution sources such as meat cooking and refuse incinerators and its emission rate
varies widely among wood types [Schauer et al, 2001]. However, there is very little
data on emissions of pollutants from wood stoves [Hedberg et al., 2002].
Zhang et al. [1999] found in their study that CO emission factors were dependent
upon not only fuel types, but also stove types. For example, the range of fuel mass
based CO Ef (g/kg) for the following fuel/stove combinations was close to an order
of magnitude: 10 combinations of crop residue/stove, 15 wood/stove, 11 coal/stove,
and 4 kerosene/stove. The same authors mention that among the fossil fuels tested,
coal had the highest CO Ef. The CO Ef for coal was comparable to those for biomass
97
fuels. Performing the same cooking task using any gas fuels, LPG, and kerosene
would emit significantly less CO than using biomass and coal. Occasional carbon
monoxide (CO) poisoning cases are reported, mainly as a consequence of the
improper use or inadequate ventilation of appliances [Zhang & Smith, 2003].
Diseases associated with use of solid fuels and populations affected include asthma,
acute lower respiratory infections (ALRI) for children aged <5 years, chronic
obstructive pulmonary disease (COPD) for females and males aged ≥30 years and
lung cancer (for coal use only) for females and males aged ≥30 years, perinatal
effects and low birth weight, tuberculosis, nasopharyngeal cancer [Smith et al].
Epidemiological studies suggest that long-term exposure to NO2 (through the use of
gas stoves) is a modest risk factor for respiratory illnesses compared to the use of
electric stoves. The concern about CO, on the other hand, is primarily for its acute
poisoning—i.e. its ability to bind strongly to haemoglobins (see Chapter 10). Acute
exposure to high levels of CO from improperly operated and maintained appliances is
the leading cause of poisoning death in USA and claims many lives world wide. In
modern residences, cooking and space-heating needs are usually met by fossil fuels
such as natural gas, liquefied petroleum gas and heating oil.
There may also be effects associated with the use of kerosene and gas. Among the
air pollutants they emit the major are formaldehyde, carbon monoxide, and nitrogen
dioxide [COSI, 2005]. Concerns have been reported about exposure to nitrogen
dioxide (NO2) emitted from gas stoves. Compared to combustion of solid fuels,
however, gaseous fuels in simple devices emit substantially smaller amounts of
pollution, including particulate matter (PM), CO, eye irritating volatile organic
compounds (e.g. aldehydes), and carcinogenic compounds such as benzene and 1,3-
butidiene and polycyclic aromatic hydrocarbons [Zhang & Smith, 2003].
4.4. Household products
Many interrelated factors must be considered in defining the potential health hazard
of a particular product or class of products: the chemical composition of the product;
the toxicity of the compounds contained in the product; an estimate of airborne
concentrations and exposures produced by the use of the product; the market
penetration (either at the present time or expected in the future due to changing
market conditions); and an estimate of the population potentially at risk. Volatile
98
constituents of the products can enter the gas phase during or after use. But non-
volatile constituents can also be inhaled, either because the cleaning process or air-
freshener use itself releases liquid or solid particulate matter into the air or because
residual cleaning materials are later suspended, for example through abrasion and
wear [Nazaroff et al, 2006].
The cleaning products contain compounds in order to clean the laundry, the
dinnerware or surfaces in the house. The ingredients are classified into five general
types i.e. surfactants, builders, solvents, anti-microbial compounds and
miscellaneous. The surfactants are by far the most important group of detergent
ingredients. Surfactants improve the wetting ability of water, remove soil with the aid
of wash action and they emulsify, solubilise or suspend soils in the wash solution.
Surfactants are classified in anionic, non-ionic, amphoteric and cationic surfactants
and their mixtures are used mainly for cleaning. Cationic surfactants are often used
as laundry conditioner [RIVM, 2006].
Examples of surfactants:
Anionic surfactants
- Linear Alkylbenzene Sulphonate (LAS)
- Alkyl Sulphates (AS)
- Alkyl Ethoxy Sulphates (AES)
- Soap or fatty acid salts (FAS)
- Secondary Alkane Sulfonate (SAS)
Non-ionic surfactants
- Alkyl polyethyleneglycol ethers (AEO)
- Fatty acid alkanol amides (FAA)
- Alkyl polyglucosides (APG)
Amphoteric surfactants
- Alkyl betaines
- Amino alkylamino acids
Cationic surfactants
- Quaternary ammonium chlorides e.g. dialkyl dimethyl ammonium chlorides
99
Builders
Builders improve the cleaning effectiveness of the surfactants because they soften
water by removing metal ions like calcium and magnesium. Examples of builders:
Alkalis
- Sodium (bi) carbonate
- Sodium silicate
Ion exchangers
- Zeolite
- Polycarboxylate
Complexing agents
- Citric acid/ citrate
- Phosphonates
- EDTA: ethylenediamine tetra-acetic acid
- NTA: nitroloacetic acid
Solvents
Solvents are added to increase the cleaning effect of surfactants by dissolving oil and
grease. Their positive influence only exerts itself when the cleaner is used undiluted.
Besides they dry quickly on the cleaned surface. The water-soluble solvents can be
divided into three categories:
- alcohols: ethanol and isopropanol
- glycols: glycerol and propylenglycol
- glycol ethers: butyl(di)glycol, ethyl-glycol and propylene-glycol ethers
Miscellaneous
Other ingredients such as bleaching agents, enzymes, abrasives, acids, fragrances,
dyes, and preservatives may be added to cleaning products.
The bleaching systems in household products are:
- Peroxide or active oxygen bleach
Hydrogen peroxide is the base of the bleaching agents which contain active oxygen.
In household products compounds such as sodium perborate tetrahydrate or sodium
100
percarbonate are preferred. Tetra-acetyl-ethylenendiamine, TAED, is an activator for
the bleaching agent and the compounds sodium carbonate and hydrogen peroxide
are formed. Activated bleaching systems provide effective bleaching at today’s lower
wash temperatures for the laundry or machine dishwash. In toilet cleaners, active
oxygen bleach is used for surface cleaning and sanitizing.
- Hypochlorite bleaches
Hypochlorite bleaches are used in hard surface cleaning and sanitizing. This can be
done in a separate step of the cleaning task e.g. cleaning the toilet with bleach or
the bleach is an incorporated ingredient in the cleaning product e.g. an abrasive
liquid containing bleach.
Additionally, enzymes can be found in laundry products, machine dishwasher
products, in spot removers and household cleaners. Abrasives can be found in
scouring products and consist of small particles of minerals. They are differentiated
by their relative hardness. In scouring cleaners, the used minerals are silica, feldspar,
aluminium oxide and calcium carbonate.
Acids like formic acid, lactic acid, sulphuric acid or phosphoric acid can dissolve
calcium and metal salts; they find use in tub, tile, sink and toilet bowl cleaners.
Polymers are compounds whose molecules are very large, compared to most of the
other ingredients found in household cleaners. Polymers can be used as builders and
ist as thickening agents; the accompanying examples are polycarboxylates and
polyglycols respectively. In floor products, polymers such as polyethylene resins and
polyacrylates form films and these protect the surface and may provide a shine as
well.
Fragrances cover the base odour of the chemicals used in cleaning products and they
leave a pleasing scent after cleaning. Terpenes are the main chemicals added to
household products for this reason.
Furthermore, secondary toxic pollutants are formed by the reaction of unsaturated
organic constituents with oxidants such as ozone, hydroxyl radicals, and nitrogen
oxides. For example, terpene, which is contained in a percentage of 5%-10%
(CleanRight) in cleaning products and air fresheners, reacts with ozone thus leading
101
to the formation of formaldehyde. Three types of terpenes (limonene, -pinene, and -
myrcene) can potentially react with ozone to generate secondary pollutants with
other oxidants such as hydroxyl radicals and nitrogen oxides [Kwon et al. 2007].
For this product category two groups can be distinguished in the exposure
assessment for consumers: the group experiencing the highest exposure during use
(in most cases the user) and the group exposed after application (e.g. children). The
person applying the product (the user) is the one actually using the formulation and,
if necessary, diluting it to the required concentration (‘mixing and loading’). It is
expected that the user will be exposed to high levels during mixing and loading and
during application [RIVM, 2006b].
4.4.1. All purpose cleaners (gel, liquid, tissue, cream)
These rinsing agents reduce the surface tension between the washed items and
water during the final rinse cycle. By achieving a uniformly draining film, there is a
good clear drying effect and there are no spots, stains and streaks left behind on the
tableware.
Kitchen cleaners contain more surfactants (5-30 %) and more alkalis (1-35 %), such
as ammonia, caustic soda or caustic potash. This is necessary for removing all kinds
of dirt and grease. Like the all-purpose liquids, sprays and wet tissues are formulated
with surfactants and low levels of builders; most contain an organic solvent
Table 4.2. General formula of all-purpose cleaner
All-purpose cleaner
Liquid % Spray % Wet tissues %+
Surfactants 0 – 15 < 10 Anionic surfactants 2 – 10 Soap 0.5 – 3 Non-ionic surfactants
0 – 5
Builders 1-10 + Bases (ammonium) 0-5 Sodium carbonate Sodium citrate
Solvents & hydrotropes
0 – 15 2 – 15 < 10
Solvents: alcohol, 0 – 10
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glycol Hydrotropes 0 – 10 Additives Organic polymers < 2
Skin protecting agents
< 2
Preservatives < 1 < 1 < 1 Dye < 1 < 1 Perfume < 1 < 1 < 1 Water 75 – 85 85 - 95 70 – 95
+: ingredient of wet tissues *: for the wet fraction of tissues (circa 60 % of total weight12)), the percentages of the ingredients are given 4-nonylphenol and nonylphenol ethoxylates were used and may be emitted from all
purpose cleaners, mostly consisting of SVOCs or POM [Nazaroff and Weschler,
2004]. In 2005, these surfactants (e.g. nonylphenol ethoxylates) were no longer
permitted to be used in all household cleaning products on the European market
under the Detergent Regulation. These compounds are of concern because of their
ability to mimic female estrogen hormones. These products also emit 2-
butoxyethanol, ethylene glycol monobutyl ether (2-butoxy ethanol), ethylbenzene,
toluene, α-phellandrene , α-pinene , β-pinene, α-Terpinolene carbon tetrachloride,
acetaldehyde, formaldehyde, n-hexane, dichloromethane, perchloroethylene,
trichloroethylene, trichloromethane (chloroform), 1,4-dioxane, linalool, α-terpineol, 3-
butenylpropylether, methyl methacrylate, camphene, limonene, β-myrcene. Emission
studies suggest that glycol ether released from aqueous cleaning products occurs
slowly, over periods of hours or even a few days after application [Gibson et al.,
1991; Zhu et al., 2001]. If generally true, such behaviour would have the effect of
reducing exposures during cleaning activities, but increasing exposures to building
occupants following cleaning.
All purpose cleaners sold in Korea were analyzed in the study developed by K.-D
Kwon et al. (2007) presented in the following table:
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Table 4.3. Chemical composition and concentrations of total VOCs determined by headspace
Product
Category Product Analytes
TVOC Concentration
(ng/ml)
All purpose
cleaners
A Decane, limonene, β-myrcene,
octane, α-pinene, β-terpinene 1,169
B 1,8-cineole, iso-cineole 878
C Ammonia, chloroform 4,167
In J. Zhu et al., (2001) headspace method was used for studying consumer products,
five compounds (2-butoxyethanol, camphene, limonene, β-myrcene and β-pinene)
were identified as being emitted from all purpose cleaners.
Results of simulated cleaning tasks with the use of general purpose cleaners, suggest
that airborne exposures from short-term cleaning with selected bathroom cleaners
can remain in the air even after tasks’ cessation, indicating potential exposures to
anyone entering the room shortly after cleaning (Bello et al., 2010).
Singer et al., (2006) conducted experiments to quantify emissions and
concentrations of glycol ethers and terpenoids from cleaning products and air
freshener use in a 50 m3 room ventilated at approximately 0.5/h. Emission factors
and chamber air concentrations for some VOCs associated with simulated cleaning
activities with general purpose cleaners are presented in next table. Three of the
four general cleaning products studied emitted 2-butoxiethanol. The highest chamber
air concentration of 2-butoxiethanol was associated to product 3, a “concentrated”
product sold in both trigger spray and screw-top bottles.
Table 4.4. Emission factor and initial chamber air concentrations for limonene and 2-butoxyethanol associated with simulated cleaning activities
Emission factor (mg/g product)
Chamber air concentration 0-1h (µg/m3)
Product limonene 2-BE limonene 2-BE
Counter: full strength with scrub and rinse; towels removed 1 – capped bottle 6.8 - 960 - 3 – trigger spray - 25 - 2300 4 - trigger spray 22 7.4 2200 720 Counter: full strength with scrub and rinse; towels retained 1 – capped bottle 10.2 - 1100 - 3 – trigger spray - 34 - 1600 4 - trigger spray 31 15.5 2500 680
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Counter: full-strength, spray and wipe only; towels retained 2 – trigger spray - 30 - 1410 Floor mopping with dilute solution 1 – capped bottle 1.6 - 1130 - 3 – trigger spray - 1.3 - 1300 4 - trigger spray (dilution a – more diluted)
3.7 0.7 2900 380
4 - trigger spray (dilution b)
2.7 0.7 6200 1150
2-BE = 2-butoxyethanol
Fractional emissions of terpenes and terpene alcohols from one general purpose
cleaner are presented in next table (Singer et al., 2006). The emitted fraction of
dispensed product was highest for full-strength product use with towel retention,
lower for full-strength use with towel removal, and lowest for the dilute floor-
mopping application.
Table 4.5. Emitted fraction of terpenes and terpene alcohols (cleaning product)
Compound Emitted fraction* (g emitted/g dispensed)
Full-strength counter; retain
towels
Full-strength counter; remove
towels
Dilute, floor mopping
α-phellandrene 58% 34% 9% Terpinolene 45% 24% 8% γ-terpinene 65% 37% 10% Limonene 69% 46% 11% α-terpinene 36% 20% 7% Camphene 69% 50% 12% α-pinene 52% 39% 9% 4-terpineol 30% 9% 5% β-terpineol 19% 7% 4% 1-terpineol 22% 6% 5% γ-terpineol 7% 2% 2% α-terpineol 11% 4% 3%
* Emitted fraction is defined as the mass of VOC emitted into the gas phase divided by the amount dispensed in connection with cleaning product use Limonene and other ozone-reactive terpenoids present in cleaning products can
reach milligram per cubic meter levels in air and persist at levels of tens to hundreds
of micrograms per cubic meter for many hours after cleaning (Singer et al. ,2006).
105
4.4.2. Kitchen cleaning agents (liquid, spray, tissues)
Kitchen cleaners contain more surfactants (5-30 %) and more alkalis (1-35 %), such
as ammonia, caustic soda or caustic potash. This is necessary for removing all kinds
of dirt and grease. When doing the dishes, there is dermal exposure to the diluted
dishwashing liquid. Inhalation exposure occurs due to compounds, which evaporate
from the dishwashing water.
For granules, it is assumed that a maximum of 10 % is present in the form of
powder. The inhalation exposure is therefore expected to be 10-fold lower than the
exposure of a powder. There are also tablets containing all the different substances
i.e. detergent, rinse aid and salt. For tablets, the inhalation and dermal exposure is
considered to be negligible; therefore, there are no defaults given for tablets. The
exposure of loading salt is not regarded and there are no defaults given.
Filling the (dish) wash machine with liquid products or mixing and loading liquid
cleaners into water, may lead to inhalation exposure due to evaporation of volatile
chemical substances. Dermal exposure can also occur, due to liquid spills around the
opening of the bottle, which depends on the size of the opening and the way a
product is used. The consumer can use the cap for loading the liquid; when replacing
the cap, the remnants of the cleaning product may drip down. Furthermore, when
mixing and loading a liquid cleaner in a bucket, there could be spatters of the
cleaning product (RIVM report 320104003/2006).
Table 4.6. The general formula of a liquid hand dishwashing detergent is
Hand dishwashing detergent
Liquid %
Surfactants Anionic surfactants 10 – 30 Non-ionic surfactants 0 – 20 Amphoteric surfactants 0 – 5 Solvents Alcohol: isopropanol/ ethanol 0 – 10 Additives Sodium citrate 0 – 2 Skin protecting agents < 2 Preservatives 0 – 1 Dye < 0.1 Perfume < 0.5 Water 45 - 80
106
When doing the dishes, there is dermal exposure to the diluted dishwashing liquid.
Inhalation exposure occurs due to compounds, which evaporate from the
dishwashing water. Oral exposure can occur because of residues on washed
dinnerware. The quantity depends on the concentration of the detergent and on the
washing-up temperature. The residue quantity increases with the detergent
concentration or with the dishwaters temperature. Not drying the dinnerware results
in a higher amount of residue on the dishes and glassware. Comparing to the
machine dishwashing products, the amount of residues on dinnerware is much
higher when doing the dishes with hand-wash and without drying with a dishcloth,
because the crockery during the machine wash, is rinsed with clean water [RIVM
report 320104003/2006].
Some of chemicals in general use in kitchen cleaners include borax (boric acid) as a
cleaning agent to dissolve grease. It acts as a mild antiseptic and removes odours.
Many of the products used in the kitchen are poorly labelled and often give no
indication as to the chemical constituents they contain. For example, a general anti-
bacterial cleaner Pine-O-Cleen™ states that its active ingredient is benzalkonium
chloride 0.1% w/w. That means that 999 mL of each litre of Pine-O-Cleen™ is a
mixture of undisclosed chemicals [Patterson, 2004]. However, since 2005 in Europe
the Detergent Regulation requires all ingredients to be disclosed on companies’
websites and main constitutes to be indicated on pack, including concentration
ranges.
Many antibacterial products have been developed to provide fast and effective
cleaning to food preparation areas, replacing the traditional two-step detergent and
rinse cleaning method. Many of these products such as sprays and wipes are
cleaners containing an antibacterial agent and the instructions do not advocate
rinsing after their use, despite evidence showing that rinsing is a vital step in the
cleaning of domestic food contact surfaces (DeVere and Purchase, 2007).
J. Zhu et al. (2001) identified chemicals in the headspace of one product named as
“Lemon fresh and antibacterial spray” which may indicate a possible kitchen
application. Five compounds were detected: toluene, 2-butoxyethanol, α-pinene, β-
pinene and limonene.
107
4.4.3. Hard surface (floor) cleaner (powder, spray, gel, disinfectants)
4-nonylphenol and nonylphenol ethoxylates were used and could be emitted by
disinfecting cleaners while diethylene glycol monobutyl ether, 3-carene, (2-(2-
butoxyethoxy) ethanol), styrene, n-hexane, formaldehyde, dicyclopentadiene alcohol,
dihydromyrcenol, linalool, a-terpineol are emitted from liquid floor detergents
[Nazaroff and Weschler, 2004]. In 2005, these surfactants (e.g. nonylphenol
ethoxylates) were no longer permitted to be used in all household cleaning products
on the European market under the Detergent Regulation.
Table 4.7. A general formula of floor cleaning and protecting products is:
Floor products
Cleaner liquid %
Combined product %
Polish %
Sealer %
Stripper A %
Stripper B %
Surfactants 0-5
Anionic surfactants 5-15 < 5 0-15
- soap
1-30 1-15 0-5
Non-ionic surfactants
5-15 < 5 0-5
Builders
< 5
0-5
3-7
NTA, phosphates, sodium silicate
Bases 3-10
Ammonia / caustic soda
Solvents 0-15
Alcohols 5-25
2-butoxyethanol 10-50
Alkylphenoxy-polyethoxy ethanol (nonoxynol)
2-5
Glycols / glycolethers
1-5 0-5 0-5 0-15 0-20
Monoethanolamine 3-15 10-30
Hydrotropes 0-5
Cumeensulphonate
Waxes
1-10 1-5 0-5
Polyethyleen wax
Carnaubawax
Resins and polyacrylates
1-10 10-25 10-80
Plasticizers 0-5 1-10 0-5
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Tributoxy ethylphosphaat
Phtalaten, glycolethers
Additives
Preservatives < 1 < 1 < 1 < 1 < 1
Perfume < 1 < 1 < 1 < 1
Water > 50 50-70 80 70-85 60-80
Exposure to these products can occur during mixing and loading, and during cleaning
[RIVM report 320104003/2006]. Consumers can be exposed through inhalation,
dermal exposure.
Formaldehyde emissions from floor cleaners were studied by Solal C. et al. (2008), in
realistic use conditions (in emission test chamber or in an experimental house). This
work studied floor cleaners with and without Savon de Marseille in a pure or diluted
state. Except for the pure use of floor cleaners formaldehyde concentrations for all
floor cleaners were around or below 10µg/m3 and this trend remained steady after
use. The presence of Savon de Marseille does not influence formaldehyde emissions,
whether these floor cleaners are diluted or pure. On the contrary, the dilution of the
other floor cleaners decreased the formaldehyde concentrations. In fact, for pure use
of floor cleaners (without Savon de Marseille), formaldehyde concentrations were
around 47 µg/m3 just after use and around 10 µg/m3 after 60 – 90 min and
remained steady below 10 µg/m3 after 90-120 min. In this product category, the
formaldehyde concentrations for floor wipe A were the highest among all the tested
products: from 1249 μg/m3 (0-30 min) to 128 μg/m3 (see the following table). This
may be explained by the presence of formaldehyde or formaldehyde releasers within
the product (“anti-bacterial” wipes).
Table 4.8. TVOC and specific VOCs concentrations of tested products
Tested Product
TVOC (μg/m3)
VOCs of concern (μg/m3)
Formaldehyde (μg/m3)
Floor wipes A 103 Benzene: 1 Trichloroethylene: 55
1249
Floor wipes B 49790
Trichloroethylene: 30 1-(1-methylethoxy)-2-propanol: 45927 Terpineol: 14
6
J. Zhu et al. (2001) identified chemicals in the headspace of some consumer
products namely “floor shine clear for no-wax and regular floors”. Five compounds
109
were detected: n-butyl ether, α-pinene, β-pinene, limonene and 2-(2-
butoxyethoxy)ethanol.
Martins A. (2003) studied one soft cleaner detergent for varnished wood floors or
laminate floors covered by PVC layer. This detergent is a fat dissolver, support dirt
cleaning and gives a silky look to floors. The soft cleaner was applied in a room floor
and then indoor air was analyzed. After soft cleaner application new compounds
were not identified, however concentrations of some compounds measured before
(tetrahydrofuran, toluene, 1-metoxy-2-propanol, m/p-xylene, trimethylbenzene,
phenol, 2-(2-ethoxyethoxy)ethanol, 1-methyl-2-pirrolidionene and 1-methoxyethanol
benzoate) increased and then decreased. Some of the increased compounds (toluene
and m/p-xylene) were also detected in headspace studies of the same detergent.
