Survey and risk
assessment of
chemical substances
in bicycle helmets
Survey of chemical
substances in consum-
er products No. 162a
February 2018
Publisher: The Danish Environmental Protection Agency
Editing: Pia Brunn Poulsen, Charlotte Merlin, Anders
Schmidt, FORCE Technology
ISBN: 978-87-93614-66-6
The Danish Environmental Protection Agency publishes reports and papers about research and development projects
within the environmental sector, financed by the Agency. The contents of this publication do not necessarily represent
the official views of the Danish Environmental Protection Agency. By publishing this report, the Danish Environmental
Protection Agency expresses that the content represents an important contribution to the related discourse on Danish
environmental policy.
Sources must be acknowledged.
Contents
Preface 5
Summary and conclusions 6
1. Introduction 10
1.1 Purpose 10
1.2 Delimitation 10
2. Standards and legislation 11
2.1 Standards 11
2.2 Legislation regarding content of chemical substances 11
2.2.1 The Product Safety Act 11
2.2.2 REACH Annex XVII restrictions 12
2.2.3 Danish legislation regarding heavy metals 12
2.2.4 The POP regulation 12
2.2.5 Overall overview of legislation regarding chemical substances 13
3. Collection of information 15
3.1 Contact to the trade 15
3.1.1 Contact to the trade association “Danish Bicycle Dealers” 15
3.1.2 Contact to suppliers of bicycle helmets 15
3.2 Internet search 17
3.3 Visits in shops 17
3.4 Use of the app ”Check the Chemistry” 18
3.5 Literature search 18
3.5.1 Consumer test of bicycle helmets 18
3.5.2 Information about materials in bicycle helmets 19
3.6 Results of the information collection 20
3.7 Analysis of information 36
3.7.1 Prices of bicycle helmets 36
3.7.2 Materials 36
3.7.3 Producers and brands 38
3.7.4 Materials in contact with the skin 39
4. Selection of products for analysis 43
4.1 Purchase of products for analysis 43
4.2 Use of the app ”Check the Chemistry” 44
5. Screening analyses 45
5.1 Analysis methods 45
5.1.1 SEM-EDS 45
5.1.2 Determination of fluorine 45
5.2 Analysis results 45
5.2.1 Analysis results – determination of elements (SEM-EDS) 46
5.2.2 Analysis results – Determination of fluorine 49
5.2.3 Discussion of analysis results 49
6. Quantitative analyses 51
6.1 Analysis methods 51
6.1.1 Quantitative analysis of chlorinated phosphorus-based flame retardants 51
6.1.2 Quantitative analysis of PFASs 51
6.2 Results of the quantitative analyses 52
6.2.1 Analysis results for chlorinated phosphorus-based flame retardants 52
6.2.2 Analysis results for PFASs 53
6.2.3 Summary of analysis results 57
7. Migration analyses 58
7.1 Migration conditions 58
7.2 Analysis methods 58
7.2.1 Migration analysis for chlorinated phosphorus-based flame retardants 58
7.2.2 Migration analysis of PFASs 59
7.3 Results of the migration analyses 59
7.3.1 Analysis results for chlorinated phosphorus-based flame retardants 60
7.3.2 Analysis results for PFASs 61
7.3.3 Summary of results for the migration analyses 61
8. Hazard assessment 62
9. Exposure calculations 66
9.1 Method for calculation of dermal exposure 66
9.2 Method for calculation of oral exposure 67
9.3 Used exposure values 68
9.4 Exposure calculations 69
10. Risk assessment 71
10.1 Method for calculation of the risk 71
10.2 Risk assessment 72
10.3 Conclusion 73
11. References 75
Preface
This project describes which materials bicycle helmets for young children are made of and
which chemical substances that can be found in bicycle helmets for children. An information
collection was made and based on this, selected bicycle helmets for children were analysed
for selected chemical substances. The results of the information collection and the chemical
analyses are presented in this report.
This project was carried out in the period March 2017 to December 2017.
The project is conducted by FORCE Technology with subcontractors for some of the analyses.
Eurofins have made a quantitative analysis of foam material for content of chlorinated phos-
phorus-based flame retardants as well as a quantitative analysis of bicycle straps for content
of different perfluoroalkyl and polyfluoroalkyl substances (PFASs). Furthermore, Eurofins have
also made migration analysis for the same groups of substances.
The participants of the project were:
Pia Brunn Poulsen, FORCE Technology (project manager)
Charlotte Merlin, FORCE Technology
Anders Schmidt, FORCE Technology (quality assurance)
The project was followed by a working group consisting of Jesper Gruvmark, Bettina Ørsnes
Larsen and Shima Dobel from the Chemical Division, Danish EPA as well as Pia Brunn
Poulsen, FORCE Technology.
The project was financed by the Danish Environmental Protection Agency
Summary and conclusions
Today, most children wear bicycle helmet, also the quite young children. Parts of the bicycle
helmet have direct skin contact at the forehead, at the ears and the strap has direct skin con-
tact on the cheeks and under the chin. It might also be expected that the youngest children put
some parts of the bicycle helmet into the mouth, for instance the strap and the closing mecha-
nism.
The purpose of the project
The purpose of this project has been to investigate which materials that bicycle helmets typi-
cally consist of and if there are any problematic substances in the parts of the bicycle helmets
which have direct contact with the skin or in the parts which the youngest children can be
expected to put into the mouth. Furthermore, the purpose of the project has been to examine
whether the content of the possibly problematic chemical substances in bicycle helmets can
be hazardous to children’s health .
The scope of the project
The project is limited to focus on bicycle helmets for young children, i.e. primarily children at
the age under 3 years. Focus has been on bicycle helmets intended to a cranial circumference
of between 42 and 52 cm corresponding to the cranial circumference of children up to 3 years.
Neither ski helmets nor bicycle airbag/inflatable bicycle helmets have been included in this
report.
Survey
In the first phase of the project, information about bicycle helmets for children was collected.
The following methods were used:
Contact to the trade, for instance trade association and selected suppliers of bicycle helmets
Internet search
Shop visits
Use of the app “Check the chemistry” made by the Danish Consumer Council and the Dan-
ish EPA
Literature search, for instance the Danish EPA’s previous projects regarding chemicals in
consumer products as well as foreign tests of bicycle helmets for children
The survey showed that a lot of different bicycle helmets for children are available on the mar-
ket. In total 39 different brands/producers of bicycle helmets were identified. Each of these
produces different types of bicycle helmets in different colours and printed patterns. The differ-
ent types of bicycle helmets can be the more common bicycle helmets with vent holes (‘racer
helmets’), skater helmets (a more closed helmet with a few vent holes) and more special bicy-
cle helmets designed as for instance animal heads.
The price of the analysed bicycle helmets for children in this project varies between 89.90 DKK
and 769 DKK. The bicycle helmets are mainly produced in China but a few European brands
have their own production in Europe (Germany or Italy).
The survey shows that bicycle helmets consist of the following parts which are mainly pro-
duced in the following materials:
Outer shell in PC (polycarbonate). However, they are also produced in ABS (acrylonitrile
butadiene styrene), and in a few cases in PVC (polyvinyl chloride), PS (polystyrene) or EPS
(expanded polystyrene).
Inner shell in EPS (expanded polystyrene).
Pads/padding and possibly chin pad in PU (polyurethane) foam either with a thin textile layer
or entirely encircled by textile (a pocket of textile) most likely of PES (polyester). The pads in
the helmet might be glued on or be fastened with Velcro. In the latter case, there are several
small pads (pockets of textile with foam filling).
Possibly a hard plastic strap inside (of unknown material) making the helmet adjustable to
the size of the head.
Strap of nylon, PES (polyester) or PP (polypropylene)
Chin buckle of hard plastic (of unknown material or POM (polyoxymethylene)).
Parts in contact with the skin when the bicycle helmet is worn
When a bicycle helmet is worn correctly the child is not in direct skin contact with either outer
shell or inner shell. They are only in direct skin contact with:
The pads inside in the helmet – i.e. there is a direct contact with the textile on or around the
foam. Direct skin contact is primarily on the forehead – at other places the child’s hair will be
in between.
The bicycle strap at the ears, cheeks and under the chin where a direct skin contact will
occur at several places on the strap.
The chin buckle where direct skin contact will occur with the plastic buckle or possibly the
padding around the buckle (which is typically made of the same material as the padding in-
side the helmet).
Content of potentially problematic chemical substances in bicycle helmets
Use of the app “Check the chemistry” made by the Danish Consumer Council and the Danish
EPA showed that none of the six bicycle helmets where the app was used contained sub-
stances from the candidate list in a concentration above 0.1%. In 7 other cases, where the app
was used, no reply was received.
According to previous consumer tests of bicycle helmets from 2010, 2012 and 2013,
phthalates have been found in small amounts in the padding as well as organic tin compounds
and PAHs (polyaromatic hydrocarbons). PAHs are today restricted via REACH for plastic
products in contact with the skin, and organic tin compounds are today restricted via REACH
in all kinds of articles. Previous surveys have identified phthalates in small amounts – howev-
er, small amounts are more an indication of impurities than a deliberate use. It was therefore
decided that the focus had to be on other problematic substances for the analyses. It was
decided to focus on a possible use of flame retardants in the foam material and a possible use
of perfluoroalkyl and polyfluoroalkyl substances (PFASs) in the bicycle strap. For examination
of a content of possibly other problematic substances, an element analysis/screening analysis
was performed on both the bicycle strap and the foam material.
Screening analyses of 16 bicycle helmets for young children
In total 16 different bicycle helmets for young children in different brands and in different price
ranges (from 90 DKK to 599 DKK) were purchased. Most of these were (‘racer’) bicycle hel-
mets (10 pcs.), 5 pcs. were skater helmets and one bicycle helmet was designed as an animal
head. The vast majority of the purchased bicycle helmets were produced in China (11 pcs.), 3
pcs. were produced in the EU and for the remaining 2 pcs., the country of origin was unknown.