4.4.4. Glass and window cleaner (Liquid, spray, tissues)
Based on the general composition, it is assumed that the non-volatile part in glass
cleaning sprays is about 5 % (RIVM report 320104003/2006).
Table 4.9. General formula of glass cleaners
Glass cleaners Liquid spray %
Surfactants
Anionic surfactants 0 – 10
Non-ionic surfactants 0 - 5
Bases 0 – 5
Ammonia
Solvents and hydrotopes 5 – 20
Alcohols, glycols or glycol ethers
Additives: < 1
Preservatives, perfume
Water 75 - 95
Additionally, 2-butoxyethanol, Camphene, 3-Carene, Limonene, b-Myrcene, a-
Phellandrene, a-Pinene, b-Pinene are also contained and may be found in the
emissions of these products [Nazaroff and Weschler, 2004].
110
In J. Zhu et al. (2001) two glass and surface cleaners were studied using headspace
method: one clear and one blue. The clear glass and surface cleaner emitted 2-
butoxyethanol and 2-hexyloxyethanol. The blue glass and surface cleaner emitted 2-
butoxyethanol, 2-hexyloxyethanol and limonene. In addition antibacterial glass and
surface cleaner was analysed and the study shown that 2-butoxyethanol, α-pinene,
camphene, β-myrcene, β-pinene, α-phellandrene, limonene, 3-carene and 2-
hexyloxyethanol were emitted.
Glass cleaners sold in Korea were analyzed in the study developed by K.-D Kwon et
al. (2007). This study shows that 2-butoxyethanol, ethanol and limonene were
emitted from one of the glass cleaners and 1,8-cineole, ethanol an limonene were
emitted from another. Concentrations of total VOCs determined in the two glass
cleaners from headspace phase were 4.026 ng/ml and 1.989 ng/ml.
Solal et al. (2008) report experimental results of emission test chamber and
measurements of indoor formaldehyde and VOCs concentrations associated with the
use of various cleaning products, namely glass cleaners. All experiments were
conducted in emission test chambers or in an experimental house. The TVOC level
for glass cleaners was 2662 µg/m3. The specific VOCs of concern were
trichloroethylene (14 µg/m3), 1-butoxy-2-propanol (1475 µg/m3) and 1,1-
diethoxyethane (1121 µg/m3). The formaldehyde emission profile for glass cleaners
shown that despite formaldehyde concentrations remain below 10 µg/m3 just after
use, emission profiles increase although the overall product volatilization rate is
declining. This may result from varying volatilization, chemical reactions between
airborne pollutants or sorption behaviour among the constituents.
Airborne exposures from short-term cleaning tasks with selected glass cleaners can
remain in the air even after tasks’ cessation, suggesting potential exposures to
anyone entering the room shortly after cleaning according to simulation studies
conducted (Bello et al., 2010).
Emission factors and chamber air concentrations for some VOCs associated with
simulated cleaning activities with glass/surface cleaner are presented in the following
table (Singer et al., 2006).
111
Table 4.10. Emission factor and initial chamber air concentrations for 2-
butoxyethanol and 2-hexyloxyethanol associated with simulated cleaning activities
with one glass/surface cleaner
Emission factor (mg/g product)
Chamber air concentration 0-1h (µg/m3)
2-BE 2-HE 2-BE 2-HE
Counter: full strength with scrub and rinse; towels removed 2.6 1.9 270 170 Counter: full-strength, spray and wipe only; towels retained 8.0 4.8 330 190
2-BE = 2-butoxyethanol; 2-HE = 2-hexyloxyethanol;
4.4.5. Bathroom cleaning agents (liquid, sprays, tissues)
Table 4.11. A general formula of bathroom cleaners is:
Bathroom cleaner
Liquid, mild%
Liquid, Strong %
Spray %
Surfactants 1 - 5
Anionic surfactants 1 – 15 0 – 5 Non-ionic surfactants
1 – 5 1 – 5
Cationic surfactants 5 – 15 Builders 1 - 10
NTA or polycarboxylates
0 – 15
Acids + Citric acid 0 – 15 Sulfonic -, lactic -, formic acid
5 – 30
Solvents 0 – 15 Isopropanol
Additives
Thickening agents < 1 < 1 < 1 Preservatives < 1 < 1 Dye < 1 < 1 < 1 Perfume < 1 < 1 Water 50-90 65-95 70 - 95
+: ingredient of bathroom sprays
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During leaving on and cleaning, compounds evaporate from the product, and
inhalation exposure takes place while during cleaning the surface, dermal exposure
could also occur.
Solal et al. (2008) report formaldehyde emissions for two categories of toilet
products: block and gel. For both categories, formaldehyde concentrations are
increasing with successive flushes, leading to a formaldehyde concentration above 10
μg/m3 for one of the toilet blocks studied.
The household ammonia-containing cleaners that were evaluated in the study of
Fedoruk et al. (2005) include a typical ‘‘store brand’’ ammonia concentrate (5%
ammonia by volume per the product label) sold for general use as a floor and tile
cleaner, as well as ready-to-use formulas of a ‘‘name brand’’ glass cleaner (1% and
3% ammonium hydroxide per the material safety data sheet) and a ‘‘store brand’’
glass cleaner (ammonia content not stated). The study has determined the content
of ammonia in the products and has performed exposure studies. One simulated an
accidental spill in order to evaluate the exposure to ammonia other assessed
exposures to airborne ammonia while a person performing household cleaning of
bathroom with these products. The authors conclude that routine household uses of
ammonia are unlikely to produce significant exposures when using standard cleaning
solutions (0.1–0.2%), but spillage or use of concentrated ammonia solutions (e.g.,
3%) in poorly ventilated areas can lead to potentially hazardous airborne ammonia
exposures.
Akland and Whitaker (2000) reported toluene as a disinfectant bathroom cleaner
constituent (cited in Nazaroff and Weschler, 2004).
Furthermore, Odabasi (2008), reported that inhalation exposure of bathroom
cleaning products is higher if the derivatives of combined use with bleach are
considered, due to the existence of halogenated VOCs. Gorguner et al., (2004) also
state that many cases with Reactive Airways Dysfunction Syndrome (RADS) brought
to their emergency (64%), were exposed to inhalation of gases during bathroom or
kitchen cleaning.
113
Bleach
As above referred, the majority of disinfectant and general purpose cleaners are
used in kitchens and/or bathrooms on a routine basis. Furthermore, a large number
of bathroom cleaning detergents contain bleach.
NaOH is generally added into bleach containing products as pH adjuster and
stabilizer. Also, some proprietary stabilizers are added into these products to
minimize the reaction of hypochlorite with the organic constituents. However, it is
not known if the stabilizers and pH adjustment can be 100% effective to prevent
hypochlorite-surfactant reactions. Considering the relatively long contact time from
production to use (several days to months), hypochlorite-surfactant reactions are
possible and cleaning products containing chlorine bleach may contain significant
amounts of chlorinated organics.
The objective of the Odabasi M. (2008) study was to investigate the presence of
halogenated VOCs in different chlorine bleach containing household products (in
pure and diluted forms) and their emission characteristics to determine the indoor air
halogenated VOC concentrations resulting from the use of selected household
products. Some experiments were conducted in an apartment in the bathroom,
kitchen and corridor (floor cleaning) before, during and 30 min after the product
applications. Measurements are summarized in the following table.
Table 4.12. Summary of indoor halogenated VOC concentration measurements
before, during and 30 min after chlorine bleach use
Compound Average ± SD (µg/m3)
Before During After 30 min
Chloroform 0.41 ± 0.25 9.5 ± 6.7 5.3 ± 9.5
Carbon tetrachloride 0.27 ± 0.11 55.2 ± 144 22.7 ± 66.4
1,1-dichloroethane 0.01 ± 0.001 0.18 ± 0.29 0.10 ± 0.16
1,2-dichloroethane 0.09 ± 0.13 0.09 ± 0.13 0.09 ± 0.12
1,1-dichloroethene 0.03 ± 0.01 0.86 ± 1.8 0.36 ± 0.89
1,2-dichloropropane n.d. 0.42 ± 0.33 0.30
1,1,1-trichloroethane 0.02 ± 0.003 0.02 ± 0.003 0.02 ± 0.004
Trichloroethene 0.04 ± 0.02 0.04 ± 0.02 0.04 ± 0.02
Tetrachloroethene 0.11 ± 0.05 0.11 ± 0.05 0.13 ± 0.05
Chlorobenzene 0.002 ± 0.001 0.01 ± 0.004 0.005 ± 0.001
114
1,4-dichlorobenzene 0.004 ± 0.003 0.005 ± 0.004 0.01 ± 0.01
1,2-dichlorobenzene 1.1 ± 0.62 1.4 ± 0.85 1.4 ± 0.63
1,3-dichlorobenzene 0.005 ± 0.001 0.01 ± 0.002 0.01 ± 0.002
Bromodichloromethane 0.13 ± 0.06 0.34 ± 0.09 0.53 ± 0.68
Dibromochloromethane 0.08 ± 0.03 0.18 ± 0.05 0.28 ± 0.34
Bromoform 0.02 ± 0.01 0.03 ± 0.01 0.04 ± 0.03
n.d. – not detected
In addition to halogenated VOCs, several other compounds (aromatics, aldehydes
and some oxygenated compounds) were also detected. Chloroform (2.9-24.6 µg/m3)
and carbon tetrachloride (0.25-459 µg/m3) concentrations significantly increased
during the use of bleach products. Compounds detected frequently in the
headspaces of pure and diluted products (carbon tetrachloride, chloroform, 1,1-
dichloroethene, 1,1-dichloroethane, and chlorobenzene) were also detected in indoor
air with during/before concentration ratios significantly >1, confirming their
association with bleach products.
Several halogenated compounds, especially the trihalomethanes (THMs) (chloroform,
bromodichloromethane, dibromochloromethane, and bromoform) are known as
disinfection by products forming as a result of drinking water chlorination. Since
there was no contact to any other organic matter (i.e., on dirty surfaces or in tap
water), the detected halogenated VOCs were those resulted from the reactions of
hypochlorite and organic matter (surfactants, fragrances and other organic
compounds) in the products.
THMs other than chloroform were also detected in all samples with increased
concentrations measured during and 30 min after the applications. Tap water was
used to dilute bleach products and to rinse the surfaces after/during the applications.
The results show that the increase in the concentration of these THMs was mainly
due to their presence in tap water. On the other hand, their during/before
concentration ratios (2–4) were significantly lower than that of chloroform.
Considering that chloroform and other THMs have comparable air–water partition
coefficients (KAW) and tap water concentrations, these ratios indicated that the indoor
chloroform was mainly contributed from bleach products or from the reactions of
bleach and organic matter on the surfaces being cleaned.
115
Another study, indicates that inhalation exposure of bleach on some of those who
inhale high-dose gas, developes reactive airways dysfunction syndrome (RADS),
(Yoshikawa et al., 2002).
4.4.6. Furniture polishes (liquid, spray, tissues)
Polishing products are usually available in three forms: aerosol (spray), liquid
(emulsion cleaner/polishes and "oil type" polishes) and semi-solid (paste waxes). The
products frequently referred to as "paste waxes" are actually a very concentrated
solution of waxes in an organic solvent or aqueous emulsion.
These products are intended to remove dust and stains from wooden furniture
surfaces, to produce shine and to provide protection against (water) spots. For this
reason, silicone fluids, wax, lemon oil or tung oil are added as ingredients. Lemon oil
and tung oil are used in products without water.
Table 4.13. The general formula for furniture polish products is as following [RIVM
report 320104003/2006]:
Cleaning & caring products
Furniture products, liquid %
Furniture products, aerosol spray can %
Waxes 51 Oil Turpentine oil 22 Mineral oil < 10 Solvents Naphtha 20 < 20 Petroleum distillate Additives Stearic acid 7 Water 55 – 65 Propellants < 18
Ethylene glycol monobutyl ether (2-butoxy ethanol) and styrene are contained in
liquid wax while benzene, toluene, ethylbenzene, n-hexane in paste and liquid wax.
Caryophyllene, Longifolene, a-Cedrene, Oleic acid and a-humulene are substances of
116
the wood polishes and waxes [Nazaroff and Weschler, 2004]. Dermal exposure
occurs by hand contact with the cloth sprinkled with the firniture polishing product.
Furniture polish may contain some of the following substances: nitrobenzene,
petroleum distillates, phenol, diethylene glycol.
Kwon et al. [2007] studied three different furniture polishes. One of the products
presented a value of total VOC emission of 1354 ng/ml, being the major compounds
acetone, 2,7-dimethylundecane, limonene, β-myrcene and α-pinene. Other product
presented hexane and limonene as the major compounds and a value of total VOC of
1252 ng/ml, while the third emitted decane and limonene and a value of total VOCs
of 1167 ng/ml.
In another study Kwon et al. [2008] studied the volatile organic compounds emitted
by three different furniture polishes. They identified 113 compounds in the purged-
gas phase, as for example acetone, 2-buthoxyethanol, decane, ethanol,
ethylbenzene, hexane, limonene, tetrachloroethylene, phenol, 1-propanol, toluene
and o-xylene.
Horii and Kannan [2008] studied the presence of organosilicone compounds
including cyclic and linear siloxanes in household products, including one furniture
polish. The study was done by direct injection of the product. The highest
concentration of octamethylcyclotetrasiloxane was found in the furniture polish, with
a value of 9380 mg/g.
Weschler and Nazaroff [2008] inform readers that waxes and polishes emit also
some SVOCs as stearic acid (octadecanoic acid), linoleic acid and caryophyllene.
Ozone is likely to be an important indoor oxidant only for those SVOCs that have
unsaturated carbon–carbon bonds, such as sesquiterpenes, linoleic acid, linolenic
acid and oleic acid, compounds present in the waxes and polishes. It will be
important to study the impact of ozone in this class.
In the study conducted by Guo and Murray [2001] three different kinds of furniture
polish (aerosol spray, emulsion and solvent) are characterized in terms of emissions
of TVOC in test chambers. The amount of TVOCs released from emulsion polish was
117
higher than the released from other polishes. This may be explained by the fact that
the emission rate of TVOCs from emulsion polish decreased much more slowly than
that from other furniture polish. Although the solvent furniture polish had the highest
initial emission rate of 4120 mg/m2h, it decreases rapidly to 0.05% within 24h.
Similarly, for the aerosol spray furniture the emission rate started at 879 mg/m3 and
decrease until 0.2% after 24h. However, for the emulsion polish the emission rate
after 24h was still 15% of the maximum emission rate (around 300 mg/m2h).
A study conducted in France by Solal et al. [2008] in test room MARIA from CSTB
identified as major VOCs emitters from furniture polish, nonane and decane. The
maximum value achieved for TVOC was 17531 μg/m3.The product presented also
emissions of formaldehyde and it was observed an increase of the concentration with
the time, reaching values of 5 and 11 µg/m3 after 120 min of the application of the
product.
4.4.7. Floor polishes (liquid, spray, tissues)
Floor-polishes contain ingredients such as waxes and polymers. Liquid floor polishers
for vinyl, cork, linoleum etc., contain approximately 10 μg/ml of N-ethyl
perfluorooctane sulfonamide (EtFOSA) [DEPA, 2006].
Liquid and paste waxes emit diethylene glycol monobutyl ether (2-(2-butoxyethoxy)
ethanol), n-hexane, acetaldehyde, 3-Carene, limonene, 2-butanone, carbon
tetrachloride, Propylene dichloride (1,2- dichloropropane), acetophenone, a-Pinene,
b-Pinene, caryophyllene, longifolene, a-Cedrene, Oleic acid and a-humulene
[Nazaroff and Weschler, 2004].
Dermal exposure occurs by hand contact with the cloth sprinkled with the floor
polishing product.
Floor polish is used worldwide, both in homes and in workplace buildings to maintain
the floor surface. According to an article from Wieslander and Norbäck [2010]
besides a case report on occupational dermatitis from ethylenediamine in a floor
polish remover (from 1989), they have found no previous publications on exposure
levels or ocular or respiratory effects of floor polish emissions in medical research
118
data bases such as Pub Med or Toxline. According consumer product declarations
available in Sweden, floor polish contain partly similar chemicals as in water-based
paints, mainly glycol ethers, as well as some compounds specific for polish removers
and floor polish.
In the study performed by Wieslander and Norbäck [2010] the exposure levels and
effects on medical symptoms and physiological signs from the ocular and nasal
mucosa in subjects exposed to a commonly used water-based floor polish system
with a polish remover and a floor polish are reported. The product from Johnson &
Johnson was commonly used for professional floor polishing in Sweden at the time of
the study. The product was applied in a large floor area situated in the basement of
a hospital. The work was organized to get a larger number of cleaners equally
exposed. Environmental measurements were performed and six glycol ethers were
detected during the work with the floor polish; ethylene glycol monoethyl ether
(EGEE), ethylene glycol monobutyl ether (EGBE), diethylene glycol monoethyl ether
(DEGEE), dipropylene glycol monomethyl ether (DPGME), diethylene glycol
monobutyl ether (DEGBE) and ethylene glycol phenyl ether (EGPE), with the highest
levels for DEGEE and DPGME. Measurements 2–17 days after the polish work
showed a rapid decay of the glycol ethers levels in the hospital ward (following
table).
119
Mean exposure to glycol ethers during polish removal and application, and after
application (with decimal correction)
Another compound reported as a component of floor-polishes is tris(2-
butoxyethyl)phosphate (TBEP). In the study of Korpi et al. [2008] the concentration
of TBEP in the air of a building school during floor polishing and daily floor cleaning
was measured. The TBEP concentrations in the air during floor polishing ranged from
160 to 330 ng/m3, and during floor cleaning the concentration was 60 ng/m3.
Some nanofilm spray products for floor protection (coating for non-absorbing floor
materials and coating for ceramic tiles) were studied [Nørgaard et al., 2009, 2010].
Some of the VOCs identified were: 1-propanol, 1,1-diethoxy ethane, diisopropoxy
methane, 2-butanone, 3-metyl-2-butanone, 6-methyl-3-heptanone, 1-chloro-2-
propanone, 1,1-dichloro-2-propanone, 1,3-dichlor-2-propanone, isopropylacetate and
1H,1H,2H,2H-perfluorooctyl triisopropoxysilane. The particles which have been
reported to be released during application of those products (Nørgaard et al., 2009)
are mainly consisting of aerosolized silanes/siloxanes and their condensates
identified in this study.
Full-scale emission experiments performed by Vejrup in a climate chamber (41 m3
with a dilution ventilation of 0.5-1.5 h-1) showed peak concentrations of the order of
10-20 mg/m3 of 2-2-ethoxyethoxyethanol about 1-2 h after the application of an
undiluted polish agent on a floor surface made of polyvinyl chloride -PVC [Wolkoff et
al., 1998]. The time concentration profile is show in
Personal sampling during polishing of a PVC floor showed concentrations of the order
of 4 mg/m3, primarily of terpenes.
120
Figure 1. The time-concentration profile of butoxyethoxyethanol after PVC flooring was polished with an undiluted polish agent in a climate chamber with dilution ventilation (41.2 m3 and floor area = 18.8 m2, air exchange rate = 0.59 h-1). Photoacoustic detector (wavelengths 1070-1135 cm-1 (A) and 2760-2840 cm-1 (B)).
Start of polishing at time = 0 min [taken from Vejruo, 1996]. The study performed
by Martins et al [2002] evaluate the influence on the indoor air composition of a real
room (80 m3 with a dilution ventilation of 1.29 h-1), in terms of VOCs, after the
application of a self-polishing care agent in a vinyl coated cork flooring material. The
results obtained also shows that the major compound emitted by the floor polishing
product (V-Care from Wicanders) is a glycol ether, 2-(2-ethoxyethoxy)ethanol that
presented a fast decrease of emissions (see Figure 2). It was observed also that the
successive application of the care product did not produce either an increase of the
emissions of the compounds emitted by the material, or the formation of secondary
VOCs, during the 72-day study.
Singer et al. [2006] investigated the formation of secondary pollutants resulting from
household product use in the presence of ozone, being one of the products studied
the pine oil-based cleaner (POC) to apply to the floor. The emissions were studied in
a 50-m3 chamber designed to simulate a residential room. POC emissions were
dominated by terpene hydrocarbons and alcohols: α-pinene, camphene, α-
phellandrene, α and γ-terpinene, d-limonene, terpinolene, 1-terpineol, β-terpineol, 4-
terpineol, α-terpineol, γ–terpineol, p-cymene and eucalyptol. VOC profiles following
application of POC are shown in Figure 3.
121
Figure 2. 2-(2-ethoxyethoxy)ethanol emissions by the floor polishing product
Figure 3. Constituent concentrations in chamber air following floor mopping with a dilute solution of the pine oil cleaner (POC). Data for Exps G and H have been adjusted to account of ozone-induced degradation of analytes on Tenax; the symbol represents the corrected value and the T-bar extends down to the measured value. Adjustments based on Figs. 1 and 2 of Calogirous et al. (1996).cited from Singer et al. [2006]. Some nanofilm spray products for floor protection (coating for non-absorbing floor
materials and coating for ceramic tiles) were studied in a test chamber (Nørgaard et
al., 2009, 2010). Some of the VOCs identified were: 1-propanol, 1,1-diethoxy ethane,
122
diisopropoxy methane, 2-butanone, 3-metyl-2-butanone, 6-methyl-3-heptanone, 1-
chloro-2-propanone, 1,1-dichloro-2-propanone, 1,3-dichlor-2-propanone,
isopropylacetate and 1H,1H,2H,2H-perfluorooctyl triisopropoxysilane. The particles
which have been reported to be released during application of those products are
mainly consisting of aerosolized silanes/siloxanes and their condensates [Nørgaard et
al., 2010].
4.4.8. Oven cleaners
Oven cleaners are strong degreasers and they are suitable for removing sticked dirt
of ovens, grills etc. Oven cleaners contain strong alkaline ingredients and therefore,
they can be irritating and caustic. Strong alkali is necessary to remove burned-on
soils. There are trigger sprays and spray cans. When applying theses products
inhalation and dermal exposure can occur.
Table 4.14. In the following table the general formula of oven cleaners is shown
Liquid % Foam spray can %
Surfactants: 1 – 15 - anionic and non-ionic surfactants
Builders: 0 – 15 - NTA Bases: 1 – 15 1 – 5 - caustic soda or caustic potash
Solvents: Glycols or glycol ethers 0 – 5 1 – 30 Mono-ethanolamine 0 – 5 Additives Thickening agents e.g. smectite
< 5
Perfume & dye < 1 Water 85 – 95 60 – 90 Propellants < 10
4.5. Air fresheners
These products mainly emit terpenes (such as d-limonene, linalool, α-pinene, and β-
pinene), acetaldehyde, acetone, ethanol, ethyl acetate, benzaldehyde, isopropyl,
alcohol. Terpenes can react with indoor ozone to produce potentially substantial
123
levels of secondary pollutants, including aldehyde compounds (such as
formaldehyde), ultrafine particles, glycol ethers, secondary organic aerosols, and the
hydroxyl radical (ECA, 2007). Air fresheners can produce steady-state levels of tens
to hundreds of micrograms per cubic meter of ozone-reactive terpenoids. Exposure
to such products, as suggested by some studies, have potential associations with
adverse health effects, including asthma and asthmatic exacerbations, headaches,
mucosal symptoms, and, the emphasis of most priorwork, epidermal exposure
effects such as allergic contact dermatitis. In the U.S., manufacturers of consumer
products, and owners of chemical formulations (such as fragrances) in those
products, are not required to disclose all ingredients to consumers. Depending on the
product, the word “fragrance” may or may not need to be listed, and this section
looks at the two main cases.