The following screening analyses of the 16 bicycle helmets were performed:
Element determination (SEM-EDS) on the foam material in the helmet
Element determination (SEM-EDS) on the bicycle strap
Fluorine determination on the bicycle strap
Among interesting results, the screening analyses showed a small content of both chlorine and
phosphorus in a single bicycle helmet (C10). Bromine above the detection limit of 1000 ppm
was not identified. A content of fluorine just above the detection limit of 5 ppm was identified in
C6 and C10 as well as a high fluorine content of 92 ppm in C4.
Quantitative analyses
Quantitative analyses of certain chlorinated phosphorus-based flame retardants in the pad
material in C10 were performed as well as of certain perfluoroalkyl and polyfluoroalkyl sub-
stances (PFASs) in bicycle straps on C4, C6 and C10. The results showed that in the pad
material in C10, the flame retardants TCPP and TDCP were identified in large amounts
(19,550 ppm (2%) and 7,170 ppm (0.7%) respectively) and that TIBP, TCEP and TPHP were
identified in small amounts (approx. 2 ppm (0.0002%), 1 ppm (0.0001%) and 60 ppm (0.006%)
respectively). A few PFASs were identified in the strap in C4 in small amounts (maximum
0.012 ppm) but no PFASs above the detection limit were identified in the straps from C6 and
C10.
Migration analyses
Due to identification of chlorinated phosphorus-based flame retardants in the pad material in
C10 and PFASs in the strap on C4, a migration analysis to water was subsequently performed
for both the pad material in C10 and the strap on C4.
The results of the migration analyses on the pads inside the bicycle helmet showed that the
same chlorinated phosphorus-based flame retardants were identified in the migration liquid as
identified at the content analysis carried out on C10. TCPP and TDCP were identified in the
largest amounts in the migration liquid, 440 ppm (0.044%) and 10 ppm (0.001%) respectively,
for migration for 1 hour. TIBP, TCEP and TPHP were identified in small amounts in the migra-
tion liquid (approx. 0.025 ppm, 0.0140 and 0.014 ppm respectively) for 1 hour of migration).
The results of the migration analyses on the bicycle strap on C4 showed that no PFASs mi-
grates above the detection limit of between 0.3 and 0.7 µg/kg/hour of bicycle strap dependent
on the individual PFAS.
Risk assessment
Based on the results of the migration analyses, exposure calculations and a subsequent risk
assessment of the following exposure scenarios were performed:
Skin contact with the pads inside C10 for 1 hour every day.
Skin contact with bicycle straps on C4 for 1 hour every day.
Oral exposure (if the child sucks the strap) for the bicycle strap on C4 for 10 minutes every
day. Here a shorter exposure time was applied as the part of the strap where the PFASs
were identified cannot be put into the mouth during normal use of the bicycle helmet. The
strap is only situated around the ears.
It must be noted that for the last two exposure scenarios for C4, the detection limit of the
PFASs is applied as no migration of the PFASs above the detection limit was identified. The
conclusion of the risk assessment of PFAS illustrates that there is no health risk when a child
wears the bicycle helmet C4 or when a child sucks the strap of C4 each day for a long period.
The total RCR-value for both dermal and oral exposure for all PFASs is well below 1 for the
chemical substances investigated in this report.
The conclusion of the risk assessment is from an isolated point of view that even if flame re-
tardants are identified inside in the pads in a single bicycle helmet (out of 16) and that these
problematic substances migrate from the bicycle helmet (C10) and thus can be absorbed
through the skin of the young children who wear these bicycle helmets, the amounts in ques-
tion do not constitute a health risk of liver damages which is the critical effect of the flame
retardant TCPP (which has the most significant risk in the risk assessment). The flame retard-
ants do neither constitute a health risk, when the amount of the individual flame retardants with
the same effects is added. However, even if the calculated RCR values are below 1 for the
bicycle helmet C10 which is examined in this project, the values contribute to the total expo-
sure of these flame retardants in different children’s products which children use on a daily
basis.
Looking only at the bicycle helmets, none of the investigated helmets constitutes a health
problem with regard to the chemical substances investigated in this report. Moreover, it should
be emphasised that it was only in two bicycle helmets out of 16 analysed helmets where either
flame retardants were identified in the pads or where PFASs were identified in the strap. Most
of the examined bicycle helmets investigated in this project do not contain neither the investi-
gated chlorine phosphorus-based flame retardants nor PFASs.
1. Introduction
Today, most children use bicycle helmets and according to “the Danish Council for Traffic
Safety” and the Danish foundation TrygFonden, in total 89% of the 6 to 9 age group used
bicycle helmets on their way to school in 2015. The tendency has been increasing from 52% in
2004 to the 89% in 2015 (The Danish Council for Traffic Safety).
Parts of the bicycle helmet have direct skin contact with for instance the forehead and espe-
cially the strap under the chin. It can also be expected that young children put some parts of
the bicycle helmet into the mouth, for instance the straps and the closing mechanism. With this
project, the Danish Environmental Protection Agency wishes to obtain knowledge about sub-
stances in those parts of the bicycle helmets which have direct contact with the skin or parts
which children can be expected to put into the mouth.
1.1 Purpose
The project aims to provide an overview of which materials bike helmets typically consist of
and whether problematic substances are present in the parts of the bicycle helmets which
have direct contact with skin or the parts which children can be expected to put into the mouth.
Furthermore, the project aims to examine whether the content of the possibly problematic
chemical substances in bicycle helmets can be harmful to health for children.
In this project, focus will be on the youngest children who use bicycle helmets, i.e. from the
time when children start sitting in the child’s seat on the bicycle as this group is regarded to be
the most sensitive to chemical substances. This is partly due to the lower weight of this age
group compared to the size of the body and thus a higher total exposure, and partly the fact
that the body is still under development. At the same time, these young children are the group
of children who have the largest tendency to put parts of the bicycle helmet into the mouth.
1.2 Delimitation
The project is delimited to focus on bicycle helmets for young children, i.e. primarily children at
the age under 3 years.
According to WHO, girls in the 1 to 3 age group have cranial circumference between 42 and
51 cm and boys between 43 and 52 cm (WHO). On their home page with bicycle helmets for
children, eCykelhjelm.dk writes that suggested sizes of bicycle helmets for children under 1
year are up to 48 cm, that the size for children between 1 and 2 years is 50 cm, and that the
size for children between 2 and 5 years is 52 cm (eCykelhjelm.dk, 2016). This means that it is
primarily bicycle helmets intended for a cranial circumference of between 42 and 52 cm which
are included in this survey.
The project is exclusively limited to focus on bicycle helmets. Ski helmets which some use as
bicycle helmets (for instance in the winter period) are not included in the project. Neither the
new type of bicycle helmet called bicycle airbag, inflatable bicycle helmet nor invisible bicycle
helmet is included in this survey. This type of bicycle helmet is in-stead worn as a collar which
is only released/inflated in case of an accident. This new type of bicycle helmet has become
incredibly popular in Sweden but according to the producer, it is only approved for children
from 15 years and upwards as it is designed for adult movement pattern
1
.
1
http://cykelairbag.dk/; http://ecykelhjelm.dk/hovding-usynlig-cykelhjelm-airbag.html;
http://www.hovding.com/faq?_ga=2.231964959.1485808113.1494403325-1433767112.1494403325;
2. Standards and legislation
In this chapter, a short description states the standards and legislation in which bicycle hel-
mets are included.
2.1 Standards
For bicycle helmets, the following standards apply:
DS/EN 1078 + A1:2012 ”Helmets for pedal cyclists and for users of skateboards and roller
skates”
DS/EN 1080:2013 ”Impact protection helmets for young children”
The common fact for them is that none of them deals with requirements to chemical substanc-
es but exclusively safety requirements. Therefore, the standards are not mentioned further in
this survey.
2.2 Legislation regarding content of chemical substances
For bicycle helmets, the following legislation applies regarding content of chemical substanc-
es:
Produktsikkerhedsloven (the Danish Product Safety Act based on EU Product Safety Di-
rective)
REACH Annex XVII: Restrictions on the manufacture, placing on the market and use of
certain dangerous substances, mixtures and articles (different specific chemicals)
Danish legislation regarding heavy metals in products (Pb, Cd and Hg)
The POP Regulation (PFOS-like substances)
REACH is an EU regulation which regulates chemical substances in compounds and articles,
for instance through requirements on registration and approval. An EU regulation is directly
valid in Denmark. Annex XVII of the REACH regulation is a list of restrictions for the content of
chemical substances in different chemical mixtures, materials and products. Similarly, the POP
regulation is European legislation which has implemented the Stockholm convention on persis-
tent organic pollutants (POP). The Product Safety Act is a European directive regarding the
safety of consumer products in general. The Product Safety Act is implemented in Denmark
through “Act on product safety” (Produktsikkerhedsloven). Finally, separate Danish legislation
regarding heavy metals in consumer products exists.
Phthalates are not restricted in bicycle helmets as bicycle helmets are not considered as nei-
ther toy nor articles for toddlers.
Below, the legislation is described shortly including the chemical substances which are re-
stricted. Chemical substances which are restricted in bicycle helmets are summarised in Table
1.
2.2.1 The Product Safety Act
According to Act no. 1262 of 16.12.2009 the “product safety act”, producers are only allowed
to sell products on the market if these are safe for the consumer. When assessing whether a
product is safe, the composition of the product, including its chemical composition, is taken
into consideration and whether the product is used under normal or reasonably foreseeable
conditions of use (Act no. 1262, 2009).
There is no clear requirement concerning chemical substances in consumer products in the
product safety act but with legal basis in the product safety act, the products can be withdrawn
from the market if a risk assessment shows that a possible content of a hazardous substance
might constitute a health risk for the consumers.