Caress and Steinemann [2004, 2005] found that 17.8% and 20.5% (first and second
study) reported headaches, breathing difficulties, or other health problems when
exposed to air fresheners. This study relies on a questionnaire approach which is
subject to recall bias and did not verify the symptoms using clinical methods cf.
Singal et al., 2011. For instance, among asthmatics, 29.7% and 37.2% reported
breathing difficulties, headaches, or other health problems when exposed to air
fresheners. Fragrance ingredients in consumer products are exempted from
disclosure in the US, in any product. Depending on the product, the word “fragrance”
may or may not need to be listed, and this section looks at the two main cases
[Steinemann, 2009]. Ingredients can also be exempt from disclosure through “trade
secrets” protection.
Air fresheners can produce steady-state levels of tens to hundreds of micrograms per
cubic meter of ozone-reactive terpenoids. Use of cleaning products and air
fresheners in the presence of elevated indoor ozone is of concern because of the
formation of secondary air pollutants that pose health risks (Singer et al., 2006).
124
4.5.1. Combustible air fresheners
4.5.1.1. Insense Lee and Wang [2004] performed a study with the objective of characterize and
compare the emissions of air pollutants before, during and after incense burning in a
large environmental chamber. In this study, the emission factors for PM2.5, PM10,
CO2, CO, NOx, CH4 and NMHC (in mg/g incense burned), VOCs and carbonyl
compounds concentrations were measured for ten different types of incense. It was
observed that the CO peak levels of seven incense types greatly exceeded the value
of 800 ppm. The formaldehyde concentrations of six types of incense were higher
than the 100 µg/m3 and the benzene concentrations of all tested incense were
significantly higher than 16 µg/m3. This implies that indoor incense combustion has
adverse effects on human health. It is also concluded that there is variability among
the ten types of incense (with regards to carbonyl compounds, VOCs, PM and gas
pollutants). The following table shows the values of emission factors measured for
the ten types of incense.
Table 4.15. Emission rates (a) and emission factors (b) of incense
Eight carbonyl compounds were monitored: formaldehyde, acetaldehyde, acetone,
acrolein, propionaldehyde, methacrolein, butyraldehyde and valeraldehyde. It was
observed that high concentrations of formaldehyde (> 100 µg/m3) were measured
for seven of the ten types of incense. The emission factors are show in Figure 4.
125
Figure 4. Normalized carbonyl compounds emission of incense burning
Concerning VOCs it was found that benzene, toluene, methyl chloride and methylene
chloride concentrations increased significantly during burning of the ten incense
types (see next table). In addition, the average concentrations of other individual
VOCs, such as ethylbenzene, m,p-xylene, styrene and o-xylene were also observed
to increase with incense combustion. The concentrations for some VOCs were even
higher after burning than during burning, which implies that human exposure periods
may be long.
126
Table 4.16. Temporal changes of (a) VOCs concentrations and (b) normalized VOCs
concentrations for ten types of incense.
Jetter et al. [2002] present a study on the characterization of emissions from burning
incense. Emissions of particulate matter were measured for 23 different types of
incense using a cyclone filter method. Incense emissions tests were performed in a
test chamber specifically designed for measuring fine particle emissions. Emission
rates for PM2.5 (particulate matter less than 2.5 mm in aerodynamic diameter)
ranged from 7 to 202 mg/h, and PM2.5 emission factors ranged from 5 to 56 mg/g of
incense burned. Emissions of carbon monoxide (CO), nitric oxide (NO), and sulfur
dioxide (SO2) were also measured for seven types of incense. Emission rates of CO
ranged from 144 to 531 mg/h, of NO from 0.16 to 4.39 mg/h and for SO2 from 1.4 to
25.5 mg/h.
Studies have indicated that exposure to incense smoke may be linked to health
effects including cancers, asthma, dermatitis, mutagenesis, and genotoxic effects. An
127
increased risk of childhood brain tumors has been associated with maternal contact
with nitrosamine-containing substances such as burning incense. An increased risk of
leukemia was found for children whose parents burned incense in the home before
pregnancy or during the nursing period. It has also been found that increased
relative risks for lung cancer for exposure to incense smoke in Chinese females in
Singapore.
Incense has been found to emit particulate matter (with a geometrical diameter 0.05
and 0.5 μm), carbon monoxide (CO), sulphur dioxide (S02), nitrogen dioxide (NO2),
isoprene, benzene, and nitromusks (musk ambrette, musk ketone and musk xylene).
Aldehydes and other volatile organic compounds (VOCs), polycyclic aromatic
hydrocarbons (PAHs) have also been found in incense smoke [Lee & Wang, 2004;
Jetter et al., 2002].
Maupetit and Squinazi [2009] present a methodology to characterise the emissions
of VOCs and formaldehyde from burning incense and scented candles indoors. VOCs
and formaldehyde emissions from 43 products were measured in a test room of the
Centre Scientifique et Technique du Bâtiment (CSTB) experimental house. A testing
protocol was established to characterise time-dependent emissions from burning
incense and candles. For incense sticks and cones, the highest benzene and
formaldehyde emissions were measured during combustion and for an hour
afterwards: the concentrations measured then decreased significantly as the
pollutants were removed by the ventilation system (0.6 vol/h). Incense cones
emitted more formaldehyde than incense sticks, and for incense in general, the
higher the burnt mass, the higher the emissions. Benzene and formaldehyde
emissions from scented candles were far lower than from incense. Nevertheless,
formaldehyde emissions did increase slightly during candle burning, presumably due
to secondary reactions.
Incense burning may also produce the radical concentration, e.g. (de Kok et al.,
2004) and furthermore customary practice of burning a significant quantiy (3 sticks
twice day) of incense is likely to affect the health of an exposed individual adversely
if the room is not well ventilated (See and Balasubramanian, 2011).
128
4.5.1.2. Candles
As a source of indoor contamination, the impact of candle burning on human health
cannot be ignored. The generation of particles by candle combustion and some
hazardous pollutants such as lead, aldehydes and other organic compounds were
detected from candle smoke.
When candles are burned, they emit trace of organic chemicals, including
acetaldehyde, formaldehyde, acrolein and naphthalene [Lau et al., 1997]. Some
candles also emit lead which is the primary constituent of public health concern in
candle emissions [US EPA, 2001]. Metal was originally put in wicks to keep the wick
standing straight when the surrounding wax begins to melt. Burning several candles
exceeded the USEPA’s 10_6 increased risk for cancer for acetaldehyde and
formaldehyde, and exceeded the Reference Concentration (RfC) for acrolein.
The concentrations of most VOCs from candles combustion were below the detection
limit. Among five (5) candles tested, one of them which was made by beeswax,
generated relative smaller amount of air polutants [Lee and Wang, 2006].
Some candles emit lead which is the primary constituent of public health concern in
candle emissions. Metal was originally put in wicks to keep the wick standing straight
when the surrounding wax begins to melt. It is possible for consumers to
unknowingly purchase candles containing lead wick cores and repeatedly expose
themselves to harmful amounts of lead and organic chemicals through regular
candle-burning. The study conducted by Wasson et al. [2002] conducted in test
chambers shows that individual candles emitted lead to the air at averages rates that
ranged from 100 to 1700 µg/h. In the present the lead wick were banned from the
industry of candles in USA. Replacements for lead in metal-cored candle wicks
include zinc and tin. Zinc emission factors up to 0.12 mg/h were identified by Nriagu
and Kim [2000].
Lau, Fiedler, Hutzinger, Schwind, and Hosseinpour [1997] investigated emissions of
polycyclic aromatic hydrocarbon (PAH), polychlorinated dibenzo-p-dioxins (PCDD),
dibenzofurans (PCDF) selected chlorinated pesticides and some gas-phase volatile
organic carbon (VOC) from exhaust fumes of candles. The experiments were
129
performed in test chambers. A total of eight raw material samples forming sixteen
candles, were analysed. The emissions of PCDD/PCDF range from 0.004 to 0.047 pg
I-TEQ/g and the emissions of PAH range from 4.75 to 156 ng/g. Benzo(a)pyrene was
detected in all the candles but two, with values between 0.01 and 0.13 ng/g.
Acroleyne was detected only in two candles, with emissions between 0.1 and 5.4
ng/g. Formaldehyde was detected in all the candles with one exception, and the
values ranged from 3.7 to 14.1 ng/g. Acetaldehyde was not detected only in three
candles, and the values detected in all the others ranged from 26.0 to 61.8 ng/g.
They found that candles have low PAH and VOC emission levels compared to other
indoor combustion sources. This is likely caused by the high combustion temperature
and relatively complete combustion occurring in a steady burning candle.
In another study performed by Afshari et al. [2005] the concentration of ultrafine
particles emitted by burning pure wax candles in test chamber was measured. The
maximum value of concentration measured was approximately 241.000
particles/cm2. The concentration of particles larger than 0.3 µm was very low, but
showed a sharp increase after 85 min, at the point when candles were extinguished.
Zai et al. [2006] studied the size distribution, number and mass emission factors of
candle particles associated with three different modes of burning: steady burn,
unsteady burn and smouldering. Particle emitted by a steady burning candle is
invisible, but it contains a large number of ultrafine particles, which contribute little
to mass. An unsteady burning candle produces black smoke, the size distribution of
which is bimodal in the 10–500 nm range. The particle of the unsteady burn mode
has a significant contribution to mass concentration. The emission of a smoldering
candle is hard to be directly compared with that of the other two modes, as a
smoldering candle hardly consumes any mass, and considering it lasts a very short
time, both of the number and mass emission levels are significantly high. In the
study performed by Fan and Zhang (2001) a value of 0.87 ± 0.6 mg/g for PM10
emission factor for a paraffin candle. Fine et al. [1999] obtained values for fine PM
emissions of 0.52-3.72 mg/g for paraffin candles and 1.46-2.04 mg/g for beeswax
candles.
130
Additionally, He et al. [2004], stated that PM2.5 emission rate depends on the
burning rate ranging from 0.055 to 0.443 mg/min, and this value is approximately 10
times higher that the background levels.
Citronella candles are widely used as insect repellents, especially outdoors in the
evening. Because these essential oils are unsaturated, they have a unique potential
to form secondary organic aerosol (SOA) via reaction with ozone, which is also
commonly elevated on summer evenings when the candles are often in use. The
ingredients specific to citronella candles are mostly unsaturated terpenes; these
include limonene and geraniol, as well as a host of minor constituents [Bothe & Mc
Pherson Donahue, 2010].
The aim of the study performed by Pagels et al. [2009] was to investigate the
physical and chemical properties of particle emissions from candle burning in indoor
air. Two representative types of tapered candles were studied during steady burn,
sooting burn and smouldering (upon extinction) under controlled conditions in a
walk-in stainless steel chamber (22 m3). Steady burn emits relatively high number
emissions of ultrafine particles dominated by either phosphates or alkali nitrates. The
likely source of these particles is flame retardant additives to the wick. Sooting burn
in addition emits larger particles mainly consisting of agglomerated elemental
carbon. This burning mode is associated with the highest mass emission factors.
Particles emitted during smouldering upon extinction are dominated by organic
matter. Mass emission factors corresponding to the data described above were fitted
using the boxmodel. The total mass emission factors determined in this study were
2.4±0.1 and 0.87±0.14 mg/h for the steady burning mode and 8.9±0.4 mg/h and
25.3±0.02 mg/h for the sooting burning mode, for candles I e II respectively.
One study performed by Costa [2010] shows the measurement of PM and VOC
emissions from different types of candles. In a test chamber, during the first hours of
burning. The indoor concentrations of VOCs and PM10 obtained in real room based
on the emission rate were low. It was observed that the major VOCs emitted, are
terpenes and alcohols derived by the use of essential oils. Benzene was also
detected. However, the major compound emitted was diethyl phthalate, emitted by
candle 5. It was observed that the compound diethyl phthalate sometimes is
detected in the gaseous phase and sometimes in the particulate phase, showing the
131
importance of monitoring both types of emissions. It was observed a high variation
between the tests, always performed in duplicate. The values of PM10 emissions
obtained for the candles studied are show in the following table.
Table 4.17. Emission values (µg/h per g of candle burned) of PM10 determined in
test chamber experiment for five different types of candles
candle FE (µg/h per g of candle
burned)
1 9.00
3.24
2 18.6
12.7
2 19.5
15.1
4 6.33
7.81
5 130
11.1
The values for the VOCs detected by candle 5 are show in following table.
Table 4.18. Emission values (µg/h per g of candle burned) of VOCs identified in test
chamber experiment for candle 5
candle
FE (µg/h per g of candle
burned)
Test 1 Test 2
Benzene 0.04 0.08
Ethylbenzene 0.04 0.05
Styrene 0.05 0.19
Benzaldehyde 0.38 0.39
Acetophenone 0.21 0.29
acetic acid, phenylmethyl ester 0.08 0.12
Isobornyl isovalerate 1.1 0.98
Vanilin 0.39 0.45
132
Ethyl Vanilin 0.44 0.47
Diethyl phtalate 12.9 33.4
In the study performed by Glytsos et al. (2010) candle burning experiments indicated
that this common indoor activity is a major source of nano particles (particles with
diameter below 50 nm). At the beginning of the candle burning process, the
emission of particles smaller than 50 nm represented more than 85% of total
particles and the average maximum concentration was 2.97 x 105 ± 1.94 x 105 # cm-
3. The average maximum total particle concentration recorded by the Grimm SMPS
and the P-Trak was 3.2 x 105 ± 2.02 x 105 # cm-3 and 4.92 x 104 ± 3.23 x 104 # cm-
3 respectively. Maximum concentration was observed before the end of the process
of candle burning in contrast to the majority of other simulated sources in the
current study. Average maximum PM2.5 mass concentration, while the source was
active, was 376±176 µg/m3 and it was observed just before the candle was
extinguished. During the simulation of incense stick burning maximum concentration
of particles ranged between 8.3 x 104 and 13.6 x 104 # cm-3 (SMPS data), while
maximum PM2.5 concentration ranged between 600 and 700 µg/m3.
4.5.2. Air fresheners (spray)
These products mainly emit terpenes (such as d-limonene, linalool, α-pinene, and β-
pinene), acetaldehyde, acetone, ethanol, ethyl acetate, benzaldehyde and isopropyl
alcohol. Terpenes can react with indoor ozone to produce potentially substantial
levels of secondary pollutants, including aldehyde compounds (such as
formaldehyde), ultrafine particles, glycol ethers, secondary organic aerosols, and the
hydroxyl radical (ECA, 2007)(Nazaroff and Weschler, 2004). Air fresheners can
produce steady-state levels of tens to hundreds of micrograms per cubic meter of
ozone-reactive terpenoids. The air fresheners’ use can represent a continuous
emission source and therefore presents a different set of exposure considerations.
Exposure to such products, as suggested by some studies, have potential
associations with adverse health effects, including asthma and asthmatic
exacerbations, headaches, mucosal symptoms, and, the emphasis of most prior
work, epidermal exposure effects such as allergic contact dermatitis.
133
Caress and Steinemann (2004, 2005) found that 17.8% and 20.5% (first and second
study) reported headaches, breathing difficulties, or other health problems when
exposed to air fresheners. This study relies on a questionnaire approach which is
subject to recall bias and did not verify the symptoms using clinical methods cf.
Singal et al., 2001. For instance, among asthmatics, 29.7% and 37.2% reported
breathing difficulties, headaches, or other health problems when exposed to air
fresheners. Fragrance ingredients in consumer products are exempted from
disclosure in the U.S., in any product. Depending on the product, the word
“fragrance” may or may not need to be listed, and this section looks at the two main
cases (Steinemann, 2009). Ingredients can also be exempt from disclosure through
“trade secrets” protection.
In a study performed by Afshari et al. (2005) the concentration of ultrafine particles
emitted by a spraying air-freshener applied in a test chamber was measured. The
maximum value of concentration measured were approximately 30 000 particles/cm2.
The generation of particles reached their maximum concentration after 4 minutes.
The concentration of particles sized between 0.3 and 1.0 µm increased when the
ultrafine particles decreased, which indicates that the ultrafine particles are the
primary pollutants, being the others generated by condensation of vapours.
Kwon et al. (2007) studied four different air fresheners but did not specify the type
of product. The total VOC concentration determined by headspace phase and the
major compounds identified are presented in the following table.
Table 4.19. Total VOC concentration determined in air fresheners headspace
Air freshener Major compounds
Total VOC
concentration
(ng/ml)
AL Decane, limonene 1354
AW Acetaldehyde, decane, dodecane, ethyl
acetate, nonadecane, undecane
5132
DFA Camphene, ethanol, α-pinene 1356
GR Hexane, 2-methylpentane 1354
134
In the study performed by Steinemann (2009) one spray air freshener was studied
through headspace analysis. It was a wall-mounted unit that emits a fragranced
spray and that is used primarily in lavatories in industrial and institutional
environments, including schools and health care facilities. The VOCs identified were
d-limonene, 3-methoxy-3-methylbutanol, linalool, careen isomer, nonanal, 2,4-
dimethyl-3-cyclohexene-1-carboxaldehyde, 2-methyl-2,4-dimethoxybutane, α-
phenylethyl acetate, β-pinene, 3-hexen-1-ol, octanal and ethanol.
4.5.3. Passive units (air fresheners)
Passive units used as air fresheners include plug-in products, wall-mounted units,
solid deodorant disks or gels which emit a pleasant smell.
The analysis of a solid deodorant disk that is used in lavatories showed that these
products emit d-limonene , 4-tert-butylcyclohexyl acetate, acetaldehyde, benzyl
acetate, 2,7-dimethyl-2,7-octanediol, acetone, ethanol, careen, citronellyl acetate,
hexanal, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde (Triplal 1), allyl heptanoate,
1-methyl-4-(1-methylethyl)-cyclohexane, ethyl butanoate, 3-hexen-1-ol , o, m, or p-
cymene, α-pinene, carene isomer [Steinmann, 2009]. Toilet deodorant blocks also
contain and emit naphthalene [Wan-Kuen et al., 2008].
In the study performed by Guerrero and Corsi (2009), three different products were
tested: closet air freshener (hanging product consisting of p-DCB cakes in a slotted
plastic shield), toilet bowl deodorizer (tablet suspended from edge of toilet bowl),
and moth crystals (crystals stored in a cylindrical box with an open top). Products
were each placed inside a ventilated walk-in laboratory chamber. The mean (of three
replicates) emission rates for each product are shown as a function of time in Figure
5 . Emission rate for the moth crystals and closet air freshener were initially lower
than corresponding emission rate for the toilet bowl deodorizer. In the case of the
moth crystals, the crystals were located 2.7 cm below the lip of the container they
were stored in, thus shielding them from air movement and requiring molecular
diffusion through the container headspace as the primary emission mechanism.
135
Figure 5. Emissions rates of p-DCB products
4.5.4. Ethereal oils
Exposure to essential oils or perfume can cause respiratory problems, especially in
high-risk populations, and the compositions of evaporating essential oil gas involving
terpenes and aromatics can contribute to these adverse effects. If ingested in high
doses, they may be toxic causing central nervous system symptoms such as
dizziness or unconsciousness or hypersensitivity manifested in rashes and other
allergic reactions. Eye irritation, cough, chest tightness and dyspnea might occur
following exposure to fragrances, especially for predisposed subjects [Chiang et al.,
2010].
Geraniol is a constituent of rose and citronella oil,citronellal is present in balm mint
and citronella oil, geranial in lemon grass, rose and orange oil and Neral is present
in rose and orange oil [Nazaroff and Weschler, 2004].
The vaporization of essential oil in different microenvironments depends on the
microenvironment conditions, such as ambient temperature, humidity, ventilation
rate, and operation conditions such as, heating rate mixture composition. The
following table presents the VOCs concentration (ppm) from the 5 essential oils at
40ºC.
136
Table 4.20. VOCs concentration (ppm) from 5 essential oils at 40 ºC.
Compound Rose Lemon Rosemary Tea tree Lavender
Toluene 8.89 +
3.98
4.58 +
0.92
8.47 +
3.03
3.22 +
0.22
3.70 +
1.13
1,2,3-
Trimethylbenzene
5.90 +
0.49
5.31 +
0.69
7.68 +
1.12
8.37 +
2.35
5.87 +
2.15
1,2,4-
Trimethylbenzene
5.74 +
0.48
5.72 +
1.27
14.15 +
4.85
16.47 +
8.11
9.13 +
6.13
n-Undecane 5.59 +
1.54
9.82 +
0.43
10.55 +
4.86
13.14 +
1.77
11.97 +
4.11
p-Diethylbenzene 5.28 +
0.40
6.17 +
0.43
7.09 +
0.74
7.91 +
2.69
6.21 +
1.26
m-Diethylbenzene 5.01 +
0.31
6.52 +
0.71
6.84 +
2.04
8.08 +
1.60
6.07 +
1.46
n-Decane 4.19 +
0.75
2.9 + 0.02 3.41 +
0.12
3.07 +
0.03
2.51 +
0.13
Styrene 4.14 +
1.48
1.77 +
0.12
2.63 +
0.11
2.06 +
0.11
1.57 +
0.04
1,3,5-
Trimethylbenzene
3.69 +
0.52
2.82 +
0.18
4.95 +
1.17
4.71 +
1.34
3.10 +
1.11
o-Ethyltoluene 3.66 +
0.65
2.63 +
0.12
4.62 +
1.26
4.54 +
1.32
3.02 +
1.08
o-Xylene 3.60 +
0.88
2.29 +
0.13
5.79 +
2.52
6.67 +
3.04
3.36 +
1.53
m,p-Xylene 3.44 +
0.85
2.14 +
0.21
3.89 +
1.20
3.58 +
0.93
2.42 +
0.19
m-Ethyltoluene 3.40 +
0.70
2.46 +
0.12
5.59 +
2.26
5.43 +
2.17
3.13 +
1.34
p-Ethyltoluene 3.38 +
0.63
2.34 +
0.42
4.01 +
0.16
3.06 +
0.74
2.37 +
0.15
Ethylbenzene 3.20 +
0.95
1.79 +
0.18
2.83 +
0.70
2.33 +
0.26
1.81 +
0.10
n-Propylbenzene 2.48 +
0.55
1.55 +
0.23
2.38 +
0.41
2.31 +
1.20
1.56 +
0.25
137
Isopropylbenzene 1.60 +
0.35
0.97 +
0.10
1.28 +
0.09
1.31 +
0.11
0.88 +
0.12
n-Nonane 1.53 +
0.37
0.91 +
0.01
1.17 +
0.07
1.07 +
0.08
0.89 +
0.15
n-Hexane 1.50 +
0.47
1.26 +
0.03
2.14 +
0.59
2.59 +
0.06
2.00 +
0.14
Benzene 0.91 +
0.38
0.36 +
0.01
0.47 +
0.12
0.42 +
0.05
0.44 +
0.09
Tea tree oil is a complex mixture of terpene hydrocarbons and tertiary alcohols
distilled mainly from plantation stands of the Australian native plant Melaleuca
Alternifolia. Currently, the composition of tea tree oil is regulated by an international
standard (International Organisation for Standardisation) which sets maxima and/or
minima for 14 components of the oil, as described in the following table (Hammer et
al., 2006).