2.2.2 REACH Annex XVII restrictions
The following restrictions in the REACH regulation No. 1907/2006 are relevant for bicycle
helmets:
TRIS (No. 4) – is not allowed to be used in textiles intended to come into contact with skin
TEPA (No. 7) – is not allowed to be used in textiles intended to come into contact with skin
Polybrominated biphenyls (PBB) (No. 8) – are not allowed to be used in textiles
Organic tin compounds (No. 20) – are not allowed to be used in articles
Cadmium (No. 23) – is not allowed to be used in plastic materials
Nickel (No. 27) – for buckles of metal, if any, in direct and prolonged contact with the skin
Azo colourants (No. 43) – limited in textiles in contact direct and prolonged contact with skin
Octabromo diphenylether (No. 45) – is not allowed to be used in articles
Nonylphenol ethoxylates (No. 46a) – are not allowed to be used in textiles which reasonably
can be expected to be washed in water (however, not until 3 February 2021)
PAH (No. 50) – limited in plastic and rubber parts which come into direct as well as pro-
longed or short-term repetitive contact with skin or oral cavity
DMFu (No. 61) – is not allowed to be used in articles
Lead (No. 63) – is not allowed to be used in articles which can be placed in the mouth by
children
Decabromo diphenylether (No. 67) – is not allowed to be used in articles (however, from 2
March 2019)
2.2.3 Danish legislation regarding heavy metals
The following Danish legislation regarding heavy metals is relevant for bicycle helmets.
Statutory order No. 856 of 5.9.2009 regarding ban on import and sale of products containing
lead – applies to articles containing chemical lead (with certain exemptions), and is not valid
for products regulated through other legislation
Statutory order No. 858 of 5.9.2009 regarding ban on import, sale and production of cadmi-
um-containing goods – applies to the use of cadmium as colour pigment, plastic inhibitor or
surface treatment
Statutory order No. 73 of 25.1.2016 regarding ban on import, sale and export of mercury-
containing products – applies for all articles
2.2.4 The POP regulation
The POP regulation No. 850/2004 sets the following restrictions which are relevant for bicycle
helmets:
Tetrabromo diphenylether – is not allowed in articles
Pentabromo diphenylether – is not allowed in articles
Hexabromo diphenylether – is not allowed in articles
Heptabromo diphenylether – is not allowed in articles
PFOS and PFOS derivates – are not allowed in articles
Hexabromo cyclododecane – is not allowed in articles (however, only valid from March
2016) and there is an excep-tion for use in EPS (expanded polystyrene) until 26 November
2019
It should be noted that it is exclusively PFOS and PFOS-like substances which are limited
through the POP regulation and not the alternative polyfluoroalkyl substances e.g. with shorter
chain length.
2.2.5 Overall overview of legislation regarding chemical substances
Table 1 below shows an overall overview of which chemical substances that are limited in
bicycle helmets through legislation.
Table 1: Overview of legislation regarding content of chemical substances in bicycle
helmets
Name of sub-
stance/ group of
substance
CAS no
Legislation
Applies for
Limit value
Heavy metals
Cadmium
7440-43-9
REACH Annex
XVII, No. 23
Certain types of
plastic
100 ppm
DK-BEK 858, 2009
Plastic which is not
included in REACH
and as colour in-
hibitor
75 ppm
Nickel
7440-02-0
REACH Annex
XVII, No. 27
In articles intended
for prolong contact
with the skin
0.2 µg/cm
2
/week
(migration)
Lead
7439-92-1
REACH Annex
XVII, No. 63
In articles which
can be placed in
the mouth (< 5 cm)
500 ppm
DK-BEK 856, 2009
All articles
100 ppm
Mercury
7439-97-6
DK-BEK 73, 2016
All articles
100 ppm
Impregnation agents
TRIS (Triphos-
phate (2,3-
dibromopropyl))
126-72-7
REACH Annex
XVII, No. 4
Textiles intended
for contact with the
skin
Not stated
TEPA
(Tris(aziridinyl)pho
sphinoxide)
545-55-1
REACH Annex
XVII, No. 7
Textiles intended
for contact with the
skin
Not stated
PFOS and deri-
vates
-
POP
All articles
1000 ppm
(textiles 1 µg/m
2
)
Flame retardants
PBB (Polybromin-
ated biphenyles)
-
REACH Annex
XVII, No. 8
Textiles intended
for contact with the
skin
Not stated
BDE’s (polybrominated biphenylethers)
tetraBDE
POP
All articles
10 ppm
pentaBDE
POP
All articles
10 ppm
hexaBDE
POP
All articles
10 ppm
heptaBDE
POP
All articles
10 ppm
octaBDE
REACH Annex
XVII, No. 45
All articles
1000 ppm
decaBDE
REACH Annex
XVII, No. 67
All articles, howev-
er, not until 2
March 2019
1000 ppm
HBCDD (Hexa-
bromcyclododec-
an)
25637-99-4 et al..
POP
All articles
100 ppm
Organic tin compounds
TBT and TPT
REACH Annex
XVII, No. 20
All articles
1000 ppm
DBT
REACH Annex
XVII, No. 20
Articles for private
use
1000 ppm
DOT
REACH Annex
XVII, No. 20
Textiles intended
for contact with the
skin
1000 ppm
Biocides
DMFu (dime-
thylfumerat)
REACH Annex
XVII, No. 61
All articles
0.1 ppm
Colourants
Azo colourants
-
REACH Annex
XVII, No. 43
Textiles and leath-
er intended for
contact with the
skin
30 ppm (release of
of carcinogenic,
aromatic amines)
Other substances
PAHs (polycyclic
aromatic hydrocar-
bons)
8 different sub-
stances
REACH Annex
XVII, No. 50
Rubber and plastic
parts in contact
with the skin
1 ppm
Nonylphenol eth-
oxylates (NPE)*
-
REACH Annex
XVII, No. 46a
Textiles which are
expected to be
washed in water,
however, not until
3 February 2021
100 ppm
* Legislation regarding NPE only applies for textiles which ”can reasonably be expected to be washed in
water during their normal lifecycle”. Whether the future legislation will be applicable for bicycle helmets will
depend on the design of the bicycle helmets as some bicycle helmets have detachable inside pads
(mounted with Velcro) which might be taken off and washed. In other bicycle helmets, however, the pads
are firmly fixed and thus cannot be expected to be washed.
3. Collection of information
In the first phase of this project, information on bicycle helmets for young children was collect-
ed. The following methods were used for the collection:
Contact to the trade, for instance trade association and selected suppliers of bicycle helmets
Internet search
Shop visits
Use of the Danish Consumer Council’s and the Danish Environmental Protection Agency’s
app “Check the Chemistry”
Literature search, for instance previous consumer projects from the Danish EPA and foreign
tests of bicycle helmets for children
Initially, contact to the trade association and selected suppliers of bicycle helmets on the Dan-
ish market. The purpose was partly to get information about materials used in bicycle helmets,
partly to get information about where bicycle helmets are produced as well as which brands of
bicycle helmets for children that are available on the Danish market.
This information was supplemented with an internet search for bicycle helmets for children as
well as shop visits in a few bicycle shops and large supermarkets. At the shop visits, the Dan-
ish Consumer Council’s and the Danish EPA’s app “Check the Chemistry” was used, when
possible.
Finally, a literature search for previous studies of bicycle helmets for children was made.
3.1 Contact to the trade
3.1.1 Contact to the trade association “Danish Bicycle Dealers”
The trade association “Danish Bicycle Dealers”
2
was contacted. The “Danish Bicycle Dealers”
is a trade association which according to their home page has approx. 400 bicycle and moped
shops as members, including dealers of bicycle helmets.
The trade association was asked about the materials of the bicycle helmets but they referred
to the Danish suppliers of bicycle helmets who are members in their association, i.e.:
ABUS (German company with sales office in Denmark)
Bjarne Egedesø (dealer of the American brands GIRO and BELL)
AGU (Dutch company with sales office in Denmark)
3.1.2 Contact to suppliers of bicycle helmets
Subsequently, contact was taken to selected suppliers of bicycle helmets on the Danish mar-
ket to get further information about which materials the bicycle helmets are made of and about
the suppliers/dealers of bicycle helmets and brands of bicycle helmets who are available on
the Danish market. The following suppliers/dealers were contacted:
ABUS-Gruppen Nordic A/S
Bjarne Egedesø A/S
AGU Denmark
C. Reinhardt as
COOP
2
http://www.danskecykelhandlere.dk/
Dansk Supermarked (Danish Supermarket)
Among other things, the suppliers/dealers were asked which suppliers/dealers of bicycle hel-
mets are available on the Danish market and besides the above suppliers/dealers, the con-
tacted suppliers/dealers informed that the following dealers might be relevant to include in the
collection of information:
thansen
Silvan
Harald Nyborg
Biltema
The contacted suppliers/dealers were generally asked about suppliers/dealers who might be
relevant to contact as well as which brands that are the most dominant on the Danish market.
The below brands were mentioned by the suppliers/dealers (or it could be found on their home
pages). However, it ought to be mentioned that some brands do not necessarily produce bicy-
cle helmets for children but for juniors and/or adults.
GIRO
BELL
Lazer
MET
Limar
ABUS
Crazy Safety
CSI
Puky
Bluegrass (but the size seems only to be size 51-55 cm and above
The general information from the contacted suppliers/dealers was that the main part of the
bicycle helmets is produced in the East where China is mentioned as a specific production
place by several suppliers/dealers. Only a few brands are produced in Europe (Germany is
mentioned as a specific production place).
Generally, there was not much knowledge about the materials in the bicycle helmets at the
contacted suppliers/dealers as in many cases they are only sales offices in Denmark. Howev-
er, in some cases, the inquiry was forwarded to the main company abroad. Of the returned
answers (the number is stated in brackets) regarding materials in bicycle helmets, it is seen
that bicycle helmets consist of:
Outer shell of PC (polycarbonate) (2)
Inner shell/’skeleton’ of EPS (expanded polystyrene) (2)
Pads/foam of PES textile (polyester) outside and PU (polyurethane) foam (1) or unknown
material (1) – a supplier states that pad material in the chin and inside is of the same mate-
rial.