Table 4.21. Composition of tea tree oil
Component Composition (%)
ISO 473 range (1996) Typical composition
Terpinen-4-ol ≥30 40.1
δ-Terpinene 10-28 23.0
-Terpinene 5-13 10.4
1,8-Cineole ≤15 5.1
Terpinolene 1.5-5 3.1
q-Cymene 0.5-12 2.9
-Pinene 1-6 2.6
-Terpineol 1.5-8 2.4
Aromadendrene Traces-7 1.5
d-Cadinene Traces-8 1.3
Limonene 0.5-4 1.0
Sabinene Traces-3.5 0.2
Globulol Traces-3 0.2
Viridiflorol Traces-1.5 0.1
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Three popular essential oils in the market (lavender, eucalyptus and tea tree) were
used to perform a study aimed to characterize the profiles and concentrations of
emitted volatile organic compounds when evaporating essential oils indoors (Su et
al., 2007). Two different types of indoor environments were chosen for the
experiment: one bedroom (space volume 21.6 m3; air change rate 1.8 h) and one
small office (space volume 28.2 m3; 1.3 h). The emissions of VOCs mostly occurred,
both at home and office environment, during the first 20 min of initial evaporation of
eucalyptus and tea tree oil. The emissions of VOCs of lavender oil seemed to be
slower than eucalyptus and tea tree oils, yet, also reaching steady state within 30–45
min, either at home or at office space. The levels of indicative volatile organic
compounds during the testing periods (180 min) are described in the next table.
139
Table 4.22. Levels of indicative volatile organic compounds during the testing periods
Concentration
(µg/m3)
Office Home
1st 2nd 3rd 1st 2nd 3rd
Lavender
Linalool 533 496 604 987 779 594
D-limonene 12 6 2 32 21 28
Terpinene-4-
ol
100 74 56 198 89 48
Eucalyptus
Eucalyptol 523 1541 503 263 203 522
D-limonene 69 36 34 13 13 32
ρ-cymene 58 46 _ 14 16 28
Terpinene-4-
ol
71 77 33 31 27 _
Tea tree
Eucalyptol 94 97 42 80 53 34
D-limonene 23 19 6 3 5 _
ρ-cymene 132 119 72 173 157 91
Terpinene-4-
ol
882 903 623 954 840 468
4.5.5. Pluged-in units
Steinmann (2009) investigated also a plug-in air freshener, used in residential,
industrial, and institutional environments for its emissions. It was found that this
product emits d-limonene, α-pinene, β-pinene, ethanol, ethyl butanoate, ethyl
acetate, 3-hexen-1-ol, 1-butanol, 3-methyl-acetate β-phellandrene, acetaldehyde,
benzaldehyde, carene isomer, 1-methyl-3-(1-methylethyl)-cyclohexene, isopropyl
alcohol, 1-butanol, 2-methyl-, acetate, camphene, acetone, methyl butanoate,
dimethyl ethyl cyclohexene and α-phellandrene.
140
4.6. Pests control
It is often for consumers not to comply with the written directions of use for these
products. The main routes of exposure are inhalation and through the skin. For
spraying products, a much higher exposure occurs in a situation where spraying is
carried out above the head than when it is aimed at the floor. This can be attributed
to the contact with the aerosol cloud.
There are three main aspects when characterizing the exposure of spray applications
that is [RIVM, 2006b]:
- the type of spraying device (spray can or trigger spray);
- whether the formulation still needs to be processed before application (mixing and
loading);
- the target of the application.
Exposure to high levels of cyclodiene pesticides, commonly associated with
misapplication, has produced various symptoms, including headaches, dizziness,
muscle twitching, weakness, tingling sensations, and nausea. In addition, EPA is
concerned that cyclodienes might cause long-term damage to the liver and the
central nervous system, as well as an increased risk of cancer.
There is no further sale or commercial use permitted for the following cyclodiene or
related pesticides: chlordane, aldrin, dieldrin, and heptachlor. The only exception is
the use of heptachlor by utility companies to control fire ants in underground cable
boxes. It is clear that there is little information available on exposure and health
effects for many of these compounds while exposure to these compounds should be
limited where possible (Rudel and Perovich, 2009).
4.6.1. Electric units (insecticide tablets, air fresheners)
In the study performed by Steinemann (2009) one passive air fresheners was
studied through headspace analysis. It was a plug-in air freshener, used in
residential, industrial, and institutional environments. The VOCs identified were d-
limonene, α-pinene, a-pinene, ethanol, ethylbutanoate, ethylacetate, 3-hexen-1-ol,
141
1-butanol-3-methyl-acetate, phellandrene, acetaldehyde, benzaldehyde, carene
isomer, 1-methyl-3-(1-methylethyl)cyclohexene, isopropyl alcohol, 1-butanol-2-
methyl- acetate, camphene, acetone, methylbutanoate, dimethylethylcyclohexene
and phellandrene.
Singer et al. (2006) investigated the formation of secondary pollutants resulting from
household product use in the presence of ozone, being one of the products studied
an air freshener device to plug to electricity (AFR). The emissions were studied in a
50 m3 chamber designed to simulate a residential room. AFR emissions were
essentially d- -citr -citral,
benzylacetate and bornyl acetate.
4.7. Clothes and fabrics
The exposure of the consumer to textile fabrics, such as curtains, tablecloths,
clothes, bed linen, and bed blankets, varies according to the end-use of the textile.
The Danish Environmental Protection Agency (EPA-Denmark) performed an
evaluation by exposure scenarios where the exposure was considered the highest.
This means usage with close bodily contact, such as clothes and bed linen. The
direct exposure from e.g. curtains, tablecloths and blankets, is estimated to be lower
and more of another character, like inhalation of volatile compounds or compounds
adsorbed to dust fibres [COSI, 2005]. EPA-Denmark considered the duration of the
contact exposure too short to involve a significant migration of chemical compounds
to the skin from household textiles, such as towels being wet or via sweat. The
exposure to children is, however, considered increased if they e.g. place the textile in
the mouth and are sucking or chewing on it.
For a textile fabric made of 100% viscose, contents of formaldehyde of 43mg/kg
have been determined [DEPA, 2006]. Highest formaldehyde content has been
reported to a textile existing of 100% cotton. The content of DEHP has been
determined to 2-8 mg/kg fabric samples of cotton, wool, flax, PET and viscose
[DEPA, 2006].
142
4.7.1. Coating products for (hard surfaces, leather, textiles)
Perfluorooctane sulfonamide (PFOSA) has been determined and may be emitted
from spray products meant for impregnation of leather, hide and textiles [DEPA,
2006].
A total of 1159 common household products were analysed for 31 volatile organic
compounds as potential sources of indoor air pollution (Sack et al., 1992). The
products were distributed among 65 product categories within 8 category classes:
automotive products (14.4% of the products); household cleaners/polishes (9.6%);
paint-related products (39.9%); fabric and leather treatments (7.9%); cleaners for
electronic equipment (6.0%); oils, greases and lubricants (9.6%); adhesive-related
products (6.6%); and miscellaneous products (6.1%). For fabric and leather
treatment products tested, such as shoe polishes, water repellents and spot
removers, chlorinated solvents were found to occur with the highest frequency. The
chemical occurring most frequently and having the highest average concentration in
the fabric and leather treatments was 1,1,1-trichloroethane. Methylene chloride and
tetrachloroethylene were also found in a large number of the products and at
relatively high average concentrations. Toluene was also observed in many of the
products in this class, but at relatively low levels. One of the three products in this
class which was analysed for o, p-xylene has a concentration of 0.1%. Twenty two of
the target chemicals were found in fabric and leather treatments.
A study from Kwon et al. (2007) investigated the emissions composition for
household products sold in Korea by using a headspace analysis, for the
determination of VOCs. The compounds emitted by two fabric deodorizers were:
ammonia, ethanol, 1-chloro-2-methyl benzene, ethanol, limonene, β-myrcene, α-
pinene, β-pinene and γ-terpinene.
Nanofilm spray products (NFPs) are a relatively new type of industrial and consumer
products for surface coating. Most of the NFPs induce non-stick properties when
applied to surfaces. The NFPs are available for a wide range of different surfaces,
e.g. bathroom tiles, floors, textiles and windows. Some nanofilm spray products for
floor protection (coating for non-absorbing floor materials and coating for ceramic
tiles) were studied (Nørgaard et al., 2009, 2010). Some of the VOCs identified were:
1-propanol, 1,1-diethoxy ethane, diisopropoxy methane, 2-butanone, 3-metyl-2-
143
butanone, 6-methyl-3-heptanone, 1-chloro-2-propanone, 1,1-dichloro-2-propanone,
1,3-dichlor-2-propanone, isopropyl acetate and 1H,1H,2H,2H-perfluorooctyl
triisopropoxysilane. The particles which have been reported to be released during
application of those products (Nørgaard et al., 2009) are mainly consisting of
aerosolized silanes/siloxanes and their condensates identified in this study.
4.7.2. Fabric deodorisers
No data available
4.8. Personal care products
According to the EU Cosmetic Directive 76/768/EEC up to 35% (w/w)
dichloromethane (DCM) and 1,1,1-trichloroethane (1,1,1-T) are allowed in cosmetic
products. In Denmark, the use of DCM and 1,1,1-T in aerosol-products is not
allowed. In the past, DCM and 1,1,1-T had been used in the formulation of cosmetic
products for hair-care: hair spray, hair lacquers, etc. [Rastogi, 1994].
As the use of CFCs is now regulated in many countries, the commonly used
propellants in aerosol hair cosmetics appear to be HCFCs, propane, butane,
isobutane and mixtures of HCFCs and propane, butane, etc.
Chlorinated solvents have also been used to dissolve the active ingredient, polymers,
in hair fixative formulations and in some other cosmetics as well. However, it
appears that the bad image of chlorinated solvents together with the developments
in polymer synthesis, followed by the developments in cosmetic formulations, have
led the cosmetic industry to use alcohol/ water/glycolether soluble polymers in
cosmetics.
Today, it is prohibited to produce, import or sell toys and some infants’ articles to
children at the age of 0-3 years, if the products contain more than 0.05 weight %
phthalates. In some toothbrushes plasticised PVC or printing ink containing
phthalates might also occur.
144
Nickel is another immediately problematic substance, which might be found in
toothbrushes. Nickel constitutes a problem for the patients in the form of nickel
allergy, for which reason the Ministry of Health of Denmark has dictated an upper
threshold limit value for nickel content of max. 0.05% Ni for dental materials for e.g.
crowns of teeth and bridges. In some toothbrushes nickel is used for fixation of the
bristle [Danish Technological Institute, 2004].
4.8.1. Hair styling products (spray, gels etc.)
Low molecular weight cyclic volatile methylsiloxane (cVMS) compounds have been
used in a variety of cosmetics and personal care products and many other consumer
products. Wang et al. (2009) study provides information on the levels of cVMSs in
cosmetics and personal care products sold in Canada with an attempt to estimate the
consumer dermal exposure to cVMSs from these products.
Measurements obtained to hair styling products are summarized in the following
table.
Table 4.23. cVMS concentrations (mg/g wet weight) in hair styling products
Product Concentration (mg / g wet weight)
D4 D5 D6
Hair spray (HS)
HS 1 0.01 0.02 0.01
HS 2 1.69
Hair mousse 0.04
Hair gel (HG)
HG 1 0.1
HG 2 0.07 0.08
HG 3 0.04
D4 = octamethylcyclotetrasiloxane; D5 = decamethylcyclopentasiloxane;
D6 = dodecamethylcyclohexasiloxane
Wallace et al. (1991) studied a broad variety of consumer product categories.
Products were tested using a canister collection in microenvironments (15
commercial establishments expected to contain scented products (potpourri stores,
craft and hobby stores, etc.) and a few homes) and in the headspace of products
145
followed by GC-MS analysis. If canister recoveries were low or variable, the canister
would be supplemented by a direct injection method for the headspace analyses.
Since only one semiquantitative analysis was made for each sample, the results
cannot be interpreted as indicative of that sample's "actual" or "typical" composition.
All chemicals were identified but only semiquantitative estimates were provided for
their concentrations in the microenvironmental and product samples. The chemicals
with the highest concentrations (relative to the other chemicals) in each sample are
listed in the following table.
Table 4.24. Number of chemicals identified and principal chemicals present in
hairsprays tested and locations sampled
Product N (a) Principal chemicals (b)
hairspray #1 19 fluor compounds, benzaldehyde, silane
compound
hairspray #2 17
unknown, butene, butane, ethanol,
C11H24O, isopentone, α-terpineol,
isobutane
(a) Number of chemicals identified in headspace or canister sample
(b) In order of relative amounts
In the study of J. Zhu et al., (2001) five compounds (acetic acid, propylene glycol, 2-
butoxyethanol, benzyl alcohol and phenylethyl alcohol) were identified in the
headspace of one permanent hair colorant.
Concentrations of compounds released from hairdressing products were measured in
hairdressing salons (Van der Wal J. F. et al., 1997). Some results are summarized
below.
Total and respirable dust: The main sources of aerosol particles in hairdressing
salons are hairspray and smoking. The concentration of respirable dust particles
measured in the spray area during spraying varied between 40 and 100 mg/m3. The
concentration decreased rapidly after finishing the spraying and returns to the
background level (<0.5 mg/m3) within a few seconds.
Hydrogen peroxide: The highest concentrations in the breathing zone of the
hairdressers were measured during perming, up to 1 µL/L (spot measurement). The
146
exposure was limited to a maximum of 15 min. A survey of the spot measurements:
1) during perming fluid application: <0.05 µL/L; 2) during colour rinsing: <0.05 µL/L;
3) during bleaching: 0.1 µL/L; and, 4) during neutralising of perms (fixation): 0.1-1
µL/L.
Ammonia: The spot measurements in the breathing zone of the hairdressers showed
the highest concentrations during the application of perming liquid: 2-150 µL/L (1.4-
105 mg/m3). The period of application was about 3 min. During the other
applications, concentrations of 1 µL/L or less were measured.
Volatile organic compounds: The main sources, of volatile organic compounds are
the solvents in the hair spray and the gel. The main solvent is ethanol. Minor
concentrations of diethylether (propellant), acetone, methanol, and butanol were
found. In the winter, the average, median, and maximal concentrations of ethanol
were a factor 2 higher than in the summer. Peak concentrations were measured with
a photoionisation detector of up to 150 µL/L (toluene equivalents) during the use of
hair spray and hair gel. The background concentration then increased from 1-2 µL/L
to 10 µL/L.
In the following table the highest peak concentrations are given expressed as
percentages of the short time exposure limit (STEL) = TLV (threshold limit value) –
TWA (time-weighted average) - 15 min. The activities where these maximal
concentrations were measured are also mentioned.
Table 4.25. Maximal peak concentrations during activities
Compound Activity
Max.
Concentration
period
STEL Max. % of
STEL
RSP Hair spray 100 mg/m3 5 s 10 mg/m3 5
H2O2 Neutr. Permanent 1 µL/L 2 min 2 µL/L 7
NH3 Application permanent 150 µL/L 2 min 50 µL/L 40*
Butane Hair spray 30 µL/L 1 min 1200 µL/L 0.2
Ethanol Application hair gel 150 µL/L < 1
2000 µL/L < 0.5
147
min
* Overestimated by method
STEL = short time exposure limit (= TLV – TWA – 15 min)
4.8.2. Deodorants (sprays)
Perfumes are composed of 10 to 300 fragrance substances, which are chosen from
among thousands of fragrances. The composition of perfumes is kept a trade secret
by the fragrance industry, which means that important information regarding
exposure is not available for risk assessment. Allergic contact dermatitis is among the
more severe unwanted effects arising from the use of cosmetics. The majority of
allergic reactions to cosmetics can be attributed to the perfume in the product. The
use of fragrances (perfumes) in cosmetics is associated with pleasure and sometimes
with therapeutics. All known fragrance substances are organic compounds or
mixtures of organic compounds, derived from natural sources or produced
synthetically. Deodorants are one of the most widely used types of cosmetic
products and they are used repeatedly in an occluded environment.
For now, official regulation of ingredients that compose fragrances or the compounds
fragrances itself is still lacking in most countries. There are no requirements to test
fragrance materials for safety-use in consumer products or even to list the fragrance
ingredients concerning these same products. Nowadays, perfume industries are self-
regulating the production, development and use of perfumes, including cosmetics.
However, there is the need to perform systematic investigations to unravel the trend
of use of allergic fragrance substances in various consumer products together with
epidemiological studies in order to assess the toxic effects resulting of the use of the
respective products. In Denmark, 11 fragrance substances (cinnamic alcohol,
cinnamic aldehyde, eugenol, hydroxycitronellal, α-amylcinnamic aldehyde, geraniol,
isoeugenol, coumarin, dihydrocoumarin, citral, citronellal), which are well-known to
cause allergic contact dermatitis, have been selected for an epidemiological study. 18
cosmetic products, such as 5 shampoos, 7 creams and lotions, 2 eau de toilette, 1
deodorant spray, 1 lipstick, 1 face powder and 1 soap bar were chosen for the
development of the method due to their common use by the general population
(Rastogi, 1995). The qualitative analysis of the fragrance substances in the sample
148
products was performed by both gas-chromatography-mass spectrometry (GC-MS)
and GC-FID (flame ionization detection). Citral, hydroxy citronellal, cinnamic alcohol
and coumarin were the 4 fragrances substances found in the deodorant spray
composition. The analysis of the target fragrances in the deodorant spray are
described on the next table.
Table 4.26. Analysis of the target fragrances in the deodorant spray
Fragrance
substance CAS number Chemical structure
GC retention time
(min)
Citral 5392-40-5 3,7-Dimethyl-2,6-
octadienal 12.36
Hydroxy citronellal 107-75-5 3,7-Dimethyl-7-hydroxy
octanal 12.49
Cinnamic alcohol 104-54-1 3-Phenyl-2-propen-1-ol 13.30
Coumarin 91-64-5 2H-1-Benzopyran-2-one 16.46
In order to broaden the number of microenvironments and chemical classes related
with emissions of toxic and carcinogenic volatile organic compounds, the
Environmental Protection Agency (EPA) sponsored a study of polar chemicals emitted
from 31 consumer products and 16 microenvironments. Polar chemicals such as
alcohols, aldehydes, esters and ketones are of particular interest due to their
odorous and irritant properties. The 31 scented product brands to be tested were
chosen from a broad variety of product categories such as perfumes, soaps and
deodorants. Brand names were selected based on recommendations from persons
who had experienced health symptoms or discomfort that they attributed to the
product. The headspace generation system followed by gas-chromatography-mass
spectrometry (GC-MS) analysis enabled the identification of some hundreds of polar
and non-polar VOCs emitted by the tested products. Results showed that the tested
spray deodorant emitted silane compounds and limonene, being the last one a
known terpene and a very popular additive to perfumes, soaps, polishes, room air
fresheners, soft drinks and innumerable other products.
149
In 1998, Rastogi and co-workers have performed quantitative analysis on 73
deodorants, comprising 23 vapo-spray, 22 aerosol spray, 27 roll-on products and 1
deostick. 21 well-known fragrance substances were identified by gas-
chromatography-mass spectrometry (GC-MS) and the determination of the
substances was performed by GC-FID (flame ionization detection). This study
included the 7 chemically-defined substances of the fragrance mix, cinnamic
aldehyde, cinnamic alcohol, α-amylcinnamic aldehyde, eugenol, geraniol,
hydroxycitronellal, isoeugenol, and 14 other substances that were found to be
frequently present in perfumes and cosmetics. The trend observed was that target
fragrances were more often found in vapo-spray ≥ aerosol spray > roll-on products,
but with a very small difference between vapo and aerosol-sprays. The
content/concentration range of the target fragrance substances are described in the
next table.
Table 4.27. The content/concentration range of the target fragrance substances
Vapo-sprays Aerosol sprays
Fragrance substance Concentration range (g/100 mL)
α-amylcinnamic aldehyde 0.0001-0.0617 0.0001-0.0198
Benzyl acetate 0.0001-2.6960 0.0001-0.0517
Benzyl alcohol 0.0011-0.0629 0.0045-0.0575
Benzyl benzoate 0.0012-0.1075 0.0001-0.0187
Benzyl salicylate 0.0016-1.8758 0.0001-0.1537
Cinnamic alcohol 0.0006-0.1169 0.0001-0.0424
Cinnamic aldehyde 0.0001-0.0046 0.0016-0.0184
Citronellol 0.0017-0.1392 0.0005-0.5585
Coumarin 0.0011-0.1170 0.0030-0.0260
Eugenol 0.0006-0.2355 0.0006-0.0632
Geraniol 0.0001-0.1178 0.0001-0.0206
Hedione 0.0024-1.7587 0.0001-0.2409
150
α-hexylcinnamic aldehyde 0.0015-0.1684 0.0002-0.0422
Hydroxycitronellal 0.0001-0.1023 0.0012-0.0815
Isoeugenol 0.0001-0.0458 0.0001-0.0104
Lilial 0.0025-0.1452 0.0065-0.3732
Linalool 0.0009-0.1927 0.0009-0.1028
Linalyl acetate 0.0001-0.1810 0.0009-0.1119
Lyral 0.0001-0.1874 0.0006-0.1606
α-iso-methylionone 0.0020-0.2235 0.0018-0.1942
Piperonal 0.0001-0.0526 0.0001-0.0612
Polydimethylsiloxanes (PDMSs) are the most common type of silicone that can be
found in a wide variety of industrial applications and consumer products including
silicone grease, microfluidics chip production, cosmetic products, household cleaning
products, pharmaceuticals and medical devices. Low molecular weight cyclic volatile
methylsiloxanes (cVMSs) are a particular group of PDMSs that have a cyclic ring
consisting of –Si–O– elements. These cVMSs are widely used in today's society and
their potential adverse effects have been identified in animal tests. Due to their
volatility, low surface tension, transparency, hydrophobic nature and lack of odour,
these chemical products are popular candidates to be used as solvents or ingredients
in cosmetic and personal care product formulations. Recent studies (Wang et al.,
2009) have measured the actual levels of cVMSs in a total of 252 cosmetic products
on the Canadian market. The collected samples comprised 6 product categories
including fragrances, hair care products (hair spray, gel and mousse), deodorants
including antiperspirants, nail polishes, lotions (body lotions and creams), skin
cleansers and a variety of baby products (oils, lotions, shampoos, and diaper
creams). Samples were extracted with organic solvents followed by gas
chromatography-mass spectrometry (GC-MS) analysis. Of the 252 products tested,
cVMSs were detected in 36 of them. The variation in the concentration ratios among
the cVMSs suggested that different blends of silicones in either materials or as
additives were used in the production of cosmetic products.