Buckle of plastic with no further specification (1) or of the plastic type POM (1) which is a
thermoplastic consisting of polyoxymethylene
Strap of textile - nylon (1) or PES textile (polyester) (1)
From the answers (number stated in brackets) from the contacted suppliers/producers, it could
furthermore be concluded that their bicycle helmets neither contain phthalates (3), fluorinated
substances (2) nor other substances from the REACH candidate list (2) in concentrations
above 0.1% which is the limit that applies for the obligation to provide information regarding
candidate list substances in REACH.
3.2 Internet search
An internet search for bicycle helmets for children below 3 years (i.e. up to size 52 cm) was
conducted. The search was for various brands and producers of bicycle helmets as well as
various types of bicycle helmets, for instance skater bicycle helmets, common bicycle helmets
and bicycle helmets with LED light at the back. The search was used to find examples of bicy-
cle helmets which were to be purchased for analyses in phase 2 of the project. Examples of
different bicycle helmets are listed in Table 2. At the internet search, information regarding
possible materials in the bicycle helmet was noted. This information is also stated in Fejl!
Henvisningskilde ikke fundet. and summarised in Table 3. A total overview of the identified
brands of bicycle helmets is listed in Table 4.
Furthermore, an internet search for information regarding choice of material on the home pag-
es of selected bicycle helmet producers was conducted. This search showed
3
that four hel-
mets are produced with pads/padding of EPS foam (expanded polystyrene). Regarding the
outer shell, one helmet in PS (polystyrene), two in ABS (acrylonitrile-butadiene-styrene), one
in PVC (polyvinylchloride) were identified. Additionally, one inner shell in EPS (expanded poly-
styrene) was identified.
During the searches for bicycle helmets on the internet, the term “in-mold technique” was
observed. This technique means that the outer and inner part of the bicycle helmets (outer
shell and the core) are moulded together which makes the shell solid and thus the helmet
stronger and lighter
4
. However, this has no influence on the choice of materials. This “in-mold
technique” can be used to mould different materials together.
During the internet search, a so-called ”environmental” bicycle helmet was identified
5
in one
single case. The “environmental” issue is that the inner shell is produced of reused EPS foam
(expanded polystyrene) and an outer shell in ABS (acrylonitrile-butadiene-styrene) combined
with PLA (PolyLactic Acid). PLA is a bioplastic, i.e. it is produced of starch from crops like for
instance corn.
3.3 Visits in shops
The selection of bicycle helmets in seven different shops was studied. Three of these were
special bicycle shops or shops which exclusively sell bicycle helmets. The remaining shops
were supermarkets, DIY centres or shops with auto accessories/bicycles.
The purpose of the shop visits was to supplement the information from the internet search and
to get a feeling of the shop personnel’s knowledge about the materials in the bicycle helmets.
Furthermore, the inner side of the helmets was examined to see which materials that are in
contact with the skin when the helmet is worn.
The general picture of the shop visits was that there is no knowledge about the materials in the
bicycle helmets, no knowledge about ingredients (candidate list substances) and no
knowledge about where the bicycle helmets are produced. The shops referred to the suppliers
3
Links: https://nutcasehelmets.com/collections/baby-nutty/products/petal-power?variant=1265688652,
(https://nutcasehelmets.com/collections/youth/products/black-zone?variant=25582449477,
http://www.crazy-safety.com/index.asp?secid=333, http://www.urbanwinner.dk/om-vores-cykelhjelm,
https://www.silvan.dk/rawlink-cykelhjelm-sort-m-54-58-cm?id=7400-1732201,
https://www.cykelhjelm.com/shop/melon-cykelhjelm-156c1.html
4
http://www.harald-nyborg.dk/p12176/boernehjelm-groen-s;
http://www.aldi.dk/aldi_skater_cykelhjelm_til_born_48_5_5128_25864.html
5
https://www.webike.dk/cykeltoej/cykelhjelm/kali-saha-mat-bl-cykelhjelm.html
for more information. Some bicycle helmets had the country of production printed on the hel-
met or the information was enclosed in the helmets. In all these cases (for approx. five helmets
with this information), the production had taken place in China. However, in one of the bicycle
shops, the message was that generally all bicycle helmets are produced in China and that they
only had knowledge of a German brand which is produced in Germany.
3.4 Use of the app ”Check the Chemistry”
The Danish Consumer Council and the Danish Environmental Protection Agency have devel-
oped an app “Check the Chemistry” (“Tjek Kemien”) which has the purpose to send an inquiry
about candidate list substances (referring to article 33 in the REACH regulation) in consumer
products to the dealer/producer. The function of the app is that the bar code on the product is
scanned and in this way a standard email is sent to the dealer/producer.
As far as possible, this app was used on bicycle helmets identified at the shop visits. However,
it turned out that in many cases it was not possible to use the app. Among other things, this is
because some of the bar codes were not recognised in the app. Furthermore, the bicycle hel-
mets were often shown without the packaging (where the bar code was situated) which in
some cases made it impossible to use the app at the shop visits.
At the shop visits, in total four inquiries were made via the “Check the Chemistry” app. Infor-
mation from the producer/supplier via the “Check the Chemistry” app was received in all four
cases. For all the four inquiries, the answer was that the bicycle helmet does not contain any
substances from the candidate list in a concentration above 0.1%. In the only case where
documentation was attached, it appeared that the test was made in February 2015. Thus, the
documentation does not contain information about substances on the candidate list for the last
two years.
3.5 Literature search
A literature search was made for tests or reports which describe materials or content of chemi-
cal substances in bicycle helmets.
3.5.1 Consumer test of bicycle helmets
Several consumer organisations and other institutions have tested bicycle helmets in relation
to different parameters such as safety, comfort etc. There are identified three test programmes
where the content of harmful substances was one of the test parameters. The test pro-
grammes and results are described below.
ADAC, the German sister club of FDM (the Motor Touring Club of Denmark), has carried out
tests on bicycle helmets in 2010, 2013 and again in 2016 in co-operation with Stiftung
Warentest. On a general level, the test in 2016 (ADAC, 2016) included 6 categories, including
the content of harmful substances which was weighted with 5%. The included substances
were PAH (polyaromatic hydrocarbons) and a number of non-specified plasticisers. Of the 19
tested bicycle helmets, 3 bicycle helmets got the worst grade “insufficient” in the category
harmful substances, 1 helmet got the grade “sufficient”, 1 got the grade “satisfactory”, 5 got the
grade “good”, and the remaining 10 helmets got the grade “very good”. It has not been possi-
ble to identify the detailed criteria for the marking and the specific concentrations of the ingre-
dients but it seems primarily to be the content of PAH (polyaromatic hydrocarbons) which has
contributed to the bad grades in relation to harmful ingredients.
In 2012, the Danish Consumer Council magazine ”Tænk” tested 18 bicycle helmets against 12
overall test categories, including the category “harmful chemicals” which was weighted with
5%. Within the category “harmful chemicals”, the test examined selected parts of the helmets
such as padding, chin straps and buckles for content of a number of harmful chemicals such
as phthalates, PAHs (polyaromatic hydrocarbons), organic tin compounds, azo colourants and
the flame retardant TCEP. 16 of the tested bicycle helmets got the best grade “very good”, and
the two remaining helmets got the grade “medium” and the grade “bad” respectively.
The specific occurrences of harmful chemicals are not published in the “Tænk” magazine but
in the helmet with the worst grade, phthalates were found in the padding of the chin strap in
amounts which exceed the limit values for toys, i.e. above 0.1% (Tænk, 2012).
As a part of an overall test programme with several parameters, the German OEKO TEST
(2013), which tests various consumer products, has in 2013 also tested 13 helmets for the
following selected problematic ingredients:
Aromatic amines (azo colourants which may release carcinogenic aromatic amines)
Aniline
Xylidine
Dispersion colourants
Optical brighteners
Halogenated flame retardants in printed circuit boards (for helmets with LED light)
Organic phosphorus compounds
Phthalates
Other plasticisers
Phenol compounds (in solution sample of pads and chin strap – attachment pieces made of
plastic)
The test of the 13 helmets showed that 3 of 13 helmets contained problematic substances in
the form of phthalates (2 helmets) and organic phosphorus compounds. The phthalates
(DEHP and DINP) were identified in levels of > 10,000 ppm and > 1,000 ppm respectively in
the inner pads in the two helmets. Furthermore, other plasticisers (DEHT) were identified in
two helmets.
In 2014, the German OEKO TEST (2014) describes in an article about bicycle helmets that the
protecting pads are made of PU foam (polyurethane). However, no test for content of chemical
substances is made in this OEKO test.
3.5.2 Information about materials in bicycle helmets
A few home pages were identified describing which materials bicycle helmets are made of. A
description of these home pages is presented below.
The home page Design Life-Cycle
6
is an American home page where students after having
studied a specific product have described the life cycle for the product in question. However,
their knowledge is primarily based on the home page Helmets.org which is described below.
According to this home page, American bicycle helmets consist of the following materials:
Outer shell of PET plastic (polyethylene terephthalate)
Inner shell of EPS foam (expanded polystyrene)
Straps of nylon or PP (polypropylene)
Pads can be made of EPU (expanded polyurethane), EPP (expanded polypropylene), E-
PLA (expanded polylactic acid) or “cellufoam” which is a porous material with low density
made of nanocellulose
7
)
The American home page Helmets.org
8
is a non-profit consumer-supported organisation which
gives information about helmets in general. According to their description of bicycle helmets,
6
http://www.designlife-cycle.com/bicycle-helmets/
7
http://www.cellutech.se/cellufoam.html
the below materials are generally used (on the American market). The home page also de-
scribes that more than the half of the bicycle helmets which are produced worldwide are pro-
duced in China or other Asiatic countries. But some helmets are still assembled in the USA
and in Europe.
Outer shell of PET (polyethylene terephthalate) or similar types of plastic but PC (polycar-
bonate) or ABS (acrylonitrile-butadiene-styrene) is typically used in somewhat more expen-
sive helmets.
Inner shell is typically made in EPS foam (expanded polystyrene) but in some helmets, the
use of EPP (expanded polypropylene) or EPU (expanded polyurethane) has started instead.
Straps are normally made of either nylon or PP (polypropylene).