Decamethylcyclopentasiloxane was the only cVMSs detected on deodorants
(excluding antiperspirants).
151
4.8.3. Perfumes
The odoriferous compounds that make up a perfume can be manufactured
synthetically or extracted from plant or animal sources. Plants are by far the largest
source of fragrant compounds used in perfumery. These aromatics are usually
secondary metabolites produced by plants as protection against herbivores,
infections, as well as to attract pollinators. A plant can offer more than one source of
aromatics, for instance the aerial portions and seeds of coriander have remarkably
different odours from each other. Orange leaves, blossoms, and fruit zest are the
respective sources of petitgrain, neroli, and orange oils. An example of an animal
source is beeswax or honey that can be solvent extracted to produce an absolute.
But synthetics can provide fragrances which are not found in nature. For instance,
calone, a compound of synthetic origin, imparts a fresh ozonous metallic marine
scent that is widely used in contemporary perfumes. Synthetic aromatics are often
used as an alternate source of compounds that are not easily obtained from natural
sources. For example, linalool and coumarin are both naturally occurring compounds
that can be inexpensively synthesized from terpenes. Orchid scents (typically
salicylates) are usually not obtained directly from the plant itself but are instead
synthetically created to match the fragrant compounds found in various orchids.
In a study performed by EPA chemicals that appeared in more than half of 31 tested
scented products included ethanol, limonene, linalool, β-phenethyl alcohol, and β-
myrcene. Ethanol is an alcohol used as a solvent base for many of these
preparations. Limonene is a terpene contained in citrus fruits, pine trees, etc. and is
a very popular additive to perfumes, soaps, polishes, room air fresheners, soft drinks
, and innumerable other products. Linalool is found in cinnamon and lavender. β-
phenethyl alcohol (or 2-phenylethanol) is present in many flowers, and has a roselike
scent. Β-myrcene is found in bay leaves, verbena, and hops.
Many of the other chemicals found in the fragrance products are natural chemicals
occurring in flowers, fruits, and trees. Their function in some cases appears to be to
attract helpful insects such as bees; in other cases, the scents act as a repellent
(e.g., citronella). Few of these chemicals have been tested for carcinogenicity,
152
although some (e.g., α-pinene) are known mutagens and others (e.g., camphor)
have known toxic effects at high concentrations.
In 1995 Rastogi developed a gas chromatographic-mass spectrometric method for
the routine analysis of 11 fragrance substances in cosmetics. In the ‘eau de toilette’
analysed cinnamic alcohol, geraniol and isoeugenol were found.
Since fragranced products are meant to be detected by the consumer, it seems
logical that their concentrations in the breathing zone will be at least as great as
their odor thresholds for some period of time. Lotions, perfumes and other scented
personal care products are applied to the head region and often release terpenes
and terpenoids that can participate in gas-phase reactions with ozone (Corsi et al,
2007). Among other products, three perfumes were studied to determine the extent
of secondary organic aerosol formation in the breathing zone of a subject who had
applied these products. Compounds such as d-limonene and other terpenes are often
added to perfumes as top notes that evaporate relatively quickly, e.g., within 5–10
min of application, however, the study of a model perfume suggested that peak
linalool evaporation rates from skin occur 15–75 min after product application, and
were still detected 7.25 h following application (Letizia et al., 2003).
Perfume ingredients, regardless of natural or synthetic origins, may all cause health
or environmental problems when used or abused in substantial quantities. Moreover,
due to the need for protection of trade secrets, companies rarely give the full listing
of ingredients regardless of their effects on health.
Respiratory symptoms from environmental perfume exposure are main complaints in
patients with multiple chemical sensitivities and often coincide with asthma and or
eczema (Elberling et al., 2009).
A mixture of 8 individual fragrances (fragrance mix) is used to screen for fragrance
allergy. The most common allergy-causing fragrances are cinnamic alcohol, cinnamic
aldehydes, eugenol, isoeugenol, geraniol, α-amyl cinnamic alcohol, hidroxycitronellal
and oak moss absolute (Fisher's Contact Dermatitis, 2001).
Rastogi et al investigation (Rastogi et al., 2004) aimed to quantify exposure to
chloroatranol and the chemical related substance atranol in 31 perfumes, eaux de
parfum and eaux de toilette available on the European market. Chloroatranol and
153
atranol (degradation products of chloroatranorin and atranorin, respectively) have
been identified as the main allergens in the fragrance material of botanical origin,
oak moss absolute. The two substances were found in 87% of the products. The
median concentrations of both were higher in perfumes as compared to eaux de
toilette. The median concentration of atranol in perfumes was 0.502 µg/ml and 0.012
µg/ml in eaux de toilette and 0.235 µg/ml and 0.006 µg/ml for chloroatranol,
respectively, in perfumes and eaux de toilettes. Chloroatranol was found at a
maximum concentration of 53 µg/ml and atranol at one of 190 µg/ml. The wide
exposure to oak moss allergens, together with significant amounts of these potent
allergens in at least half of perfumes and some eaux de toilettes explains the high
frequencies of oak moss absolute allergy.
More recently, they (Rastogi et al., 2007) investigate also the sensitizer isoeugenol
and hydroxyisohexyl 3-cyclohexenecarboxaldehyde (HICC) in 25 perfume products.
Isoeugenol (48–193 ppm or 0.0048–0.0193%) was present in 56% (n = 14) of the
25 investigated samples, and HICC (59–2058 ppm or 0.0058–0.2058%) was present
in 72% (n = 18) of the products. 11 of the investigated products (44%) contained
both isoeugenol and HICC, and 5 products (28%) contained neither isoeugenol nor
HICC.
In a study conducted by Hutter et al. (2010) the concentrations of 11 synthetic
musks widely used as fragrance ingredients were determined in blood plasma
samples. The two substances detected in higher percentages were galaxolide
(maximum concentration 6900 ng/L) and musk xylene (maximum concentration 190
ng/L). Regression analysis revealed a significant association of galaxolide
concentration with frequent use of perfumes, deodorants and shampoos. Frequent
use of soaps and fabric softener was associated with higher plasma concentrations of
musk xylene.
4.9. Printed material
The highest inhalation and dermal exposure from these products is expected when
the consumer turns the pages of freshly printed matters [DEPA, 2006].
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4.9.1. Magazines
Volatile aldehydes are produced-among others- during degradation of paper-based
materials. In a recent study, the emission of formaldehyde from the degradation of
cellulose contained in paper, was found to be almost constant over 30 days of
accelerated ageing of two types of papers [Ramalho et al., 2009; Strlic et al, 2010].
On the other hand, recent research has shown that paper emits reactive oxygen
species, such as H2O2 (Strlic et al., 2010), which could additionally affect
microenvironments and lead to removal of volatile aldehydes. Formaldehyde is
known to be reactive and oxidises to formic acid (the rate being dependant on
environmental conditions. Newsprint paper –probably due to its low stability-and
many contemporary papers may contain high amounts of lignin, which leads to
higher VOC emissions from these papers [Ramalho et al., 2009].
Printed material may also emit acetaldehyde, toluene, xylenes and limonene [DEPA,
2006].
The toluene emission from printed brochures was studied by (Jensen et al., 1996).
4.10. Toys
Hazardous substances can occur in childrens’ toys and relatively little is known about
the exposure via toys. A risk-analysis might be necessary for toys, as health
problems could arise due to the release of substances from toys. The questions that
arise with respect to the exposure are [RIVM, 2002]:
- how children handle toys,
- which toys are put in the mouth,
- with which toys children have intensive contact,
- to what extent substances are released from the toys.
Young children e.g. 2 year-olds are exposed to a huge number of products in their
daily life and are thereby exposed to many chemical substances. They are also
particularly susceptible because of their physical size (large surface area/small
volume). Additionally, young children have a frequent/lasting use of several products
e.g. pacifiers (12 pacifiers per year have been estimated to be used) [DEPA, 2009].
155
For these specific products, Directive 93/11/EEC regulates the emissions of N-
nitrosamines and N-nitrosatable substances from baby’s bottle teats and pacifiers
made with elastomers and rubber. This Directive states that pacifiers and bottle teats
must not release N-nitrosamines and N-nitrosatable substances, which are
dissolvable in saliva in amounts that exceed the following:
0.01 mg total amount released N-nitrosamines/kg (from those parts of the
pacifier or bottle teat made with elastomers or rubber).
0.1 mg total amount emitted N-nitrosatable substances/kg (from those parts
of the pacifier or bottle teat made with elastomers or rubber).
The route of exposure relevant for an individual toy product will depend on the
product type and the chemical substance in question. Assessment of exposure is
based on ingestion, skin exposure and inhalation of volatile substances from the
product. For example, a 2 year-old may be affected via inhalation of substances from
substances that evaporate from soft and scented toys. Skin exposure (dermal
exposure) must, on the other hand, be considered relevant, as children have direct
skin contact with all these products. Ingestion, resulting from a young child sucking a
product, is also pertinent. Additionally, if the young child holds the toy in his hand,
exposure occurs not only via dermal uptake but also when the he/she sucks on their
fingers, which is something they do a lot. On the other hand, the total time of
exposure per day is quite short because it is rather sparse for a young child to play
with one item for more than half an hour per day.
The substances to be examined in toys are not always homogeneously distributed.
The toy can be made up of several materials, whereby the substance to be
investigated is present in one or more of the materials. In a painted toy metal car,
there is a metal layer and a paint layer. Another example is a cuddly toy which is
made from different sorts of textile and which is filled with a synthetic foam filling.
There are also types of toys where the substance to be investigated is not
homogeneously distributed in the material. An example of this is wooden playground
equipment, whereby the wood has been preserved using a preservative.
From the time of treatment, the concentration of the preservative in the wood will
decrease with the distance from the surface.
156
Many slimy toys are manufactured from or containing plasticised plastic. A frequently
used plasticiser for particularly PVC is phthalates [DEPA, 2005]. In the frame of the
same survey, 14 slimy toys were analysed to determine their chemical composition.
The majority (80%) of the examined products were main components in the
degassing aliphatic hydrocarbons, primarily C10-C14 and aromatic hydrocarbons
such as toluene, xylenes and trimethyl benzenes. Two of these products furthermore
contained more volatile aliphatic hydrocarbons such as C7-C8. Additionally, for two of
the examined products cyclohexanone constituted 63% and 30% of the total
degassing. Other samples were characterised by the content of alcohols. It should
also be noticed that a few of the products contained traces of D-limonene (allergenic
odorant). In the same products, the content of elements such as aluminium, calcium,
potassium, magnesium and zinc, were also detected in most of the samples. They
presumably derive from fillers or auxiliary constituents used in the production of the
products. Furthermore, the detection of traces from a few heavy metals in some of
the samples was supposed to derive from contaminations from fillers and possibly
from production equipment and production conditions.
Thinking about inhalation, we should have in mind of more or less volatile organic
compounds that evaporate from the toy. In RIVM report [2002] is reported that it is
very rare for volatile organic compounds to be able to evaporate freely from toys;
the volatile organic compounds are almost always restricted in one way or another.
The substance that evaporates from toys can also be a less volatile organic
compound, such as a fungicide that may be released from a cotton toy tent.
The available information concerning the chemical composition of toys is very sparse,
since most such products are made in the Far East. Additionally, it is often difficult to
obtain information on complete chemical composition from manufacturers. Toys
usually contain bromated flame-retardants, TCEP, phthalates, ethylene vinyl acetate,
polyurethane, isocyanates, colorants and metals (e.g. tin). According to the Danish
Ministry of the Environment (2005), it is prohibited to produce, import or sell toys
and some infants’ articles to children at the age of 0-3 years, if the products contain
more than 0.05 weight% phthalates. EU has assigned a limit value of 0.1% for
content of PeBDE and OBDE. Marketing of products containing one of these two
substances above this limit value is not legal in the EU.
157
Products produced from polyurethane (PUR), contain tin from the organic tin
compounds e.g. monobutyltin (MBT) and dibutyltin (DBT), which are used catalyst in
the production of PUR. Exposure to the organic tin compounds from toys can occur
through contact with toys consumer or via inhalation released organic tin compounds
due to wear and tear. Breathing or swallowing, or skin contact with some organotins,
such as trimethyltin and triethyltin compounds, can interfere with the way the brain
and nervous system work. In severe cases, it can cause death. Some organic tin
compounds, have been shown to affect the immune system in animals and to affect
the reproductive system. This has not been examined in people [DEPA, 2006].
The same products may contain isocyanates, when they are packed prematurely in
tight plastic. Azo colorants, colorants that are known as allergens or carcinogens,
may also be part of the chemical composition of toys. According to the Toy Standard
“Organic chemical compounds requirements”, EN71-9, the limit value of aromatic
amines (azo colorants are measured as aromatic amines) is 5 mg/kg.
Table 4.28. Exposure categories from toys
Mouthing
Toys meant for mouthing teething ring
Other toys cuddly toy, plastic doll
Ingestion
Direct ingestion modelling clay, paint from toy car,
ball pen
hand-mouth contact, direct finger paint, chalk
hand-mouth contact, indirect face paint
Inhalation
evaporation from liquids felt pen
evaporation from solid products tent
Dust chalk, cosmetics (blusher)
Skin contact
leaching from solid products cowboy suit , tent ground sheet
cuddly toy
rubbing off tent canvas, preserved wood
application on the skin cosmetics, face paint
158
intensive hand contact modeling clay, finger paint
spillage poster paint
Eye contact
leaching from solid products diving goggles
application on the skin near
the eyes
cosmetics (eye shadow), face paint
evaporation from solid products diving goggles
hand-eye contact finger paint, chalk
4.11. Pet care products
Not available data
4.12. Flowers and plants
Not available data
4.13. Decoration and maintenance
Hexanal, alkanes and chloroalkanes were found to be emitted from the gypsum
board while a water-based white paint showed a complex matrix of alkanes mainly in
the range of nonane and decane, allky-lbenzenes, ethanol,2-(2- butoxyethoxy),
ethanol, 2-(2-butoxyethoxy) acetate and of acid ester families. Linoleum flooring was
found to be source of pentanal, heptane, 2-ethyl-furan, formic, acid pentyl ester,
hexanal, heptanal, pentyl-furan, dipropylen glycol mono methyl ether, octanal,
nonanal and tridecane. Aldehydes and terpenes were the predominant compounds in
the wood based materials (melamine finished particle board and medium density
fibreboard). Ceiling tile analysis resulted in 197 chromatograms with low intensity
peaks of acetic acid, propanoic acid, hexanal, furanmethanol, benzaldehyde and
acetophenone. BTEX, alkanes, alkylbenzenes and 4-phenyl-cyclohexane were
detected in the screening of a 100% polypropylene carpet. Mainly polar compounds
(alcohols, esters) were present in the analysis of a water based adhesive.
From the results of this project was outlined that MDF is the material with the
highest contribution to formaldehyde emissions followed by the ceiling tiles and
particle board. Linoleum is the material with the highest impact on acetaldehyde
159
emissions followed by particle board, paint and MDF with similar contributions.
Xylenes are originated from the paint while particle board is the source of a-pinene
emissions. Moreover, volatile organic compounds of polar nature (e.g. short chain
acids and esters) have been found as a major fraction of the emissions of various
products.
160
5. CONSUMER PRODUCTS : EPHECT PRIORITY VERIFICATION
As stated in section 2.1. Definition of consumer products, the products discussed in
this literature review are those that are defined by the EPHECT definition of
consumer products, reported in the same paragraph. It was also stated that the
focus of the following EPHECT work packages (WP5, WP6, WP7) will be on a
selection of 15 consumer product classes. This selection of 15 will in the first place
comply with the title of the DG Sanco call “Quantification of emission of key indoor
air pollutants from consumer products such as personal care and cleansing products,
and information on the user pattern of these products in EU Member States”.
Secondly these product classes need to comply with the EPHECT project proposal
which states “… the following product classes might be selected: personal care
products, air fresheners, cleaning agents and sprays”. In the same project proposal,
this pre selection has been translated into (needs to be verified/confirmed by) 7
consumer product selection verification criteria. Applying those criteria (as alternative
to a random selection), products are prioritized for the further scope of EPHECT
These are the EPHECT product selection verification criteria:
1. They are products commonly used in households in Europe and public
buildings (e.g. schools, day care centers, offices and places of leisure) in the
course of normal use. This means that the aim is not to assess products of a
professional use, but to focus on those available to the consumer for private
use. To this direction the market share or quantity of production of the
material will be accessed via comprehensive questionnaires that will be
delivered to the greater super market chains and other companies with
products relevant to the aims of this study;
2. They emit key pollutants or other emerging pollutants as identified by INDEX,
SCHER and WHO;
3. They have a considerable indicative household frequency of use;
4. Inhalation to vapours and particulate matter is the main exposure route;
5. Their emissions may cause ( there is debate about) a health end point related
to respiratory problems;
6. Products for which gaps of knowledge exist concerning their emissions;
161
7. Exposure related to the use. More specifically, for this product class, the
exposure is related to use pattern and use scenarios.
Additionally, the consumer products will be assessed in relation to the following
parameters:
Use duration per event
Quantity of product used
Mode of application:
o product discharged directly to the air e.g. air fresheners
o product applied in water e.g. laundry detergent
o product applied to a surface e.g. general purpose cream
o product placement in the environment e.g. room deodorizer
Timing of cleaning activities relative to room occupancy
The prioritization of the product classes has been made according to the criteria set
in the EPHECT proposal. The evaluation procedure was based on several approaches,
using different classification procedures. However, the resulting list of products
classification is the same.
Here, a scheme assigning the scores 0s, 1s and 2s has been used to evaluate each
product in relation to the predefined EPHECT consumer product selection criteria.
Thus, this way of prioritization seems to be more appropriate for a quantitative
prioritization within the criterion under consideration as a result of the literature
review. Furthermore, since all criteria are considered as equally important for
EPHECT, the weight assigned to each criterion is equal.
Table 5.1. Criteria for selecting the 15 product classes for further investigation
Criteria Definition Quotation
Criterion
1:
Used in
households
The product is
commonly used in
EU households
0: the product is not used in EU
households
1: the product is used
exceptionally in EU households
2: the product is commonly used
162
in EU households
Criterion
2:
Emit key
pollutants
The product emits
pollutants that are
identified as
hazardous by INDEX,
SCHER, WHO
0: the product doesn’t emit the
identified key pollutants
1: based on its composition, the
product may emit key pollutants
2: literature confirms the emission
of key pollutants
Criterion
3:
Indicative
frequency of
use
Products from this
product class are
used by a
representative part
of the population
and are
characterized by a
significant use
frequency in an
average household
0: the product is used annually
1: the product is used on a
monthly basis
2: the product is used on a
weekly or daily basis
Criterion
4:
Inhalation
exposure
The product studied,
has inhalation as the
main exposure route
0: the use of the product causes
mainly dermal exposure or no
exposure
1: the use of the product causes
comparable inhalation and dermal
exposure
2: the use of the product causes
mainly inhalation exposure
Criterion
5:
Health
relevant
emissions
The emissions from
products in this
product class are
known to cause
health end points
(mainly respiratory
problems)
0: the emissions caused by the
use of the products are known to
be harmless
1: the emissions caused by the
use of the product are known to
cause health end points not
relevant for EPHECT
2: the emissions caused by the
use of this product may cause
163
health end points within the scope
of EPHECT
Criterion
6:
Emission gaps There are knowledge
gaps for this product
0: all emission related issues
related to the use of this product
have been studied and reported in
detail (see database)
1: few studies have been
organised to evaluate emission
related issues, related to the use
of this product
2: no studies report on emissions
related to the use of this product
Criterion
7:
Exposure
related to the
use
The exposure is
related to use
pattern and use
scenario’s.
0: there is no relation between
the exposure and the use
scenario of the product
1: some use scenario’s of the
product may cause significant
exposure
2: there is a clear relation to
exposure and the use scenario of
the product (e.g. sprays)
For the A, B, C classification, resulting from the different criteria evaluations, we
have used the methodology below.
Applying the 7 criteria for each product class implied that, the higher the sum of the
scores for the criteria, the more relevant this product class is within the EPHECT
scope. Thus, the highest category classification (A) includes product classes which
are most relevant for further investigation in EPHECT. It should be noted, however,
that in some cases the expert judgement, by nature, becomes subjective and is
based on experience, due to a lack of reported open literature data.
Products are classified using the following strategy:
164
- A product class is labelled ‘A’, when its total sum of scores is equalizing
80-100% of the maximum score (of 14). This implies a sum greater or
equal to 11;
- A product class is labelled ‘B’, when its total sum of scores is more than
50% of the maximum score (14). This implies a sum of scores greater
than 7 and smaller than 11;
- A product class is labelled ‘C’, when its total sum of scores is 50% or less
of the maximum score (14). This implies a sum of scores equal or smaller
than 7.
The resulting table of the above described evaluation and classification
strategy, is shown in Appendix 1 table 2. Each product class within a product
category was assigned a score by the different experts, involved in EPHECT
WP4. The assigned scores have been discussed and have been combined to
one final score, as reported in table 2.
Where relevant, more information on the origin of the assigned score is
indicated in the table and if needed a reference to the literature database is
made.
165
6. CONSUMER PRODUCTS SELECTION FOR EPHECT
Taking into consideration the prioritization verification of the consumer product
categories, classes and types as well as the EPHECT project proposal priorities, we
have concluded to 15 consumer products for further investigation. The procedure
strategy was first to select the product classes that have an A prioritization according
to the applied prioritisation, and then to proceed to the selection of the product
types that had an B prioritization if no sufficient quantity of products received an A
classification. These 15 products are given below.The table below (table 6.1) shows
the 15 selected consumer product classes. The last column indicates where
respectively cleaning agents, air fresheners and personal care products are
respresented in this set of EPHECT consumer products.
Table 6.1. The 15 selected consumer products for further investigation
A1 All purpose cleaners (gel, liquid, tissue, cream) Cleaning agent
A2 Kitchen cleaning agents (liquid, spray, tissues) Cleaning agent
A3 Hard surface (floor) cleaner (powder, spray, gel, disinfectant)
Cleaning agent
A4 Glass and window cleaner (Liquid, spray, tissues) Cleaning agent
A5 Bathroom cleaning agents (liquid, sprays, tissues) Cleaning agent
A6 Furniture polish (liquid, spray, tissues) Cleaning agent
A7 Floor polish (liquid, spray, tissues) Cleaning agent
A8 Combustible air fresheners (candles, incense) Air freshener
A9 Air fresheners (spray) Air freshener
A10 Passive units (air fresheners) Air freshener
A11 Electric units (insecticide tablets, air fresheners) Air freshener
A12 Coating products for (hard surfaces, leather, textiles) Cleaning agent
A13 Hair styling products (sprays, gels,…) Personal care
A14 Deodorants (sprays) Personal care
A15 Perfumes Personal care
166
7. CONCLUDING REMARKS From the literature review as well as from the existing databases accessed on the
internet, significant gaps regarding research and data were addressed concerning
the emissions from consumer products. It may be noted that most studies reported
used the technique of headspace to characterize the compounds emitted by the
consumer products, thus the emission may show an entirely different profile. The
number of studies performed in test chambers is more limited. For some of the
products of some classes of consumer products selected no data was found, as for
insecticide tablets in the class Electric unist, for example. The type of pollutants
measured is also limitated. The major part of the studies focused in VOCs or
Particulate matter. It is difficult to find an article studying several pollutants for one
type of product.
Emission data and research conducted on consumer products emissions cover only a
limited number of the available types of products on the market. New products come
into the market with significant use and they have not been studied adequately yet.
Such products include electric and electronic devices such as mobile phones (apart
from radiation), game consoles, voltage converters, electric shavers, vacuum
cleaners and hair dryers.
Additionally, further investigation is needed for products of household cleaning
(decalcifiers, unblocking agents and oven cleaners), printed material, shoe care
products, houseplant polishers and pet care products.
In the frame of the EPHECT project these addressed gaps may form an open place
for research and significant contribution to this scientific area.
167
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Table 3.1 References
Weber-Tschopp, A., Fischer, T., Gierer R., Grandjean, E. (1977) Experimentally Induced Irritating Effects of Acrolein on Man. Int. Arch. Occup. Environ. Health; 40: 117-130. (German) Wolkoff, P. and Nielsen, G.D. (2010) Non-cancer effects of formaldehyde and relevance for setting an indoor air guideline. Environ Int.; 36 (7): 788-799. Wolkoff, P., Larsen, S.T., Hammer, M., Kofoed - Sørensen, V., Clausen, P.A. and Nielsen, G.D. (2012) Acute airway effects of five common ozone-initiated terpene reaction products in indoor air, Submitted for publication
194
APPENDIX I
Table 1. Example of consumer product categories definitions
Product level Example 1 Example 2
Product category
Electronic equipment
Household cleaning products
Product class TV Kitchen cleaning agent
Product type LCD TV Kitchen cleaning agent spray
Product Philips LCD TV Mr. Clean kitchen cleaning agent spray
195
Table 2. Consumer products prioritization verification towards EPHECT criteria
No. Consumer product
1st criterion 2nd criterion 3rd criterion 4th criterion 5th criterion 6th criterion 7th criteria
Classification
Used in households
Emit key pollutants
Indicative frequency of use
Inhalation exposure
Health relevant emissions
Emission gaps
Exposure related to use
1. Electronic equipment
PC 1 1 1 1 1 1 1 C
Printers/ faxes 1 1 1 1 1 1 0 C
TV 1 1 2 1 1 1 0 C
Mobile phones 1 1 2 1 1 2 1 B
Other (games, converters, CD players)
1 1 1 1 1 1 0
C
2. Appliances
Gas cooking appliances 21 12 23 24 15 06 17 B
Clothes washers&dryers 28 19 210 011 112 113 014 B
Dishwashers 115 116 217 018 119 120 021 C
1 This product is commonly used in EU households 2 Based on its composition of its components, the product may emit key pollutants 3 This product is used on a weekly or daily basis. 4 The use of this product mainly causes inhalation exposure, but the exposure is however reduced if a suitable fume hood is installed. 5 The emissions due by the use of this product may cause a health end point not relevant in the scope of EPHECT 6 Emissions related to the household use of this product are known and have been studied thoroughly (section 4.2) 7 Some ‘wrong’ use scenario’s of the product may cause a significant exposure (i.e. use without fume hood and without sufficient building ventilation) 8 This product is commonly used in EU households 9 Based on its composition of its components, the product may emit key pollutants 10 Is this product used on a weekly or daily basis. 11 If inhalation exposure is caused by the use of this product, it is most certainly caused by using excess cleaning agent; the exposure then takes place during the wearing phase of the cloth and is not related to the equipment as such. Dermal exposure
will be more significant than inhalation exposure. 12 In the literature review, there is no information on the nature of the emissions. 13 Some studies have been reported, see literature review section 4.1
14 There is no relation between the exposure and the use scenario of the product. 15 The product is not used exceptionally, however, it is not used by the majority citizen in the EU 16 Certain compounds of the product may be emitted in the indoor air
196
Hair dryers 122 123 224 125 126 127 028 C
Vacuum cleaners 229 130 231 132 133 034 135 B
Airco &humidifying syst. 136 037 138 239 140 041 142 C
3. Fireplaces
Stoves 1 1 0 1 1 0 0 C
Gas, oil- fired and ethanol furnaces
0 1 0 1 1 1 1 C
Woodstoves 1 1 0 1 1 0 1 C
Kerosene space heaters 0 1 0 1 1 0 1 C
4. Household products
4.1. Laundry detergents
17 If people posses a dishwasher it is used more often than monthly. Should be 2 18 19 Pollutants emitted may cause a health end point, not in the main scope of EPHECT 20 Some studies have been reported, see literature review section 4.1 21 There is no relation between the exposure and the use scenario of the product. 22 The product is not used exceptionally, however, it is not used by every citizen in the EU 23 Based on its composition, the product may emit key pollutants 24 If people posses a hairdryer it is used more often than monthly. 25 26 Pollutants emitted may cause a health end point, not in the main scope of EPHECT (e.g. flame retardants or phthalates) 27 Some studies have been reported, see literature review section 4.1 28 There is no relation between the exposure and the use scenario of the product 29 This product is common used product in major part of EU households 30Based on its composition, the product may emit key pollutants 31 People that posses a vacuum cleaner use this product at least once a week. 32 The use of a vacuum cleaner mainly causes inhalation exposure; however the major effect is reduced by the use of HEPA filters in vacuum cleaners. 33 Pollutants emitted may cause a health end point, not in the main scope of EPHECT (e.g. flame retardants or phthalates) 34 Several studies have been reported, see literature review section 4.1 35 Some use scenario’s of the product may cause an exposure, e.g. incorrect maintenance 36 This products is exceptionally used in the EU households, related to certain climatic conditions 37 None of the possibly emitted compounds is a key pollutant 38 If a household possesses a HVAC system it is used on average monthly. 39 If pollutants are emitted, they mostly cause inhalation exposure. 40 Pollutants emitted may cause any health end point, depending on the nature of the pollutant. 41 Several studies on the use of HVAC systems have been performed and reported. See Literature review section 2.3.4 42 Some (wrong) use scenario’s of the product may cause significant exposures.
197
Powder detergents 243 144 245 046 147 248 249 B
Tablet detergents 250 151 252 053 154 255 256 B
Gel detergent 2 1 2 1 1 1 2 B
Fabric conditioner liquid 2 1 2 1 1 1 2 B
Fabric conditioner Tissues
2 1 0 1 1 1 2 B
Liquid bleach laundry
aid
1 1 0 1 1 1 1 C
Powder bleach laundry aid
1 1 0 1 1 1 1 C
Ironing aid 1 1 0 1 1 1 1 C
Stain removers Liquid 1 1 1 1 1 1 1 C
Stain remover Powder 1 1 1 1 1 1 1 C
4.2. Household cleaning products
Hand dishwashing liquid 257 158 259 060 161 162 163 B
43 This product is common used in EU households 44 Based on its composition it might emit key pollutants 45 The product is used on a weekly or daily basis 46 The exposure caused by the use of this product is mainly dermal, when wearing/using the fabrics that were washed with these products 47 The emissions my cause health end points, not relevant in the EPHECT scope 48 According to the literature review in WP4, no information on laundry detergent emissions is available. 49 There is a clear relation between the exposure and the use scenario (mainly when used in excess quantities) 50 This product is common used in EU households 51 Based on its composition it might emit key pollutants 52 The product is used on a weekly or daily basis 53 The exposure caused by the use of this product is mainly dermal, when wearing/using the fabrics that were washed with these products 54 The emissions my cause health end points, not relevant in the EPHECT scope 55 According to the literature review in WP4, no information on (tablet) laundry detergent emissions is available 56 There is a clear relation between the exposure and the use scenario (mainly when used in excess quantities) 57 This product is common used in EU households 58 Based on its composition it might emit key pollutants 59 The product is used on a daily basis 60 The product mainly causes dermal exposure 61 The emissions my cause health end points, not relevant in the EPHECT scope 62 According to the literature review in WP4, information on dermal exposure to hand dishwashing liquid is available. 63 Some use scenario’s may cause significant dermal exposures
198
Machine dishwashing liquid
2 1 1 0 1 1 0 C
Machine dishwashing powder
2 1 1 0 1 1 0 C
Machine dishwashing tablet
2 1 2 0 1 1 0 C
All-purpose cleaners Gel/cream
264 165 266 167 168 269 270 A
All-purpose cleaners
Liquid
271 172 273 174 175 276 277 A
All-purpose cleaners tissue
278 179 280 181 182 283 284 A
All-purpose cleaners effervescent tablets
085 186 087 188 189 190 191 C
64 This product is common used in EU households 65 Based on its composition it might emit key pollutants 66 The product is used on a daily basis 67 The use of the product causes dermal and inhalation exposure in a moderate extent 68 The emissions my cause health end points, not relevant in the EPHECT scope 69 According to the literature review in WP4,no information on emissions related to use is available. 70 There is a clear relation between the exposure and the use scenario (mainly when used in excess quantities) 71 This product is common used in EU households 72 Based on its composition it might emit key pollutants 73 The product is used on a daily basis 74 The use of the product causes dermal and inhalation exposure in a moderate extent 75 The emissions may cause health end points, not relevant in the EPHECT scope 76 According to the literature review in WP4,no information on emissions related to use is available. 77 There is a clear relation between the exposure and the use scenario (mainly when used in excess quantities) 78 This product is common used in EU households 79 Based on its composition it might emit key pollutants 80 The product is used on a daily basis 81 The use of the product causes dermal and inhalation exposure in a moderate extent 82 The emissions my cause health end points, not relevant in the EPHECT scope 83 According to the literature review in WP4,no information on emissions related to use is available. 84 There is a clear relation between the exposure and the use scenario (mainly when used in excess quantities) 85 The product is not used at all in EU households (or its use is extremely scarce) 86 Based on its composition it might emit key pollutants 87 The use of the product is almost annual 88 The use of the product causes dermal and inhalation exposure in a moderate extent 89 The emissions my cause health end points, not relevant in the EPHECT scope 90 According to the literature review in WP4, information on dermal exposure is available. 91 Some use scenario’s may cause significant dermal exposures
199
Kitchen cleaning agents Liquid
292 193 294 195 2196 1297 298 A
Kitchen cleaning agents Spray
299 1100 2101 2102 1103 1104 2105 A
Kitchen cleaning agents Tissues
2106 1107 2108 1109 1110 1111 2112 B
Hard surface cleaner liquid
2113 1114 2115 1116 1117 2118 2119 A
Hard surface cleaner
powder
2120 1121 2122 1123 1124 2125 2126 A
92 Used in most EU households 93 Based on its composition, the product may emit key pollutants 94 The product is used on a weekly/daily basis 95 The use of the product may cause an inhalation exposure, as well as a dermal exposure 96 Health end points of the emissions are probably relevant in the scope of EPHECT 97 Some studies report on emissions related to the use of this product (section 4.4.2) 98 There is a clear relation between the exposure and the use scenario of the product 99 Used in most EU households 100 Based on its composition, the product may emit key pollutants 101 The product is used on a weekly/daily basis 102 The use of this product causes mainly inhalation exposure 103 The emissions my cause health end points, not relevant in the EPHECT scope 104 Some studies report on emissions related to the use of this product 105 There is a clear relation between the exposure and the use scenario of the product 106 Used in most EU households 107 Based on its composition, the product may emit key pollutants 108 The product is used on a weekly/daily basis 109 The use of this product causes a dermal exposure and may cause an inhalation exposure 110 The emissions my cause health end points, not relevant in the EPHECT scope 111 Some studies report on emissions related to the use of this product 112 There is a clear relation between the exposure and the use scenario of the product 113 Used in most EU households 114 Based on its composition, the product may emit key pollutants 115 The product is used on a weekly basis 116 The use of the product may cause an inhalation exposure, as well as a dermal exposure 117 Due to the nature of the product 118 Some studies report on emissions related to the use of this product (section 4.4.3) 119 There is a clear relation between the exposure and the use scenario of this product 120 Used in most EU households 121 Based on its composition, the product may emit key pollutants 122 The product is used on a weekly basis 123 The use of this product causes dermal as well as inhalation exposure 124 The emissions my cause health end points, not relevant in the EPHECT scope 125 No studies have been reported on the emissions of hard surface powder cleaners 126 There is a clear relation between the exposure and the use scenario of this product
200
Hard surface cleaner spray
2127 1128 2129 2130 1131 2132 2133 A
Hard surface cleaner gel 2134 1135 2136 1137 1138 2139 2140 A
Hard surface cleaner disinfectant liquid
1141 1142 1143 1144 1145 2146 2147 B
Hard surface cleaner disinfectant powder
1148 1149 1150 2151 1152 2153 2154 B
127 Used in most EU households 128 Based on its composition, the product may emit key pollutants 129 The product is used on a weekly basis 130 The use of this product causes mainly inhalation exposure 131 The emissions my cause health end points, not relevant in the EPHECT scope 132 No studies have been reported on the emissions of hard surface powder cleaners 133 There is a clear relation between the exposure and the use scenario of this product 134 Used in most EU households 135 Based on its composition, the product may emit key pollutants 136 The product is used on a weekly basis 137 The use of the product may cause an inhalation exposure, as well as a dermal exposure 138 The emissions my cause health end points, not relevant in the EPHECT scope 139 Very few or no studies have been reported on the emissions of hard surface powder cleaners 140 There is a clear relation between the exposure and the use scenario of this product 141 This product is not common used in EU households 142 Based on its composition, the product may emit key pollutants 143 This product is rather used on a monthly basis – only in case needed 144 The use of the product may cause an inhalation exposure, as well as a dermal exposure 145 The emissions my cause health end points, not relevant in the EPHECT scope 146 Very few or no studies have been reported on the emissions of hard surface powder cleaners 147 There is a clear relation between the exposure and the use scenario of this product 148 This product is not common used in EU households 149 Based on its composition, the product may emit key pollutants 150 This product is rather used on a monthly basis – only in case needed 151 A powder may cause a more considerable inhalation exposure 152 The emissions my cause health end points, not relevant in the EPHECT scope 153 Very few or no studies have been reported on the emissions of hard surface powder cleaners 154 There is a clear relation between the exposure and the use scenario of this product
201
Toilet cleaners Liquid/Gel
2155 1156 2157 1158 1159 2160 1161 B
Toilet cleaners Tablets 2162 1163 2164 1165 1166 2167 1168 B
Toilet cleaners effervescent tablet
2169 1170 2171 1172 1173 2174 1175 B
Floor cleaning agents/ tissues
Glass and window cleaners Tissue
2176 2177 2178 1179 2180 2181 2182 A
155 Used in most EU households widely 156 Based on its composition, the product may emit key pollutants 157 The product is used on a weekly or daily basis 158 The use of the product may cause an inhalation exposure, as well as a dermal exposure 159 The emissions may cause health end points, not relevant in the EPHECT scope 160 Very few or no studies have been reported on the emissions of tablet toilet cleaner 161 Some use scenario’s may cause significant dermal exposures 162 Used widely in most EU households 163 Based on its composition, the product may emit key pollutants 164 The product is used on a weekly or daily basis 165 The use of the product may cause an inhalation exposure, as well as a dermal exposure 166 The emissions may cause health end points, not relevant in the EPHECT scope, primarily due to the nature of the product 167 Very few or no studies have been reported on the emissions of tablet toilet cleaner 168 Some use scenario’s may cause significant dermal exposures 169 Used in most EU households widely 170 Based on its composition, the product may emit key pollutants 171 This product is used on a weekly or daily basis 172 The use of the product may cause an inhalation exposure, as well as a dermal exposure 173 The emissions may cause health end points, not relevant in the EPHECT scope 174 Extremely few or no studies have been reported on the emissions of effervescent tablet toilet cleaner 175 Some use scenario’s may cause significant dermal exposures 176 The product is used widely in most EU households 177 The product emits confirmed key pollutants according to literature 178 This product is used on a weekly or daily basis 179 The use of the product may cause an inhalation exposure, as well as a dermal exposure 180 Health end points of the emissions are probably relevant in the scope of EPHECT 181 Extremely few or no studies have been reported on the emissions of liquid/gel toilet cleaner 182 There is a clear relation between the exposure and the use scenario of this product
202
Glass and window cleaner spray
2183 2184 2185 2186 2187 1188 2189 A
Glass and window cleaner Liquid
2190 2191 2192 1193 2194 1195 2196 A
Abrasives powder 1197 1198 1199 1200 1201 1202 1203 C
Abrasives Liquid/cream 1204 1205 1206 1207 1208 1209 1210 C
Decalcifier Gel 2211 1212 1213 1214 1215 1216 2217 B