The buckle is normally of plastic (the type is not specified).
Protective pads are normally used inside in the helmets but it is not stated which material
they are made of. However, it is stated that use of antibacterial pads seems to gain ground
on the expensive models of bicycle helmets. According to Helmets.org, it is primarily
(nano)silver that is used but other chemical substances are also used.
In a case regarding use of their CES Selector tool (a tool for the use of materials selection),
the American company Granta Design has described
9
that for bicycle helmets it is exclusively
EPS (expanded polystyrene), cork or balsa wood which can be used and give satisfactorily
shock-absorbing properties. It is probably the reason why EPS is the most used material for
the inner shell in bicycle helmets as it is the cheapest material and has satisfactorily shock-
absorbing properties.
3.6 Results of the information collection
The result of the collection of the information about bicycle helmets for young children below 3
years are given in Table 2. In total, approx. 65 different examples of bicycle helmets for chil-
dren of various brands are given. This list is used as basis for the selection of bicycle helmets
for the analyses in phase 2 and covers bicycle helmets identified at shop visits and via the
internet search.
For most of the brands, a few different examples of bicycle helmets have been inserted as the
bicycle helmets are partly in different price ranges and partly in different shapes (for instances
skater helmet, designer helmets (for in-stance helmets shaped like animals) and the more
common bicycle helmets (racer helmets with holes for ventilation).
A summery and analysis of the information identified through the internet search and the shop
visits are described in section 3.7 “Analysis of information”.
8
http://www.bhsi.org/howmade.htm; http://www.helmets.org/helmet16.htm
9
http://www.grantadesign.com/resources/materials/casestudies/helmet.htm
The Danish Environmental Protection Agency / Survey and risk assessment of chemical substances in bicycle helmets 21
Table 2: Bicycle helmets for young children identified in the project
Product name
Brand
Dealer
Name of producer
Head office of
producer – country*
Price
Appearance
Materials
Pictures
Princess Smiley
Child helmet from
Abus, 45-50 cm
Abus (model Smiley)
Ecykelhjelm.dk
ABUS
Germany
289 DKK
Pink helmet with prin-
cess motif.
Unknown
Nutcase Bumble-
bee Gen3 Chil-
dren, 48-52 cm
Nutcase
Ecykelhjelm.dk
Nutcase
USA
489 DKK
Black and yellow
striped skater helmet.
Unknown
Spiderman Bicy-
cle helmet Crazy
Safety, 46-52 cm
Crazy Safety
Ecykelhjelm.dk
Crazy
Denmark
299 DKK
Black with spiderman
3D figure upon hel-
met.
Shock-padding of
EPS foam (inner
shell), nylon straps
White Snoopy
Scraper Kid v.2
child helmet, 51-
55 cm
Abus
Ecykelhjelm.dk
ABUS
Germany
345 DKK
White skater helmet
with pink Snoopy
motif.
ABS shell
Limar 242 wave
bicycle helmet
children w/light,
46-51 cm
Limar
Ecykelhjelm.dk
Limar
Italy
399 DKK
Blue helmet with
yellow octopus and
red starfishes.
Antibacterial pads.
LED light with flash
function.
Product name
Brand
Dealer
Name of producer
Head office of
producer – country*
Price
Appearance
Materials
Pictures
Giro Scamp Mips,
youth extra small,
45-49 cm
Giro
Pauli Cykler
Giro
USA
549 DKK
Pink helmet with white
”giro” sticker and
orange flowers. White
buckle
Unknown
Cannondale,
approx. 48-51 cm
Cannondale
Pauli Cykler
Cannondale
USA
299 DKK
White helmet with
green and purple
small squares in ran-
dom pattern.
Unknown
Sparkling Blue
Youn-I Junior
helmet from
ABUS, 48-54 cm
ABUS
Ecykelhjelm.dk
ABUS
Germany
389 DKK
Blue helmet with
white ABUS logo,
orange straps. With
red LED light and
reflectors on the back.
Unknown
Maori Purple
MountX Child
helmet from
ABUS, 48-54 cm
ABUS
Ecykelhjelm.dk
ABUS
Germany
449 DKK
Purple and black
helmet with gold pat-
tern.
Unknown
Green tiger bicy-
cle helmet Craxy
Safety, 49-55 cm
Crazy Safety
Ecykelhjelm.dk
Crazy
Denmark
299 DKK
Green, white, yellow
and black bicycle
helmet designed as a
tiger head. LED light
in the buckle at the
back of the neck. With
chin cup of unknown
material.
Soft pads consist of
EPS foam.
The Danish Environmental Protection Agency / Survey and risk assessment of chemical substances in bicycle helmets 23
Product name
Brand
Dealer
Name of producer
Head office of
producer – country*
Price
Appearance
Materials
Pictures
Dull blue GIRO
Scamp child hel-
met, 45-49 cm
GIRO
Ecykelhjelm.dk
GIRO
USA
349 DKK
Blue bicycle helmet
with green GIRO logo.
Unknown
BELL Sidetrack
bicycle helmet for
children, mint, 47-
54 cm
BELL Sidetrack
Ecykelhjelm.dk
BELL
USA
399 DKK
Mint coloured bicycle
helmet with yel-
low/mint flower at the
side.
PC shell.
PinchGuard lock
buckle.
BELL Zipper
Puffer children,
47-54 cm
BELL Zipper
Ecykelhjelm.dk
BELL
USA
339 DKK
Blue helmet with
yellow animals on.
PC shell.
PinchGuard lock
buckle.
BELL Fraction
children blue, 48-
53 cm
BELL Fraction
Ecykelhjelm.dk
BELL
USA
399 DKK
Blue helmet with boy
on a motor cycle,
American colours and
stars.
Unknown
BELL Bellino
bicycle helmet,
children, blue
safari, 48-52 cm
BELL Bellino
Ecykelhjelm.dk
BELL
USA
399 DKK
Blue helmets with
white rhinoceros.
Unknown
Product name
Brand
Dealer
Name of producer
Head office of
producer – country*
Price
Appearance
Materials
Pictures
Urbanwinner
bicycle helmet
with light, blue,
48-54 cm
Urban Winner
Ecykelhjelm.dk
UrbanWinner
Denmark
599 DKK
Light blue skater
helmet with LED light
at the back of the
neck.
Unknown. Magnetic
catch.
Casco, Mini Gen-
eration Racoon,
44-50 cm
Casco
Ecykelhjelm.dk
Casco
Germany. Is produced
in the EU.
599 DKK
White helmet with
brim. Grey stripes and
drawing of a raccoon.
Unknown
Nutcase Moo
Baby Nutty, 47-50
cm
Nutcase
Ecykelhjelm.dk
Nutcase
USA
499 DKK
White skater helmet
with black cow
blotches.
Unknown
Thansen Child
bicycle helmet
white/pink, size
48-52 cm
Unknown, own brand?
Thansen.dk
Unknown
Unknown
99.95
DKK
White helmet with
pink flowers on.
Unknown
The Danish Environmental Protection Agency / Survey and risk assessment of chemical substances in bicycle helmets 25
Product name
Brand
Dealer
Name of producer
Head office of
producer – country*
Price
Appearance
Materials
Pictures
Rawlink Bicy-
cle/skater helmet,
junior, 48-52 cm
Rawlink
Silvan.dk
Unknown
Unknown
159.95
DKK
Turquoise skater
helmet.
Unknown
Rawlink Bicycle
helmet boy junior,
48-54 cm
Rawlink
Silvan.dk
Unknown
Unknown
129.95
DKK
Blue, white and black
with body stripes.
EPS and PVC shell.
Biltema Child
helmet, size 48-
52 cm
Unknown
Biltema.dk
Zhao Qing Bo Han
Sports Company
Ltd. Da Wang In-
dustrial Zone
China
89.90
DKK
Black and pink, looks
like a ladybird.
Unknown
Aldi Skater-
/bicycle helmet for
children, size 49-
54 cm
Unknown
Aldi.dk
Unknown
Unknown
149 DKK
Green and black. With
detachable LED light.
Shell of PC, PU
foam and inner
velvet padding.
Product name
Brand
Dealer
Name of producer
Head office of
producer – country*
Price
Appearance
Materials
Pictures
Harald Nyborg
Child helmet
Green S, 48-52
cm
Busetto
Harald-nyborg.dk
Busetto, imported
by City Light
Unknown
99 DKK
Green and black.
Unknown
On Gear Skate
Style Bicycle and
skater helmet,
matt black, 48-54
cm
On Gear
Cykelpartner.dk
On Gear
Denmark
149 DKK
Black skater helmet.
Unknown
Lazer BOB Racer
black bicycle
helmet, 45-51 cm
Lazer
Cykelpartner.dk
Lazer
Belgium
199 DKK
Black skater helmet
with check white racer
pattern in squares.
Unknown
Levior Primo
Licens bicycle
helmet with diode
light red/black,
46-51 cm
Levior Primo Licens
Cykelparnter.dk
Levior Helmet-
system
Unknown
299 DKK
Black and red with
drawing of sabres and
shark on the side.
With diode light at the
back.
Unknown
The Danish Environmental Protection Agency / Survey and risk assessment of chemical substances in bicycle helmets 27
Product name
Brand
Dealer
Name of producer
Head office of
producer – country*
Price
Appearance
Materials
Pictures
PUKY CH1 with
LED flashing light
pink, size 46-51
cm
PUKY PH1
Cykelpartner.dk
PUKY
Germany
329 DKK
Pink helmet with blue,
purple and white
flowers. LED flashing
light at the back.
Unknown
MET Buddy
white/pink bicycle
helmet with but-
terflies, size 46-53
cm
MET Buddy
Cykelpartner.dk
MET
Italy
199 DKK
White/pink helmet
with butterflies.
Unknown
BELL Segment
Junior bicycle and
skater helmet,
Blue Nitro, 48-53
cm
BELL Segment
Cykelpartner.dk
BELL
USA
299 DKK
Blue skater helmet
with drawing of ex-
haust pipe in flames.