183 The product is used widely in most EU households 184 The product emits key pollutants confirmed by literature 185 This product is used on a weekly or daily basis 186 The use of this product causes mainly inhalation exposure 187 Health end points of the emissions are most probably relevant in the scope of EPHECT 188 Some studies report on emissions related to the use of this product 189 There is a clear relation between the exposure and the use scenario of this product 190 The product is used widely in most EU households 191 The product emits key pollutants confirmed by literature 192 This product is used on a weekly or daily basis 193 The use of the product may cause an inhalation exposure, as well as a dermal exposure 194 Health end points of the emissions are most probably relevant in the scope of EPHECT 195 Some studies report on emissions related to the use of this product 196 There is a clear relation between the exposure and the use scenario of this product 197 This product is not common used in EU households 198 Based on its composition, the product may emit key pollutants 199 This product is rather used on a monthly basis – only in case needed 200 The use of the product may cause an inhalation exposure, as well as a dermal exposure 201 The emissions may cause health end points, not relevant in the EPHECT scope 202 Some studies report on emissions related to the use of this product 203 Some use scenario’s may cause significant dermal exposures 204 This product is not common used in EU households 205 Based on its composition, the product may emit key pollutants 206 This product is rather used on a monthly basis – only in case needed 207 The use of the product may cause an inhalation exposure, as well as a dermal exposure 208 The emissions may cause health end points, not relevant in the EPHECT scope 209 Some studies report on emissions related to the use of this product 210 Some use scenario’s may cause significant dermal exposures 211 The product is used widely in most EU households 212 Based on its composition, the product may emit key pollutants 213 This product is rather used on a monthly basis – only in case needed 214 The use of the product may cause an inhalation exposure, as well as a dermal exposure 215 The emissions may cause health end points, not relevant in the EPHECT scope 216 Some studies report on emissions related to the use of this product 217 There is a clear relation between the exposure and the use scenario of this product
203
Decalcifier Powder 2218 1219 1220 1221 1222 1223 2224 B
Agents for unblocking Powder
1225 1226 1227 1228 2229 2230 1231 B
Agents for unblocking Liquid
1232 1233 1234 1235 2236 2237 1238 B
Bathroom cleaning agents Liquid
2239 2240 2241 1242 2243 2244 2245 A
Bathroom cleaning agents Spray
2246 2247 2248 2249 2250 2251 2252 A
218 The product is used widely in most EU households 219 Based on its composition, the product may emit key pollutants 220 This product is rather used on a monthly basis – only in case needed 221 The use of the product may cause an inhalation exposure, as well as a dermal exposure 222 The emissions may cause health end points, not relevant in the EPHECT scope 223 Some studies report on emissions related to the use of this product 224 There is a clear relation between the exposure and the use scenario of this product 225 This product is not common used in EU households 226 Based on its composition, the product may emit key pollutants 227 This product is rather used on a monthly basis – only in case needed 228 The use of the product may cause an inhalation exposure, as well as a dermal exposure 229 Health end points of the emissions are most probably relevant in the scope of EPHECT 230 Extremely few or no studies have been reported on the emissions of liquid/gel toilet cleaner 231 Some use scenario’s may cause significant dermal exposures 232 This product is not common used in EU households 233 Based on its composition, the product may emit key pollutants 234 This product is rather used on a monthly basis – only in case needed 235 The use of the product may cause an inhalation exposure, as well as a dermal exposure 236 Health end points of the emissions are most probably relevant in the scope of EPHECT 237 Extremely few or no studies have been reported on the emissions of liquid/gel toilet cleaner 238 Some use scenario’s may cause significant dermal exposures 239 The product is used widely in most EU households 240 The product emits key pollutants confirmed by literature 241 This product is used on a weekly or daily basis 242 The use of the product may cause an inhalation exposure, as well as a dermal exposure 243 Health end points of the emissions are most probably relevant in the scope of EPHECT 244 Extremely few or no studies have been reported on the emissions of liquid/gel toilet cleaner 245 There is a clear relation between the exposure and the use scenario of this product 246 The product is used widely in most EU households 247 The product emits key pollutants confirmed by literature 248 This product is used on a weekly or daily basis 249 The use of this product causes mainly inhalation exposure 250 Health end points of the emissions are most probably relevant in the scope of EPHECT 251 Extremely few or no studies have been reported on the emissions of liquid/gel toilet cleaner 252 There is a clear relation between the exposure and the use scenario of this product
204
Bathroom cleaning agents Tissues
2253 2254 2255 1256 2257 2258 2259 A
Oven cleaners 1260 1261 1262 1263 1264 2265 1266 B
Metal cleaners 1267 1268 1269 1270 1271 2272 1273 B
Drain openers
Carpet/ textile cleaner powder
1274 1275 1276 1277 1278 2279 2280 B
253 The product is used widely in most EU households 254 The product emits key pollutants confirmed by literature 255 This product is used on a weekly or daily basis 256 The use of the product may cause an inhalation exposure, as well as a dermal exposure 257 Health end points of the emissions are most probably relevant in the scope of EPHECT 258 Extremely few or no studies have been reported on the emissions of liquid/gel toilet cleaner 259 There is a clear relation between the exposure and the use scenario of this product 260 This product is not common used in EU households 261 Based on its composition, the product may emit key pollutants 262 This product is rather used on a monthly basis – only in case needed 263 The use of the product may cause an inhalation exposure, as well as a dermal exposure 264 The emissions may cause health end points, not relevant in the EPHECT scope 265 Extremely few or no studies have been reported on the emissions of liquid/gel toilet cleaner 266 Some use scenario’s may cause significant dermal exposures 267 This product is not common used in EU households 268 Based on its composition, the product may emit key pollutants 269 This product is rather used on a monthly basis – only in case needed 270 The use of the product may cause an inhalation exposure, as well as a dermal exposure 271 The emissions may cause health end points, not relevant in the EPHECT scope 272 Extremely few or no studies have been reported on the emissions of liquid/gel toilet cleaner 273 Some use scenario’s may cause significant dermal exposures 274 This product is not common used in EU households 275 Based on its composition, the product may emit key pollutants 276 This product is rather used on a monthly basis – only in case needed 277 The use of the product may cause an inhalation exposure, as well as a dermal exposure 278 The emissions may cause health end points, not relevant in the EPHECT scope 279 Extremely few or no studies have been reported on the emissions of liquid/gel toilet cleaner 280 There is a clear relation between the exposure and the use scenario of this product
205
Carpet/ textile cleaner liquid
1281 1282 1283 1284 1285 2286 2287 B
Carpet/ textile cleaner spray
1288 1289 1290 1291 1292 2293 2294 B
Woodstove cleaners 1295 1296 0297 1298 2299 1300 1301 B
4.3. Polish products
Furniture polish liquid 2 1 1 2 1 2 2 A
Furniture polish spray 2 1 1 2 1 2 2 A
Furniture polish wipe 2 1 1 2 1 2 2 A
Houseplant polishers 0 1 0 2 1 1 1 C
Floor polishers 1 1 1 1 1 2 2 B
281 This product is not common used in EU households 282 Based on its composition, the product may emit key pollutants 283 This product is rather used on a monthly basis – only in case needed 284 The use of the product may cause an inhalation exposure, as well as a dermal exposure 285 The emissions may cause health end points, not relevant in the EPHECT scope 286 Extremely few or no studies have been reported on the emissions of liquid/gel toilet cleaner 287 There is a clear relation between the exposure and the use scenario of this product 288 This product is not common used in EU households 289 Based on its composition, the product may emit key pollutants 290 This product is rather used on a monthly basis – only in case needed 291 The use of the product may cause an inhalation exposure, as well as a dermal exposure 292 The emissions may cause health end points, not relevant in the EPHECT scope 293 Extremely few or no studies have been reported on the emissions of liquid/gel toilet cleaner 294 There is a clear relation between the exposure and the use scenario of this product 295 This product is not common used in EU households 296 Based on its composition, the product may emit key pollutants 297 The product is used annually 298 The use of the product may cause an inhalation exposure, as well as a dermal exposure 299 Health end points of the emissions are most probably relevant in the scope of EPHECT 300 Some studies report on emissions related to the use of this product 301 Some use scenario’s may cause significant dermal exposures
206
5 Air fresheners
Combustible (candles) 2302 2303 2304 2305 2306 1307 2308 A
Combustible incense 2309 2310 1311 2312 2313 1314 2315 A
Sprays 2316 2317 2318 2319 2320 1321 2322 A
Passive units 2323 2324 2325 2326 2327 1328 2329 A
Active (electric) units 2330 2331 2332 2333 2334 2335 2336 A
302 Candles are common used in EU households 303 Studies available in open literature have reported emissions of key pollutants (see section 4.5.1.2) 304 Candles are typically used on a weekly or daily basis 305 The emissions resulting from the use of the use of candles are typically cause inhalation exposure 306 The emissions caused by the use of this product may cause health end points in the scope of EPHECT 307 According to section 4.5.1.2, studies have been reported on emission data related to combustible air fresheners such as candles 308 The exposure to emissions related to candle burning are typically related to the use scenario (quantity used, distance to source, etc) 309 Incense is common used in EU households 310 Studies available in open literature have reported emissions of key pollutants (see section 4.5.1.1) 311 Incense is rather used on a monthly basis 312 The indoor use of incense causes inhalation exposure 313 Emissions caused by the use of incense may cause health end points in the scope of EPHECT 314 According to section 4.5.1.1 few studies have been organized to evaluate the emissions, related to the indoor use of incense 315 The exposure to emissions related to incense burning are typically related to the use scenario (quantity used, distance to source, etc) 316 The product is commonly used in EU households 317 Studies available in open literature have reported emissions of key pollutants (see section 4.5.2) 318 Air freshener sprays are typically used on a weekly or daily basis 319 Emissions related to air freshener sprays cause solely inhalation exposure 320 Emissions caused by the use of air freshener sprays may cause health end points in the scope of EPHECT 321 Few studies have reported on emissions related to the indoor use of spray air fresheners (see section 4.5.2) 322 The exposure is related to the use scenario of this product in households 323 This product is common used in EU households 324 According to the literature, reported in section 4.5.3, passive air fresheners may emit key pollutants 325 Passive air fresheners have a high indicative household use frequency, since once installed in the indoor environment, they start emitting 326 The use of a passive air freshener in the house mainly causes inhalation exposure 327 The emissions caused by the indoor use of these products may cause health end points in the scope of EPHECT 328 According to the literature, reported in section 4.5.3, very few studies have reported on the emissions related to passive air fresheners 329 The exposure is related to the use scenario of this product in households (quantity used, type, selected rooms, etc) 330 This product is common used in EU households and available on the market 331 Section 4.6.1 reports very few studies on emissions related to electric air fresheners. However, according to the data key pollutants may be emitted 332 Once installed to product is active on a daily basis 333 The indoor use of active air fresheners causes inhalation exposure 334 According to section 4.6.1, the indoor use of active air fresheners may cause health end points in the scope of EPHECT 335 According to section 4.6.1 the quantity of studies related to emissions due to the use of electric air fresheners is very limited 336 The indoor exposure is related to the use scenario in households (position min-max, quantity of air fresheners, type, selected rooms, etc
207
Ethereal Oils 1337 2338 1339 2340 2341 1342 2343 A
6. Pest control
Herbicides, 0 1 0 1 2 1 1 C
Animal repellent 1 1 0 1 2 2 1 B
Fungicides 1 1 0 1 2 2 1 B
Insecticides- spray 1344 1 0 2 2 2 2 B
Insecticides- active (electric units)
2345 1 1346 2 2 2 2 A
Insect repellents - spray 1347 1 0348 2 2 2 2 B
Insect repellents – cream/ lotion
1 1 1 0 2 1 1 C
Rodenticides 1 1 0 1 1 1 2 C
Wood treatment 1 1 0 1 1 1 2 C
Patio- removers
7. Clothes and fabrics
Fabric deodorizers 2 1 2 2 1 2 2 A
Shoes care products 1 1 1 1 1 2 2 B
Leather care products 1 1 1 2 1 2 1 B
337 The product is used more exceptionally in EU households 338 The product may emit key pollutants, according to the literature review reported in section 4.5.4 339 Since the indoor use usually requires some preparation, the use frequency will be lower than for other air fresheners 340 The indoor use of ethereal oils as air fresheners mainly causes inhalation exposure 341 According to the information reported in section 4.5.4, the use of ethereal oils as air fresheners, may cause the health end points in the scope of EPHECT 342 According to section 4.5.4 few studies have been organised on the composition and emissions, related to the indoor use of ethereal oils 343 The exposure is related to the use scenario (used quantity, use frequency, rooms, etc) 344 Typically used occasionally in EU households 345 This product is commonly used in EU households 346 This product is typically used on a monthly basis, rather than on an annual or weekly basis 347 Typically used occasionally in EU households, in a discontinuous way 348 This product is rather used on an annual basis, e.g. depending on season
208
Wool soap 0 1 1 0 1 1 1 C
Spot remover
8. Personal care products (Cosmetics, Toiletries and Perfumes)
8.1 Bathing and showering products (including hard- wash liquid)
Shower and bath gel 2 1 1 0 1 1 1 C
Bath oils 2 1 1 0 1 1 1 C
Bath salts 2 1 1 0 1 1 0 C
Hand wash liquid 2 1 1 0 1 1 0 C
Soaps 2 1 1 0 1 1 0 C
Aftershaves 2 1 1 1 0 1 1 C
Shaving cream 2 1 1 0 1 1 1 C
8.2. Hair care products and hair dyes
Hair decolouration products
1 2 1 2 2 2 0 B
Colour hair products 1 2 1 2 2 2 1 A
Hair maintenance products
1 1 0 0 1 1 1 C
Shampoo 1 1 2 2 1 2 1 B
Hair styling products (sprays)
2 2 2 2 1 2 2 A
Other hair and scalp care products and hair dyes
1 2 1 2 2 2 1 A
8.3. Skin care products
Skin care products,
including make up
1 1 1 1 1 2 1 B
Nail care products 1 2 1 2 1 2 2 A
209
Sun care products 0 1 0 0 1 2 2 C
Antiperspirants and Deodorants (roll on, stick)
1 1 2 1 1 2 1 B
Deodorants (spray) 1 1 2 2 2 2 2 A
Cleanser 0 1 0 0 1 2 2 C
Self tanning products 1 1 0 1 1 2 1 C
8.4. Oral hygiene products
1 1 1 0 1 2 1 C
8.5. Feet care products 1 1 1 0 1 2 1 C
8.6. Medicines
8.7. Baby care products 1 1 1 1 1 1 2 B
8.8. Perfumes 2 1 2 2 1 2 2 A
9. Printed material
Magazines 1 1 1 1 1 2 1 B
Newspapers 1 1 1 1 1 2 1 B
Books 1 1 1 1 1 2 1 B
Inks
10. Toys 2 1 1 1 1 1 1 B
11. Pet care products
Animal repellent 1 1 1 1 1 2 2 B
Flea and tick control
12. Flowers and plants
Spray to polish the leaves
13. Decorations
210
Decoration paint – indoor and outdoor
1 2 1 1 1 0 2 B
Varnishes and lacquers 1 2 1 1 1 0 2 B
Adhesives and glues 2 2 1 2 2 1 1 A
Paint 2 2 1 2 2 0 1 A
Paint thinner 2 2 1 2 2 1 1 A
14. Other
Firelighter
Fuels
211
Table 3. Reported volatile organic chemicals (VOCs) and SVOCs emitted by personal
computers during normal operation [Destailats et al., 2008]
Chemical Desktop PCs – CRT
monitor a,b
Desktop
PCs –TFT
monitorb
Notebook
computersc
Emission rate
(μgh-1 unit-1)
Chamber
conc (μg
m-3 )
Emission
rate (μgh-1
unit-1)
Emission
rate
(μgh-1
unit-1)
Chambe
r conc
(μg m-3 )
Phenol 1.7
Toluene 47 1.3 o.o4(0.1
5)
12.5
(45.6)
Styrene 7.6 0.2
Xylenes 10.3 0.3
C6-C10 aromatics 46-103 1.3 32
>C10 aromatics 58.3 1.6
Bicyclic
aromatics
41 1.1
n-Decane 11.6 0.3
n-Undecane 7.6 0.2
Formaldehyde 5.2-12.8 0.1 9.7
Aceataldehyde 3.6 1.5
Propionaldehyde 0.5
n-Butyraldehyde 1.4
212
Valeraldehyde 3.1 0.5
Hexaldehyde 4.6 2.7
Methylcarbonate 0.73
(1.3)
223
(393)
Ethylcarbonate 0.37
(0.78)
112
(240)
Cyclohexane 0.07
(0.21)
23 (65)
2-Butoxyethanol 0.82
(2.14)
217
(618)
2-ethyl-1-
hexanol
19.6 0.5 0.14
(0.52)
34 (150)
Acetophenone 0.05
(0.11)
Trimethylcyclohe
xenone
0.13
(0.34)
18 (86)
Cyclohexyl
benzene
0.16
(0.81)
50 (250)
ΣVOC 180 113
a Bako – Biro et al (2004)
b Nakagawa et al (2003)
cHoshino et al (2003) (values correspond to “idle” conditions; emissions during
operation are in parenthesis)
Chemical Emissions Chamber Equipment/experimental
213
rate (mg-1
unit -1)
concentration
(ng m-3)
conditions
Hexabromobenzene 1 Desktop PCs in
operationa,b
Resorcinol-bis-biphenyl
phosphate (RDP)
2 13 (100d)
Bisphenol A
bis(diphenylphosphate)
[BDP]
44 20 (100d)
1-3
tris(chloropropyl)phosphate
(TCPP)
24
Triphenyl phosphate (TPP) 25 85 (100d)a
94 (1d)b
8.6 (183 d)b
Brominated diphenyl ether
(BDE 47)
150 Desktop PCs after
operation (extracted from
chamber surfaces)a
BDE 100 28
BDE 99 61
Tetrabromo bisphenol A
(TBBPA )
64-446
di-n-butyl phthalate (DBP) 110/650 Notebook computerc
When available, the duration of operation (days) is indicated in parenthesis.
aKemmlein et al., (2003)/ bCarlsson et al., (2000) (video display units)/ cHoshino et
al., (2003) (idle/ operating)
214
Table 4. Compounds of interest emitted from major consumer product classes and
types
PRODUCT EMISSIONS LITERATURE
1. ELECTRONIC EQUIPMENT
Laser printers Ultrafine particles (d<0.1μm), VOC, TVOC , ozone, tri-xylyl phosphate, diisopropylnaphthalene
Wensing et al (2008)
Monitors benzene, 3-carene, Butylhydroxytoluene (BHT), di butyl phthalate, cyclohexanoxe, Phenol Toluene, 2-ethoxyethyl acetate Lactic acid, butylester, Cresole, Xylene Ethylbenzene, Ethylenbenzene (styrene), 1-(2-buthoxy)ethoxyethanol 2-tert-butylazo-2-methoxy-4-methylpentane, Benzaldehyde, Trimethylbenzene Acrylic acid, ethylester, 4-hydroxy-4-methylpentane, Nonan, Dedecane, Undecane, Dodecane, Octamethyl cyclotetrasiloxane, Dodecamethyl cyclohexasiloxane, 2-hydroxybenzaldehyde, Hydroxytoluene o-methylhydroxytoluen, Aceticacid, butylester, Acetophenone, Caprolactam 2-buthoxyethanol, Heptadecane, Butyl isobutyl phthalate, Butyl octyl phthalate Propylbenzene, Cyclohexanone, Benzoic acid, pentylester, 2,6-bis(1,1-dimethylethyl)-4-ethylphenol, 2,6-bis(1,1-dimethylethyl)-4-butylphenol 3-(1,1-dimethylethyl)phenol, Hexandioicacid, Tributylphosphate Triphenyl phosphate
Malmgren-Hansen et. Al. (2003)
Personal computers Polybrominated diphenyl ethers, VOC, TVOC , ozone, phenol, toluene, xylene, C6-C10 aromatics, >C10 aromatics,
Rudel et al (2009), Wensing et al (2008), Destaillats et al. (2008), Watanabe and Sakai
215
PRODUCT EMISSIONS LITERATURE
bicyclic aromatics, n-decane, n-undecane, formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, valeraldhyde, hexaldehyde, methylcarbonate, ethylcarbonate, cyclohexane, 2-butoxyethanol, 2-ethyl-1-heaxanol, acetophenone, trimethylcyclohexanone, cyclohexene benzene, organophosphorus flame retardants, brominated flame retardants, triphenyl phosphate (TPP), hexabromo benzene, Resorcinol-bis-biphenyl phosphate (RDP), Bisphenol A bis(diphenylphosphate) [BDP], 1-3 tris(chloropropyl)phosphate (TCPP), Brominated diphenyl ether (BDE 47), BDE 100, BDE 99, Tetrabromo bisphenol A (TBBPA ), di-n-butyl phthalate (DBP), polybrominated dibenzo-p-dioxines (PBDD),
(2003),
Game console Formaldehyde, acetaldehyde, 3-carene, di-butyl phthalate, styrene
Malmgren-Hansen et. Al. (2003)
converters Butylhydroxytoluene (BHT), Formaldehyde, acetaldehyde, ethylbenzene, 3-ethylhexanoic acid, cyclohexanone, dibutylphthalate, Toluene, Trimethylbenzene, m-,p-xylene, Ethylbenzene, 2-methyl-1-propanol,o-xylene, 2-pentylfurane, 2-ethylhexanol, 2-buthoxyethanol, Phenol, Hexanal, Tetramethylbenzene, Decanal/alcohol, Formic acid, butylester, Butanal, 2-ethylhexanoic acid, Pentanal, Formic acid, 2-methylester, Alcohol, Acetophenon Acetone, 2-hydroxybenzenethanol, A-pinen, Propanal, Butylacetate, 3-methylbutanal/pentanal, Chlorobenzene, Octanal, Benzaldehyde
Malmgren-Hansen et. Al. (2003)
Dry process Ultrafine particles Zuraimi et al. (2006),
216
PRODUCT EMISSIONS LITERATURE
photocopiers (d<0.1μm), Tetradecane, benzaldehyde, o-xylene and naphthalene, VOC, TVOC , ozone, NOx, formaldehyde
Wensing et al (2008)
Telephone Toluene, 2-ethylhexanol, n-pentadecane, Ethylmethylbenzene, n-tetradecane, Naphthalene, Tetrachlorethene, 2,6 di-tert-butyl-4-methylphenol (BHT)
Malmgren-Hansen et. al. (2003)
Mobile phone Diethyl phthalate, 2,6 di-tert-butyl-4- methylphenol (BHT), 2-Ethylbenzene, Xylenes, Benzene, 3-carene
Malmgren-Hansen et. al. (2003)
Answering machine 2-ethylhexanol, Trimethylbenzene, n-alkanes, Xylenes, Phenol, 2,6 di-tert-butyl-4-methylphenol (BHT), N,N-dimethylformamide, Benzophenone
Malmgren-Hansen et. al. (2003)
Digital answering machine
2-ethylhexanol,Toluene, Xylenes Silicones, n-tetradecane, n-dodecane, 2,6 di-tert-butyl-4-methylphenol (BHT)
Malmgren-Hansen et. al. (2003)
Electric shaver 1-ethoxy-2-propanol, Cyclohexanone 2,6 di-tert-butyl-4-methylphenol (BHT) Toluene, 2-ethylhexanol, n-alkanes, Cyclohexanone, Naphthalene, Methylnaphtalenes, Alkylbenzenes, n-alkanes, Benzene
Malmgren-Hansen et. al. (2003)