Unknown
BELL Charger
Bicycle helmet,
blue, 50-57 cm
BELL Charger
Cykelpartner.dk
BELL
USA
349 DKK
Blue bicycle helmet
with light blue BELL
label on the side.
PC shell
Product name
Brand
Dealer
Name of producer
Head office of
producer – country*
Price
Appearance
Materials
Pictures
ABUS Super Chili
pink, size 46-52
cm
ABUS Super Chili
Cykelpartner.dk
ABUS
Germany
339 DKK
Pink with white pat-
tern.
Unknown
MET Genio/Elfo
blue cheetah
bicycle helmet,
size 46-53 cm
MET Genio
Cykelpartner.dk
MET
USA
299 DKK
Blue with drawing of a
cheetah on.
Unknown
Mango Scatter
Matt black, bicy-
cle and ski hel-
met, size 49-52
cm
Mango Scatter
Cykelpartner.dk
Mango Sport Sys-
tem
Italy
429 DKK
Completely black.
Unknown
ABUS Hubble
with LED light
blue pirate, size
46-52 cm
ABUS Hubble
Cykelpartner.dk
ABUS
Germany
439 DKK
Blue with pirate motif.
Unknown
GIRO Rascal
child bicycle hel-
met, pink leopard,
size 46-50 cm
GIRO Rascal
Cykelpartner.dk
GIRO
USA
279 DKK
Pink with pattern.
With LED rear lamp.
Unknown
The Danish Environmental Protection Agency / Survey and risk assessment of chemical substances in bicycle helmets 29
Product name
Brand
Dealer
Name of producer
Head office of
producer – country*
Price
Appearance
Materials
Pictures
Mango Piuma PI-
W161 white with
print, size 45-48
cm
Mango Piuma
Cykelpartner.dk
Mango Sport Sys-
tem
Italy
459 DKK
White skater helmet
with print.
Unknown
Nutcase Little
Nutty Gen3 –
Watermelon, size
XS 48-52 cm
Nutcase, Little Nutty
Cykelpartner.dk
Nutcase
USA
499 DKK
Green skater helmet
which looks like a
watermelon.
Unknown
CSI Bicycle hel-
met for children,
Blue dots, 44-50
cm
CSI
Bilka
CSI, Cycling Supply
International (pro-
duced in China)
Denmark
189 DKK
Dark blue with dots in
white, light blue and
green.
Unknown
CSI Bicycle hel-
met skater kids,
mint, 48-53 cm
CSI
Bilka
CSI, Cycling Supply
International (pro-
duced in China)
Denmark
299 DKK
Mint skater helmet
with pink stripe.
Unknown
Disney Frost
bicycle helmet
size XS, 46-53 cm
Disney
Bilka
Stamp, SGS UK
(produced in China)
UK
199 DKK
White bicycle helmet
with the Frost girls in
light blue/pink colours.
Unknown
Product name
Brand
Dealer
Name of producer
Head office of
producer – country*
Price
Appearance
Materials
Pictures
Melon ”Pure col-
lection” Greene-
on, XXS-S, 46-52
cm
Melon
Cykelexperten
Melon Helmets
Germany
549 DKK
Green skater helmet.
Outer shell of PC.
The pads of hygien-
ic Coolmax materi-
al (soft foam). EPS
inner shell. Plastic
print on pads inside.
Scott Sports bicy-
cle helmet, 46-52
cm
Scott
Cykelexperten
Scott-Sports
USA
449 DKK
Blue bicycle helmet
with pink and purple
stripe. With LED light
at the back.
Unknown
ABUS Smiley 2.0
Helmet, Tur-
quoise Sailor, 45-
50 cm
ABUS
Cykelexperten
ABUS
Germany
339 DKK
Light blue bicycle
helmets with sailing
motifs (anchor, life
ring).
Unknown
Bontrager Sol-
stice MIPS Child
helmets, 48-55
cm
Bontrager
Fri Bike Shop
Bontrager
USA
649 DKK
Pink bicycle helmet
with pink pattern.
Unknown
Innergy bicycle
helmet Esther, S,
48-54 cm
Innergy
Fri Bike Shop
Innergy
Denmark
299 DKK
White bicycle helmet
with multicoloured
stars. With LED light
at the back.
EPS material. Mag-
netic buckle.
The Danish Environmental Protection Agency / Survey and risk assessment of chemical substances in bicycle helmets 31
Product name
Brand
Dealer
Name of producer
Head office of
producer – country*
Price
Appearance
Materials
Pictures
Lazer Nut’z Light
Blue Mips, 50-56
cm
Lazer
Cykelhjelm.com
Lazer
Belgium
399 DKK
Blue bicycle helmet.
Unknown
Casco Fun Gen-
eration Urban
White Mat, 50-55
cm
Casco
Cykelhjelm.com
Casco
Germany
599 DKK
White skater bicycle
helmet with pink stripe
and Casco logo.
Unknown
Alpina Carapax
Flash helmet pink,
51-55 cm
Alpina
Bikester.com
Alpina
Italy
569 DKK
Pink helmet with white
brim.
PC outer shell and
EPS inner shell.
Appina Ximo
Flash helmet
blue, 47-51 cm
Alpina
Bikester.com
Alpina
Italy
339 DKK
Blue helmet with red
car on.
PC outer shell and
EPS inner shell.
Axant Rider Boy
Helmet green, 48-
55 cm
Axant
Bikester.com
Axant
Germany
189 DKK
Black and green hel-
met with brim.
EPS foam
Product name
Brand
Dealer
Name of producer
Head office of
producer – country*
Price
Appearance
Materials
Pictures
Bern Nina helmet
incl. flip visor,
white/colourful,
48-51,5 cm
Bern
Bikester.com
Bern Unlimited
USA
339 DKK
White skater helmet
with hat brim and
colourful flowers.
PC outer shell
Cube Skull helmet
black, 48-52 cm
Cube
Bikester.com
Cube
Germany
109 DKK
Black helmet with
skull on.
EPS foam
C-Preme Raskullz
Kitty Tiara helmet
pink, 50-54 cm
C-Preme
Bikester.com
C-Preme Limited
LLC
USA
229 DKK
Pink helmet with cat’s
eyes and tiara.
EPS
Kali Chakra Hel-
met violet, 48-54
cm
Kali
Bikester.com
Kali Protectives
USA
259 DKK
Violet helmet with
mermaids and star-
fishes on.
Outer shell of PC,
inner shell of EPS.
KED Meggy
Trend helmet
green/turquoise,
44-49 cm
KED
Bikester.com
KED Germany
Germany
259 DKK
Green and blue hel-
met, looks like an
animal. LED at the
back.
Unknown
The Danish Environmental Protection Agency / Survey and risk assessment of chemical substances in bicycle helmets 33
Product name
Brand
Dealer
Name of producer
Head office of
producer – country*
Price
Appearance
Materials
Pictures
O’Neal Dirt Lid
Helmet Rainbow
black, 47-48 cm
O’Neal
Bikester.com
O’Neal
USA?
299 DKK
Black skater helmet
with rainbow colours
on.
100% ABS
POC POCito
Crane Helmet
Orange, 51-54 cm
POC
Bikester.com
POC Sports
Sweden
769 DKK
Orange skater helmet.
EPS
UVEX kid 2 hel-
met green/white,
46-52 cm
UVEX
Bikester.com
UVEX
Germany
229 DKK
White helmet with
grass and sheep.
EPS foam
Polisport Red
bicycle helmet
with racer motif,
XS, 46-53 cm
Polisport
COOP.dk
Polisport
Portugal
199.95
DKK
Red helmet with racer
motif (black/white
check pattern).
EPS outer shell.
Product name
Brand
Dealer
Name of producer
Head office of
producer – country*
Price
Appearance
Materials
Pictures
Limar bicycle
helmet for chil-
dren, black with
yellow flames, S,
46-51 cm
Limar
COOP.dk
Limar
Italy
349.95
DKK
Black bicycle helmet
with yellow/orange
flames. LED light at
the back.
Outer shell of PC
and inner shell of
EPS foam.
Mustang bicycle
helmet for chil-
dren – blue with
dinosaurs, XS,
45-51 cm
Mustang
COOP.dk
Mustang
Switzerland
149.95
DKK
Green helmet with
dinosaurs on.
Outer shell of PC
and inner shell of
EPS foam.
Mustang skater
helmet for chil-
dren, matt tur-
quoise, S, 48-52
cm
Mustang
COOP.dk
Mustang
Switzerland
199.95
DKK
Turquoise skater
helmet.
Outer shell of PC
and inner shell of
EPS foam.
Specialized Mio
Pink, child bicycle
helmet for the
youngest, 44-52
cm
Specialized
Webike.dk
Specialized
USA?
329 DKK
Pink, with white,
green and pink pat-
tern/figures.
Unknown
Specialized Cov-
ert Kids Hyper
Crackle, 47-53 cm
Specialized
Webike.dk
Specialized
USA?
239 DKK
Black skater helmet
with yellow and grey
cracks.
Unknown
The Danish Environmental Protection Agency / Survey and risk assessment of chemical substances in bicycle helmets 35
Product name
Brand
Dealer
Name of producer
Head office of
producer – country*
Price
Appearance
Materials
Pictures
Kiddimoto helmet
multi-dotted, 48-
52 cm
Kiddimoto
Br.dk
Kiddimoto
UK
349 DKK
White skater helmet
with different coloured
dots.
Outer shell of ABS
plastic.
* ”Head office of producer – country” indicates the country in which the headquarters of the producer is situated. The production does not necessarily take place in the same country. Next to
some country names a question mark is written. The question mark means that it was not possible to identify the country of the headquarters of the producer, but it is assumed to be the
country listed (based on information on their web site).
3.7 Analysis of information
In this section, various information from the collection of information is gathered, processed
and summarised. The following is examined:
Identified prices of bicycle helmets
Identified materials used in bicycle helmets
Identified producers and brands of bicycle helmets
Which materials are in contact with the skin when the cyclists wear bicycle helmets
3.7.1 Prices of bicycle helmets
The prices of the identified bicycle helmets for children are between 89.90 DKK for a bicycle
helmet in Biltema to 769 DKK for a bicycle helmet of the brand POC (found in a web shop).