TV sets Polybrominated diphenyl ethers (PBDE), polybrominated dibenzo-p-dioxines (PBDD), benzene, formaldehyde, acetaldehyde, 3-carene, Butylhydroxytoluen e (BHT), styrene, ethylbenzene, di butyl phthalate, Vinyl chloride Toluene, xylenes, Phenol, o,m,p-cresols, Dichloromethane, Trichlorethene, Tetrachlorethene 2-butoxyethanol, n-
Rudel et al (2009), Watanabe and Sakai (2003), Malmgren-Hansen et. al. (2003)
217
PRODUCT EMISSIONS LITERATURE
nitrosdibutylamine, Bis-(2-ethyl)-hexylphthalate, Dibutyl phthalate,PCBs, Pentabromotoluene, TCEP (Tri-(2-chloroethyl)-phosphate), Tributyl phosphate (TBP), Trikresyl phosphate (TKP), Triphenyl phosphate (TPP), Tri(2-butoxyethyl)-phosphate (TBEP), Tri(2-chlorethyl)-phosphate (TCEP), Tri(chlorpropyl)-phosphate (TCPP) Tri(dichloropropyl)-phosphate (TDCPP), Tri(2-ethylhexyl)-phosphate (TEHP), a-pinene
2. APPLIANCES
Cooking Fine particles, PAHs, VOCs, SVOCs, aldehydes, acrolein,
1,3-butadiene, nitrosamines
Zhang & Smith (2003), WHO (1987)
Air conditioning Biological pollutants (bacteria, fungi, fungal spores, viruses, and pollen and their fragments, including various antigens), particles,
Zhang & Smith (2003)
Vacuum cleaner Particles Yu et al (2009)
Hair dryer Polybrominated diphenyl ethers (PBDE), n-tetradecane, n-pentadecane, n-hexadecane, 2-ethylhexanol, Naphthalene, 2,6 di-tert-butyl-4-methylphenol (BHT)
Covaci et al (2003), Malmgren-Hansen et. al. (2003)
Electric hand mixer 2,6 di-tert-butyl-4-methylphenol (BHT), Nonanal, n-alkanes, Tert-butyl-methylphenol, Styrene,Toluene, Trichlorethylene, Cyclohexanone
Malmgren-Hansen et. al. (2003)
Portable CD player Trimethylbenzene, alkylbenzenes, n-alkanes, 2-ethylhexanol, Toluene Cyclohexanone
Malmgren-Hansen et. al. (2003)
Gameboy Several silicones, 2,6 di-tert-butyl-4- methylphenol (BHT),, Several n-alkanes
Malmgren-Hansen et. al. (2003)
218
PRODUCT EMISSIONS LITERATURE
3. HEATING
Biomass fuel Formaldehyde, benzo[a]pyrene, benzene
WHO (1987)
fireplace PAHs WHO (1987)
Kerosene heater PAHs WHO (1987)
Wood stove PAHs WHO (1987)
Gas stoves NO2 Zhang & Smith (2003)
Solid fuel stoves VOCs, PM, PAHs, NOX, SOx, 1,3-butediene, benzene, arsenic, fluorine, formaldehyde, nitrosamines
Zhang & Smith (2003), WHO (1987)
Biomass burning Particles, CO, NOx, SOx, formaldehyde, PAHs, and polycyclic organic matter, including carcinogens such as benzo[a]pyrene
WHO (2000)
Coal combustion SOx, arsenic, fluorine, Particles, NOX, CO,
Zhang & Smith (2003), WHO (1987)
4. HOUSEHOLD PRODUCTS
Laundry supply (cloth dryer sheet)
Linalool, Ethanol, Benzyl acetate, cis-rose oxide, Carene isomer, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde (Triplal 1), d-limonene, 3-methyl-2-buten-1-ol acetate, 2,7-dimethyl-2,7-octanediol, α-pinene, trans-rose oxide, Eucalyptol, α-phenylethyl acetate, β-pinene, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde (Triplal extra)
Steinemann (2009)
Laundry supply (Scented liquid fabric softener)
Ethanol, d-limonene, Methoxy ethane, α-pinene, Benzyl acetate, Isocineole, β-pinene, 2-Methoxy propane, Linalool, (Z)-3,4-dimethyl-3-hexen-2-one, Chloromethane, γ-terpinene coeluted with 2,7-dimethyl-2,7-octanediol, Acetaldehyde, 2,4-dimethyl-1,3-
Steinemann (2009), Schmeiser et al. (2001), Kwon et al (2007)
219
PRODUCT EMISSIONS LITERATURE
cyclopentanedione, 3-methyl-2-buten-1-ol acetate, α-terpinolene, Diethoxy methane, 1,5-dimethyl-1,4-cyclohexadiene, 1-methyltricyclo[2.2.1.0(2,6)]-heptane, α-terpinene, musk xylene 2-Butanol,
Laundry supply (Scented liquid detergent )
Ethanol, d-limonene, 2-methyl-2-propanol, 1,4-dioxane, 3,7-dimethyl-1,6-octadiene, Ethyl acetate, α-pinene, β-pinene, 2-butanone, 1-methyl-3-(1-methylethyl)-cyclohexene, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde (Triplal 1), Undecane, β-terpinene , musk xylene, Acetone, benzene,
Steinemann (2009), Schmeiser et al. (2001), Kwon et al (2007)
Detergents a-pinene, d-limonene, VOCs, benzene, xylenes, acetaldehyde, toluene,
3-Butenylpropylether, musk xylene (MX)
Zhang & Smith (2003), Nazaroff et al (2006), Kafferlein et al (2001)
Bleach Acetone, chloroform, 1,8-cineole, limonene, cis-limonene oxide, trans-limonene oxide, a-pinene, β-pinene
Kwon et al (2007)
Floor mopping products
d-limonene, 2-butoxy ethanol (ethylene glycol), terpinolene, a-terpineol, VOCs, styrene, formaldehyde, toluene, Dicyclopentadiene alcohol, Dihydromyrcenol, Linalool, α-Pinene, β-Pinene, tripropylene glycol monomehtyl ether, methyl ethyl ketone (2-butanone), 1,2-dichloropropane (propylene dichloride), 3-carene
Nazaroff et al., (2006), Cancer Prevention Coalition, Nazaroff & Weschler (2004)
Glass cleaner 2-butoxy ethanol (ethylene glycol), VOCs, Camphene, 3-Carene, Limonene, a-phellandrene, ethanol 1,8-
Nazaroff et al., 2006, Nazaroff & Weschler (2004), Kwon et al (2007)
220
PRODUCT EMISSIONS LITERATURE
Cineole,
General purpose cleaner
d-limonene, 2-butoxy ethanol (ethylene glycol), terpinolene, a-terpineol, γ-terpineol, VOCs, Camphene, 3-Carene, a-pinene, β-pinene, β-myrcene, 2-hexyloxyethanol, 2-Propanol, Di(propylene glycol) butyl ethers, toluene, Decane, octane, β-terpinene 1,8-Cineole, iso-cineole, Ammonia, chloroform
Nazaroff et al. (2006), Nazaroff & Weschler (2004), Kwon et al (2007)
Disinfectants 4-nonylphenol and nonylphenol ethoxylates, a-Terpineol, Camphene, 3-Carene, α-Pinene, β-Pinene, 2-butoxy ethanol, toluene, iso-Amyl acetate, ethanol, hexane, limonene, 3-methyl pentane, undecane, Camphene, decane, octane, β-pinene, toluene, Ammonia, Ethanol, Chloroform, 1,8-cineole, iso-cineole
Nazaroff et al. (2006), Nazaroff & Weschler (2004), Kwon et al (2007)
Anti-bacterial cleaner 2-butoxy ethanol, ethylene glycol, toluene, Camphene, 3-Carene, Limonene, β-Myrcene, α-Phellandrene, β-Pinene, α-Pinene
Nazaroff et al., (2006), Nazaroff & Weschler (2004)
Household cleaners Ethylbenzene, n-hexane, carbon tertrachloride, dichloromethane (methylene chloride), tetrachloro ethylene (perchloroethylene), 1,1,1-trichloroethane (methyl chloroform), benzene, trichloroethylene, xylenes, trichloromethane (chloroform), 1,4-dioxane, Methyl methacrylate, a-Terpineol, Camphene, 3-Carene, β-Myrcene, α-Pinene, β-Pinene, ammonia, ammonium chloride, calcium carbonate, toluene, cocodiethanolamide, diethanolamine, ethyl alcohol, sodium hydroxide, sodium
Nazaroff et al., 2006, Cancer Prevention Coalition, Nazaroff & Weschler (2004)
221
PRODUCT EMISSIONS LITERATURE
hypochlorite (bleach), triethanolamine, methylmethacrylate
Hard surface cleaners
diethylene glycol, 2-(2-butoxyethoxy)ethanol
Nazaroff et al., (2006)
Dishwashing detergent
Ethanol, limonene, 1-propanol, 1,4-Dioxane, ethyl acetate, β-myrcene, 3-pentanol, a-pinene, Ethanol, 1-hexadecanol, β-myrcene, 1-tetradecane
Kwon et al (2007)
toilet cleaners Toluene, 1,4-dichloro benzene, dimethyl-benzyl ammonium chloride, dimethyl- ethylbenzyl ammonium chloride, hydrochloric acid, iodine, sodium bisulfate, sodium dichloroisocyanurate dehydrate, sodium ortho-phenylphenol, sodium sulphate, tetrasodium EDTA, trisodium nitrilotriacetate
Cancer Prevention Coalition
Cleaners for electronic equipment
1,1,2-trichlrotrifluoroethane, 1,1,1-trichlroethane, tetrachloroethylene
Carpet cleaners Isopropyl alcohol Cancer Prevention Coalition
Furniture polishes and waxes
Kerosene, turpentine, morpholine, aliphatic naphtha, formaldehyde, benzene, ethylbenzene, styrene, n-hexane, acetaldehyde, caryofyllene, a-Humulene, longifolene, a-cedrene, oleic acid, Acetone, 2,7-dimethyl-undecane, limonene, β-myrcene, α-pinene, decane,
Cancer Prevention Coalition, Nazaroff & Weschler (2004), Kwon et al (2007)
Car cleaners and waxes
Kerosene, medium aliphatic hydrocarbons, medium aliphatic solvent naphtha, silicone emulsion, sodium silicate, turpentine, xylene, morpholine, ammonia, dipropylene glycol methyl ether, ethylene glycol, formaldehyde, isoparaffinic
Cancer Prevention Coalition
222
PRODUCT EMISSIONS LITERATURE
hydrocarbon, iso propyl alcohol
Dry cleaning Limonene, Ammonia, δ-3-carene, β-myrcene, octyl aldehyde, a-pinene, sabinene
Kwon et al (2007)
Oven cleaner Camphene, 1,8-cineole, iso-cineole, ethanol, limonene, β-myrcene, α-pinene, sabinene, α-terpinolene, Ammonia, ethanol
Kwon et al (2007)
Spot removers Light petroleum distillates, limonene, sodium dithionate, sodium dodecylbenzene sulfonate, tetrachloroethylene, toluene, urea, xylene, dipropylene glycol methyl ether, Ammonia, decane, Acetone, 3,7-dimethyl-3-octanol
Cancer Prevention Coalition, Kwon et al (2007)
5. AIR FRESHENERS
Air fresheners Ethylene-based glycol ethers [diethylene glycol, 2-(2-ethoxyethoxy)ethanol, 2-butoxy ethanol], terpenes, Linalool, a-terpineol, β- terpineol, γ-terpineol, Linalyl acetate, Camphene, Limonene, β-Myrcene, Ocimene, α-pinene, β-pinene, 3-carene, a-terpinene, γ-terpinene, terpinolene, dihydromyrcenol, β-citronellol, cis-citral, trans-citral, Acetic acid, isononyl ester, Isobornyl acetate a,a-Dimethylbenzene ethanol acetate, Eucalyptol, Di(propylene glycol) butyl ethers, Camphor, Isobornyl acetate, Tri(propylene glycol) methyl ethers, Benzyl acetate, 4-cis-Butylcyclohexyl acetate, 4-tert-Butylcyclohexyl Acetate, Butylated hydroxytoluene, ammonium hydroxide, iso paraffinic hydrocarbon, linalool, camphene, 4-tert-
Nazaroff et al., 2006, Cancer Prevention Coalition, Nazaroff & Weschler (2004), Steinemann (2009), Kwon et al (2007)
223
PRODUCT EMISSIONS LITERATURE
butylcyclohexyl acetate, 2,7-dimethyl-2,7-octanediol, acetone, ethanol, Citronellyl acetate, hexanal, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde (Triplal 1), Allyl heptanoate, -methyl-4-(1-methylethyl)-cyclohexane, Ethyl butanoate, 3-hexen-1-ol, o, m, or p-cymene, 3-methoxy-3-methylbutanol, nonanal, 2-methyl-2,4-dimethoxybutane, α-phenylethyl acetate, 1-butanol, 3-methyl-acetate, benzaldehyde, 1-methyl-3-(1-methylethyl)-cyclohexene, Isopropyl alcohol, 1-butanol, 2-methyl-acetate, Methyl butanoate, Dimethyl ethyl cyclohexene, Decane, Acetaldehyde, dodecane, ethyl acetate, nonadecane, undecane, Hexane, 2-methyl pentane
Air freshener (wall mounted unit)
d-limonene 3-methoxy-3-methylbutanol Linalool, Carene isomer, Nonanal , 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde (Triplal 1) , 2-methyl-2,4-dimethoxybutane, α-phenylethyl acetate, β-pinene, 3-hexen-1-ol, Octanal, Ethanol
Steinemann (2009)
Plug-in air freshener d-limonene, α-pinene, β-pinene, Ethanol, Ethyl butanoate, Ethyl acetate, 3-hexen-1-ol, 1-butanol, 3-methyl-, acetate, β-phellandrene, Acetaldehyde, Benzaldehyde, Carene isomer, 1-methyl-3-(1-methylethyl)-cyclohexene, Isopropyl alcohol, 1-butanol -2-methyl- acetate, Camphene Acetone, Methyl butanoate, Dimethyl ethyl cyclohexene, α-phellandrene
Steinemann (2009)
Lavender Dibutyl phthalate , Linalool, Diethyl Phthalate, Camphor, Linalyl acetate, Pichtosin,
Chiang et. al (2010)
224
PRODUCT EMISSIONS LITERATURE
Formaldehyde, Acetaldehyde, Acetone, Propionaldehyde, Butyraldehyde, Benzaldehyde, Isovaleraldehyde, m-Tolualdehyde, Hexaldehyde
Lemon Limonene, Hexyldecanol, Disparlure (2S-cis), Squalene
Formaldehyde, Acetaldehyde, Acetone, Propionaldehyde, Valeraldehyde, p-Tolualdehyde
Chiang et. al (2010)
Rose Isopropyl myristate, Rhodinol, Phenylethyl alcohol , 1-Nonadecene, Heneicosane, Formaldehyde, Acetaldehyde, Acetone, Propionaldehyde, Valeraldehyde, p-Tolualdehyde
Chiang et. al (2010)
Rosemary Eucalyptol , Camphor , a-Pinene, Limonene , b-Pinene Formaldehyde Acetaldehyde Acetone Propionaldehyde Butyraldehyde Isovaleraldehyd m-Tolualdehyde , Hexaldehyde
Chiang et. al (2010)
Tea tree 4-Terpineol, g-Terpinene, 4-Cymene , a-Terpinene, Eucalyptol, a-Terpineol Formaldehyde, Acetaldehyde, Acetone, Propionaldehyde, Butyraldehyde, m-Tolualdehyde , Hexaldehyde
Chiang et. al (2010)
6. PESTS CONTROL
Pesticides Dichlorvos, diazinone, D-cis trans allethrin, hydramethylnon, 1,1,1-trichloro ethane, bendiocarb, calcium oxide, D-cis trans allethrin, diazinon, fenvalerate, hydramehtylnon, N-octyl bicycloheptene dicarboximide, propoxur, pyrethrins, phthalates, chlordane, Malathion, dimpylate, limonene, 2-methyl-butane, tetradecane, tridecane,
Zhang & Smith (2003), Cancer Prevention Coalition, Rudel et al (2009), WHO (1987), Kwon et al (2007)
225
PRODUCT EMISSIONS LITERATURE
undecane, Decane, dodecane,
7. CLOTHES AND FABRICS
Fabric refresher VOCs, 1,1,1-trichloroethane, methylene chloride, tetrachloroethylene, toluene
Dry cleaned clothing Tetrachloro ethylene Zhang & Smith (2003)
Shoe polisher Titanium dioxide, turpentine Cancer Prevention Coalition
Footwear or leather care products
VOCs, butyl acetate, ethylene glycol, 1,1,1-trichloroethane, methylene chloride, tetrachloroethylene, toluene
Cancer Prevention Coalition
T shirt Alkyl phenol and alkylphenol ethoxylates, nonylphenol ethoxylates, nonyl phenol, di-octyltin, mono-octyltin, di-butyltin, di-n-butyl phthalate, di-iso-butyl phthalate, benzyl butyl phthalate, dicyclohexyl phthalate, di(2-ethylhexyl) phthalate, di-isononyl phthalate
Ruud (2005)
Fabric deodorizers Ammonia, ethanol, 1-Chloro-2-methyl benzene, ethanol, limonene, β-myrcene, α-pinene, β-pinene, γ-terpinene
Kwon et al (2007)
8. PERSONAL CARE PRODUCTS
Deodorizers p-dichloro benzene, hydrochloric acid, iodine
Zhang & Smith (2003), Cancer Prevention Coalition
Showering Chloroform Zhang & Smith (2003)
Hair styling products VOCs, phthalates, parabens Rudel et al (2009)
Hand and body lotion
diethyl phthalate (DEP), polycyclic musks (galaxolide), musk xylene (MX)
Houlihan et al (2002), Hutter et al (2005), Kafferlein et al (2001)
Hair mousse diethyl phthalate (DEP) Houlihan et al (2002)
Hair gel diethyl phthtalate (DEP) Houlihan et al (2002)
226
PRODUCT EMISSIONS LITERATURE
Hair spray diethyl phthalate (DEP), Di-n-butyl phthalate (DBP), Butylbenzyl phthalate (BBzP)
Houlihan et al (2002)
aftershaves Momoethyl phthalate (MEP) Duty et al (2005)
cream Parabens (methyl paraben, ethyl paraben, butyl paraben, benzyl paraben)
Rudel et al (2009), Rastogi et al (1995)
Lip-care products Propyl paraben, butyl paraben, methyl paraben
Rastogi et al (1995)
Sun care products Methyl paraben, ethyl paraben, propyl paraben
Rastogi et al (1995)
Perfume Di-n-butyl phthalate (DBP), diethyl phthalate (DEP), Momoethyl phthalate (MEP), Butylbenzyl phthalate (BBzP), Diethylhexyl phthalate (DEHP), musk xylene (MX)
Rudel et al (2009), Duty et al (2005), Houlihan et al (2002), Hutter et al (2005), Kafferlein et al (2001)
Eye-make up remover
Parabens (methyl paraben, ethyl paraben)
Rastogi et al (1995)
Shampoo Parabens Rudel et al (2009), Rastogi et al (1995)
deodorant Parabens, diethyl phthalate (DEP), Momoethyl phthalate (MEP), Di-n-butyl phthalate (DBP, Dimethyl phthalate (DMP), Ammonium chlroride, dimethylbenzyl ammonium chloride, iodine, sodium bisulfate, sodium dichloroisocyanurate dihydrate, sodium sulfate
Rudel et al (2009), Duty et al (2005), Houlihan et al (2002), Cancer Prevention Coalition
Liquid soap Phthalates Rudel et al (2009)
Nail polish Di-n-butyl phthalate (DBP), Benzene, ethyl acetate, limonene, 2-propanol, Ethanol, toluene
Rudel et al (2009), Duty et al (2005), Kwon et al (2007)
Nail polish remover Acetone, cyclohexane, butyl acetate, 2,2,4-trimethyl-1,3-dioxolane
Kwon et al (2007)
227
PRODUCT EMISSIONS LITERATURE
Eye shadow Phthalates Rudel et al (2009)
Shaving gel VOCs
Wood cleaners VOCs
Baby care products Musk ketone, musk galaxolide, di-ethyl phthalate, nonyl phenol ethoxylate
Ruud (2005)
Baby detergents Nonylphenol, nonylphenol ethoxylate, musk galaxolide, musk ketone, musk tonalide, diethyl phthalate, musk xylene
Ruud (2005)
Baby lotion Alkyl phenol, alkylphenol ethoxylates, musk galaxolide, musk ketone, musk xylene, musk tonalide, diethyl phthalate, benzylbutyl phthalate
Ruud (2005)
Steel wool soap Benzene, xylenes, ethylbenzene, Musk xylene
Nazaroff & Weschler (2004) Schmeiser et al (2001)
9. PRINTED MATERIAL
10. TOYS
Toys Phthalates (di-isononyl phthalate, di-isodecyl phthalate, di-iso-butyl phthalate, dicyclohexyl phthalate, di(2-ethylhexyl) ohthalate, di-iso-nonyl phthalate), organotins (monobutyltin di-butyltin, tributyltin, tetrabutyltin, di-octyltin, mono-octyltin,) nonyl phenol, nonylphenol ethoxylate, octylphenol ethoxylate,
Ruud (2005)
11. PET CARE PRODUCTS
Pet care products Allethrin, carbaryl (Sevin), cyfluthrin, diazinon, dichlorvos (DDVP), d-limonene. D-trans allethrin, fenvalerate, tetrachlorvinphos, tetramethrin, methoxychlor, naled,
Cancer Prevention Coalition
228
PRODUCT EMISSIONS LITERATURE
permethrin, petroleum distillates, phenothrin (sumithrin), pyrethrins, resmethrin, rotenone
12. FLOWERS AND PLANTS
13. DECORATION AND MAINTENANCE
Adhesives
Benzene, ethylbenzene, toluene, xylenes, styrene, halogenated hydrocarbons, vinyl acetate, ethers
Solvent based adhesives for walls and ceilings
Toluene, styrene, n-decane, n-undecane, C10-C11 branched alkanes, C10 cyclohexanes
Flooring adhesive 1,2-propanediol, 2-ethylhexanol, 2-(2-butoxyethoxy)ethanol, 4-phenylcyclohexene, β-caryophyllene, a-humene, methyl cyclopentane
Vinyl & rubber flooring adhesive
2-phenoxyethanol, 2-(2-butoxyethoxy)ethyl acetate, tetradecane, Β-caryophyllene, tridecane, 2-propyldecanol
Adhesive for carpets Toluene, 1,2,4-trimethylbenzene, 1,2-dimethylcyclohexane, cymenes, 1,2,3-trimethylbenzene, naphthalene, xylenes, low molecular weight alcohols, n-octane, n-dodecane, C8-C9 branched alkanes, methyl cyclohexane, C8-C9 cyclohexanes, n- decane, n-undecane,
Cork adhesive Diethylamine, CS2, 4-vinyl-1-cyclohexane, 4-phenylcyclohexane,
Waxes Benzene, trimethylcyclohexane, methyloctane, methylethyl cyclohexane, nonane, dimethyloctane, p-ethyltoluene, trimethyl benzene, n- decane, undecane, toluene, octane, dodecane, tridecane, teradecane, heptadecane, hexadecane, ethylbenzene,
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PRODUCT EMISSIONS LITERATURE
xylenes, styrene, ethyltoluene, 1,3,5- trimethylbenzene, 1,2,4- trimethylbenzene, 1,2,3- trimethylbenzene, 1,2,4,5- tetramethylbenzene, a-pinene, d-limonene, dichloromethane, chloromethane, 1,1,1-trichloromethane, 1,2-dichloroethane, carbontetrachloride, trichloroethylene, 1,2- dichloroethane, ethylacetate, acetone, nonanal, decaal, ethanol, propanol, butanol
Varnishes Toluene, xylenes, ethylbenzene, chlorobenzene, 1,2,3-trimethylbenzene
230
Table 5. Compounds emitted from specific products
COMPOUNDS PRODUCTS
Fine particles
Laser printers, dry process photocopiers, cooking, vacuum
cleaning, biomass burning, coal combustion
Formaldehyde
Floor mapping products, furniture polishes and waxes, car
cleaners and waxes, air fresheners (levanter, lemon, rose,
rosemary, tea tree), biomass fuel, biomass burning, dry
process photocopiers, TV sets, game consoles,
consenters, solid fuel stoves, personal computers
Benzene
Monitors, mobile phones, electric shavers, TV sets,
biomass fuel, solid fuel stoves, detergents, household
cleaners, furniture polishes and waxes, nail polishes, steel
wool soap
Toluene
Monitors, personal computers, telephones, digital
answering machines, electric shaver, TV sets, electric
hand mixer, portable CD players, detergents, floor
mapping products, general purpose cleaners,
disinfectants, antibacterials, household cleaners, toilet
cleaners, spot removers, fabric refresheners, footwear or
leather care products, nail polishes
Xylenes
Monitors, personal computers, mobile phones, converters,
answering machines, TV sets, detergents, household
cleaners, spot removers, dry process photocopiers, car
cleaners and waxes, hand and body lotions, perfumes,
baby detergents, baby lotions, steel wool soaps
Acetaldehyde
Detergents, furniture polishes and waxes, air fresheners,
personal computers, game consoles, converters, TV sets
Limonene
Detergents, fabric softeners, bleach, florr mapping
products, glass cleaners, general purpose cleaners,
disinfectants, antibacterials, dishwashing detergents,
furniture polishes and waxes, oven cleaners, spot
removers, air fresheners, fabric deodorisers, nail polish,
pet care products
a-pinene TV sets, cloth dryer sheet, fabric softeners, liquid
231
COMPOUNDS PRODUCTS
detergents, bleach, floor mapping products, general
purpose cleaners, disinfectants, antibacterials, household
cleaners, dishwashing detergents, furniture polishes and
waxes, dry cleaning, oven cleaners, air fresheners, fabric
deodorisers
Naphthalene
Dry process photocopiers, telephone, electric shavers,
hair dryer
Ammonia
Disinfectants, household cleaners, car cleaners and
waxes, dry cleaning, oven cleaners, spot removers, fabric
deodorisers, general purpose cleaners
Ozone Laser printers, personal computers, dry process
photocopiers
CO Coal combustion
PAHs
Cooking, fireplace, kerosene heaters, wood stoves, solid
fuel stoves, biomass burning
Phthalates
Monitors, PCs, game consoles, converters, mobile phones,
TV sets, air fresheners, pesticides, T-shirts, hair styling
products, hand and body lotions, aftershaves, perfumes,
deodorants, liquid soaps, nail polish, eye shadows, baby
detergents, baby care products, toys
Styrene
Floor mapping products, furniture polishes and waxes, TV
sets, electric hand mixers, monitors, game consoles
NOx
Dry process photocopiers, solid fuel stoves, coal
combustion, biomass burning
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Table 6. Target compounds for the EPHECT project.
Compound INDEX SCHER WHO Emerging pollutants
Formaldehyde √ √ √
CO √ √
NO2 √ √ √
Benzene √ √ √
Naphthalene √ √ √
Acetaldehyde √
ETS √
Particles (fine & ultrafine) √ √
Limonene √ √
O3 √
PAHs √
PCBs √
PCDDs √
A-pinene √
Toluene √ √
Xylenes √
Styrene √ √
Siloxanes (perfluorinated) √
linalool √
isoprene √
2-butoxyethanol √
SO2 √
ammonia √
Ammonium chlorides √