During the shop visits, prices of bicycle helmets up to 1,999 DKK were observed but these
were for adults and seemed to be for more professional sportsmen.
3.7.2 Materials
According to the search on the internet and the shop visits, the collection of information about
bicycle helmets shows that the helmets consist of the following parts:
Outer shell
Inner shell
Protective pads which are typically built-up in two different ways:
Foam material which is fully encircled by a layer of textile (a pocket of textile)
Foam material with a thin layer of textile at the top (towards the user)
Potential plastic strap inside which has the purpose to create a better fit as it can be tight-
ened/opened by turning a wheel rearmost in the helmet
Strap
Chin buckle (in different designs)
Potential chin pad (probably of the same material as the pads on the inside of the helmet)
Potential LED lamp at the back of the helmet
Potential reflectors at the back of the helmet
These parts are made of different materials as described in Fejl! Henvisningskilde ikke fun-
det. below. It should be noted that information about the materials do not solely come from the
helmets which are included in Fejl! Henvisningskilde ikke fundet. but also include infor-
mation about helmets for older children (above 3 years) even if they are not shown as exam-
ples in Table 2.
An observation of various home pages with specification of the materials is that the outer shell
of the skater helmets seems to be made of ABS (acrylonitrile-butadiene-styrene) whereas the
more common bicycle helmets (sports bicycle helmets) are made of PC (polycarbonate).
However, exceptions were also found.
A literature search on the home pages
10
of the bicycle helmet producers has identified four
helmets with pads/padding of EPS foam (expanded polystyrene), and for the outer shell, one
helmet in PS (polystyrene), two in ABS (acrylonitrile-butadiene-styrene) and one in PVC (poly-
vinyl chloride) were identified. Furthermore, an inner shell of EPS (expanded polystyrene) was
identified. Other information from the literature search shows that the foam material is PU
(polyurethane) foam (Oeko-Test, 2014).
10
Links: https://nutcasehelmets.com/collections/baby-nutty/products/petal-power?variant=1265688652,
https://nutcasehelmets.com/collections/youth/products/black-zone?variant=25582449477,
http://www.crazy-safety.com/index.asp?secid=333, http://www.urbanwinner.dk/om-vores-cykelhjelm/
Table 3: Overview of materials in bicycle helmets for children at the age below 3 years
based on information from web shops (the number of home pages with the mentioned
material is stated in brackets)
Part of the bicycle
helmet
Materials
Comments
Outer shell
ABS-shell (5)
Polycarbonate shell (13)
PVC (1)
PS (1)
EPS (1)
LED light at the back (8)
PS shell is seen on a bicycle helmet for
older children or adults and therefore it
is not included in Fejl! Henvisningskil-
de ikke fundet.
Inner shell
EPS (17)
Pads/paddings and
possible chin pad
EPS foam (1)
PU foam (1)
Antibacterial pads (1)
EPS is a hard material and it is possibly
an error that it is stated as used in pads.
PU foam with velvet padding.
The applied biocide is not stated
Plastic strap inside
Hard plastic of unknown material
Strap
Nylon (1)
Chin buckle
Hard plastic of unknown material
Magnetic catch (2) or click buckle of
plastic
The information from the contacted suppliers (2) shows that the outer shell is made of PC
(polycarbonate) (2), the inner shell is made of EPS (expanded polystyrene) (2), the strap of
nylon (1) or PES (polyester) (2), and the protective pads can consist of an outside polyester
textile layer with PU (polyurethane) and with foam inside (1). The plastic buckle is made of the
thermoplastic type POM (polyoxymethylene) (1).
A more general literature search shows that bicycle helmets are typically made in the following
materials:
Outer shell of PET (polyethylene terephthalate) or similar types of plastic but PC (polycar-
bonate) or ABS (acrylonitrile-butadiene-styrene) is typically used in somewhat more expen-
sive helmets
Inner shell is typically made of EPS foam (expanded polystyrene) but in some helmets, the
use of EPP (expanded polypropylene) or EPU (expanded polyurethane) has been initiated
instead
Straps are normally made of either nylon or PP (polypropylene)
The buckle is normally made of plastic (the type is not specified)
Protective pads are normally used inside the helmet but the material in question is not stated
The information on typical material use can be summarized as:
Outer shell – primarily PC (polycarbonate) and then ABS (acrylonitrile-butadiene-styrene)
but it is also observed in PVC (polyvinylchloride), PS (polystyrene), EPS (expanded polysty-
rene) etc.
Inner shell – to a great extent of EPS (expanded polystyrene)
Straps – in nylon, PES (polyester) or PP (polypropylene)
Buckle – normally in hard plastic (unknown material) – in one single case it is stated to be of
the plastic type POM (polyoxymethylene)
Protective pads – not much information but they seem to be made of PU foam (polyure-
thane) either with a textile layer PES (polyester) or fully encircled by a layer of textile (a
pocket of textile)
3.7.3 Producers and brands
According to the search on the internet and the shop visits, the collection of the information
about bicycle helmets shows that the following 39 brands and producers of bicycle helmets
have been identified. These are presented in the table below.
Table 4: Overview of identified producers and brands of bicycle helmets
Brands
Name of producer
Head office of producer
– country
Produced in
ABUS
ABUS
Germany
Alpina
Alpina
Italy
Italy
Axant
Axant
Germany
BELL
BELL
USA
China
Bern
Bern Unlimited
USA
Biltema
Zhao Qing Bo Han Sports
Company Ltd
China
China
Bontrager
Bontrager
USA
Busetto (Harald Ny-
borg)
Cannondale
Cannondale
USA
Casco
Casco
Germany
EU
C-Preme
C-Preme Limited LLC
USA
Crazy Safety
Crazy
Denmark
China
CSI
CSI (Cycling Supply Interna-
tional)
Denmark (part of ABUS,
is behind Crazy Safety)
China
Cube
Cube
Germany
GIRO
GIRO
USA
China
Innergy
Innergy
Denmark
Kali
Kali Protectives
USA
KED
KED Germany
Germany
Germany
Kiddimoto
Kiddimoto
UK
Lazer
Lazer
Belgium
China
Levior
Levior Helmetsystem
Germany
Germany
Limar
Limar
Italy
China
Mango
Mango Sport System
Italy
Italy
Melon
Melon Helmets
Germany
China
MET
MET
Italy
China
Mustang
Mustang
Switzerland
Nutcase
Nutcase
USA
China
O’neal
O’neal
USA?
On Gear
On Gear
Denmark
Outtrek (Thansen)
Outtrek
China
Polisport
Polisport
Portugal
POC
POC Sports
Sweden
PUKY
PUKY
Germany
Germany
Rawlink (Silvan)
Scott
Scott-Sports
USA
Specialized
Specialized
USA?
Brands
Name of producer
Head office of producer
– country
Produced in
Stamp
Stamp
France
China
Urbanwinner
UrbanWinner
Denmark
UVEX
UVEX
Germany
Europe, mainly
Germany
Empty fields mean that the identification of the producer, producer country and/or place of production
has failed.
3.7.4 Materials in contact with the skin
In connection with the shop visits, the inner side of the bicycle helmets were closely examined
to identify the materials which are in contact with the skin when the consumers (in this report,
children) wear the bicycle helmet. On some home pages, photos of the inner side of the bicy-
cle helmets could be examined as well.
3.7.4.1 The inner side of the bicycle helmet
The inner side appearance of the various brands of bicycle helmets is very different and the
type of the used pad material as well. However, common to all helmets is that the consumer is
not in contact with neither outer shell nor inner shell but only with the pad material. Some bicy-
cle helmets might have a piece of plastic around the inner shell which is covered with pad
material almost the whole way around but in some cases, direct contact with plastic, typically
in the back of the head, might occur where the helmet (the plastic material) can be tightened
by turning a button. However, it is relatively hard plastic which means that the probability of
use of plasticisers here is very small.
Typically, the pad material is a layer of foam covered with a thin layer of textile. In many cases,
the pad material, however, consists of a sewed “pocket” of textile filled with unknown “cotton-
like” material. Often the pad material is fastened to the inner side of the helmet by use of Vel-
cro but the consumers have solely skin contact with the textile pad.
The information from one of the bicycle shops was that more and more of the brands start to
produce pads consisting of a textile pocket with padding. This is a question of quality as a
layer of foam covered with a thin layer of textile can quickly fray at the edge. According to one
of the bicycle helmet shops, only a few bicycle helmets use pads of foam material covered
with a thin layer of textile today (see picture of white/pink bicycle helmet in fact box). Different
types of bicycle helmets are shown in the fact box on the next page.
The inner side of different bicycle helmets
Bicycle helmets with foam material covered with a thin layer of textile (white helmet,
white foam material with pink textile and black helmet with black foam material with
black textile)
Bicycle helmets with a ”pocket” of textile filled with ”cotton-like” unknown foam material.
Some bicycle helmets have padding material all around the head while some only have
in the top, at the side and in the front (see red lining).
Some bicycle helmets contain pads with plastic print (helmet with “melon” print below)
3.7.4.2 Straps and buckle
When the bicycle helmet is tightened, there will be skin contact with the strap at the
ears/cheeks and under the chin for all bicycle helmets. Furthermore, there will be contact with
the buckle (made of hard plastic) unless, in some cases, this buckle is hidden behind a chin
pad of the same type of material like the pad material inside the helmet.
3.7.4.3 Conclusion of materials in contact with the skin
Therefore, the material types in contact with the skin are:
Textile (upon or around the foam material) in the inner side of the helmet or at a possible
chin pad. Largest and direct skin contact is in the forehead. At the top of the head and in the
sides, the user’s hair is typically between the bicycle helmet and the skin. There might be
skin contact with textile on bicycle helmets which have chin pads in front of the buckle.
Straps of textile have contact with the skin under the ears, at the cheeks and under the chin.
Plastic buckles under the chin (if no chin pad is used) or possible plastic holders to collect
the straps at the ears.
As described in Table 1 in the section about standards and legislation (see chapter 2), a num-
ber of limitations for chemical substances are restricted by legislation. These limitations also
apply to textiles used in bicycle helmets due to the skin contact with the textiles in the pad
material inside the bicycle helmets. Even if these substances (for instance azo colourants)
have been identified in previous tests of bicycle helmets, they are restricted by legislation and
thus not relevant to examine in detail in this project as it is not a control project.
During the information collection, a single brand of bicycle helmet with plastic print on top of
the pad material was seen. This plastic print might contain phthalates but the use of plastic
print on the pad material is not common according to the survey carried out in this project.
Furthermore, during the information collection, one single bicycle helmet was identified where
it was stated that the pad material was “antibacterial treated”. The chemical substance in
question used for the antibacterial treatment is not known but the impression from the infor-
mation collection is that this is not a common phenomenon. Thus, it is considered to be irrele-
vant to examine the textile for the content of these chemical substances.
Certain fluorinated compounds are applied for impregnation of textile, i.e. to make textile or
straps dirt- and water/sweat-repelling. However, only PFOS or PFOS-like compounds are
restricted by legislation – other applied fluorinated compounds like perfluoroalkyl and
polyfluoroalkyl substances (PFASs) are not. Therefore, it was decided to examine the straps in
the bicycle helmets for the content of fluorine to get an indication of a possible use of PFASs,
although two dealers of bicycle helmets gave information that fluorinated compounds are not
applied in their bicycle helmets.
According to a former survey, the foam material has turned out to contain phthalates in small
amounts (described as > 1% and > 0,1% respectively) in some cases (2 out of 13 bicycle
helmets). These results indicate that they are impurities and not phthalates which are added to
get a softening function. Therefore, it is considered to be irrelevant to analyse the foam mate-
rial for content of phthalates in this project.
In previous survey projects
11
from the Danish Environmental Protection Agency, foam material
has turned out to contain flame retardants – primarily CI/P-based flame retardants. Therefore,
it was decided to examine whether the foam material in bicycle helmets for young children
might also contain flame retardants.
It is considered irrelevant to examine the content of chemical substances in the buckle which
is made of hard plastic in nearly all cases. It is not expected that these buckles contain prob-
lematic chemical substances which can migrate in amounts that might constitute a risk for the
user’s health. In the meantime, undesirable substances like PAH (polyaromatic hydrocarbons),
which have been identified in previous tests of bicycle helmets, have been restricted in plastic
and rubber parts which come into direct long or repeated short contact with skin.
11
Kortlægning nr. 135 ”Kemiske stoffer i autostole og andre produkter med tekstil til børn”, 2015
(http://mst.dk/service/publikationer/publikationsarkiv/2015/apr/kemiske-stoffer-i-autostole/). Kortlægning
nr. 126 ”Kortlægning, sundheds- og miljøvurdering af flammehæmmere i tekstiler”, 2014
(http://mst.dk/service/publikationer/publikationsarkiv/2014/mar/kortlaegning,-sundheds--og-
miljoevurdering-af-flammehaemmere-i-tekstiler/).
4. Selection of products for
analysis
Based on the information gathered through the information collection in this project, it was
decided to carry out the following analyses of 16 different bicycle helmets for children:
Determination of fluorine on the straps to get an indication of a possible use of perfluoroalkyl
and polyfluoroalkyl substances (PFAS) (for impregnation of the straps).
Screening analyses (analyses of elements) of both straps and foam material (not the textile
in the pad material) to get an indication of possible use of flame retardants.
Potential quantitative analyses of selected flame retardants if the screening analyses show
an increased content of for instance chlorine, phosphorus or bromine.
It was not possible within the allocated budget to investigate both strap and textile in the pad-
ding material inside the bicycle helmet. The focus was therefore on the bicycle strap for sever-
al reasons:
PFAS chemicals are relatively expensive chemicals and are therefore presumably used in
more expensive products.
The bicycle strap has direct contact with the skin for a large part of the strap, whereas the
pads inside the helmet often do not have direct contact with the skin (hair will be in between)
– except for the forehead.
A young child may be further exposed by chewing/sucking on the bicycle strap. This is not
considered to be possible for the pads, which are situated inside the helmet.
4.1 Purchase of products for analysis
For the above-mentioned analyses, in total 16 different bicycle helmets for children were pur-
chased, based on the following guidelines (in prioritised order):
1. Bicycle helmets in various brands are purchased.
2. Bicycle helmets with different types of pad material are purchased – however, it seems
that most bicycle helmets today are with textile “pockets” with padding. The aim is to pur-
chase several different types (appearance) of pad material.
3. Bicycle helmets in different price ranges are purchased (the cheap bicycle helmets below
DKK 200, the expensive bicycle helmets from approx. DKK 400 and up as well as bicycle
helmets in the intermediate price range). However, most bicycle helmets in the cheapest
price range and the intermediate price range are bought.
4. Bicycle helmets of various types (skater helmets, common bicycle helmets, special bicycle
helmets designed as animals) are bought.
Regarding item 1 on purchase of different brands, it must be noted that the list of the most
common brands, which suppliers of bicycle helmets gave (see section 3.1.2 “Contact to sup-
pliers of bicycle helmets”), as well as the most used brands and models found on different
home pages through the internet search were taken into consideration.
The purchased 16 bicycle helmets for children are distributed as described below in Table 5.
All the purchased models are in the sizes starting with 44-49 cm in head size, i.e. for the quite
young children from 0-3 years. Some helmets have sizes up to 52-55 cm, i.e. some helmet
can also be used by children above 3 years.
Table 5: Overview of the 16 bicycle helmets purchased for analysis
Brands
Price
Produced in
Type of helmet
Type of pad material
16 various
brands were
purchased
Cheapest: 90 DKK
Most expensive: 599
DKK
Average: 320 DKK
< 200 DKK: 5 pcs.
200 - 400 DKK: 7 pcs.
> 400 DKK.: 4 pcs.
China: 11 pcs.
Germany: 1 pc.
Italy: 1 pc.
EU: 1 pc.
Unknown: 2 pcs.
Common: 10 pcs.
Skater: 5 pcs.
Special: 1 pc.
Foam material with
top layer of textile: 5
pcs.
Textile pocket with
foam padding: 11 pcs.
4.2 Use of the app ”Check the Chemistry”
The Danish Consumer Council’s and the Danish Environmental Protection Agency’s app
“Check the chemistry” was used on all the 16 bicycle helmets purchased for analyses. For 7
bicycle helmets, the result was that the app could not be used because the bar code could not
be recognised. For the 9 bicycle helmets where an inquiry on candidate list substances was
sent, in total 2 answers were returned stating that the bicycle helmets do not contain candidate
list substances in concentrations above 0.1%. For the remaining 7 bicycle helmets, no infor-
mation was received about content of candidate list substances within the deadline of the 45
days.
5. Screening analyses
First screening analyses were performed in the form of SEM-EDS (Scanning Electron Micro-
scope – Energy Dispersive x-ray Spectroscopy) for determination of certain elements, partly in
the foam in the pad material inside in the bicycle helmet, partly in the straps. Furthermore, the
content of fluorine in the straps was determined by means of a calorimeter bomb method to
reach a lower detection limit than by SEM-EDS.
5.1 Analysis methods
Analysis methods for SEM-EDS (determination of elements) and determination of fluorine are
described in detail below. These analyses were performed by FORCE Technology.
5.1.1 SEM-EDS
The surface of the selected samples (both straps and foam from the pads in the bicycle hel-
mets) was screened for content of elements in Scanning Electron Microscope (SEM). The
selected areas were analysed by use of Energy Dispersive x-ray Spectroscopy (EDS) which
can determine elements with atom number higher than 5.
The detection limit of elements analysed by SEM-EDS depends on among other things the
homogeneity and other element composition of the sample material. In general, the detection
limit is typically approx. 0.1%.
The uncertainty of measurements also depends on a number of parameters where the most
important issue is the concentration of the element. Typical relative uncertainties for this semi-
quantitative analysis method are:
2-3% for content of elements from 20-100%
4-6% for content of elements from 5-20%
10-20% for content of elements from 1-5%
50-100% for content of elements from 0.1-1%
5.1.2 Determination of fluorine
A representative partial sample of the straps (approx. 1 g) was burnt in a calorimeter bomb
with 30 atmospheric oxygen. At the oxidation, the contained fluorine compounds are trans-
formed to hydrogen fluorine which is absorbed in the calorimeter bomb solution. The liquid
collected was analysed for fluorine by ion chromatography. The content of fluorine was deter-
mined by use of calibration curve.
The analysis was conducted as real duplicate determination.
The detection limit of the applied method is 5 mg/kg (5 ppm). The uncertainty of the analysis is
approx. 20-30%.
5.2 Analysis results
The analysis results for the determination of elements and the determination of fluorine are
stated below.
5.2.1 Analysis results – determination of elements (SEM-EDS)
The analysis results for the determination of elements (SEM-EDS) are stated in Table 6 and
Table 7 below. Table 6 contains determination of elements for straps and Table 7 contains
results of the determination of elements for the padding/foam material in the pads inside in the
bicycle helmets.
In general, for the straps, the selected material is the material with the largest amount con-
tained in the bicycle helmet or the material with the largest contact with the skin (i.e. primarily
at the cheeks). One single bicycle helmet had two types of strap material. In this case, the
material with the largest amount was analysed, i.e. the part of the strap which goes from the
helmet, around the ears and down along the cheeks where it is gathered in one different type
of strap under the chin.
In general, regarding the pad material, the selected foam material is the material with contact
to the forehead. In the few cases, where this was impossible or the pad material was thinner
here, foam material was taken from the pads in the top of the bicycle helmet.
It should be noted that only results for the elements which are identified above the detection
limit of 0.1% are stated. From the results, it can be seen that no content of bromine has been
identified in any of the samples, i.e. a possible content of bromine will be found in concentra-
tions below 0.1% which indicates no use of brominated flame retardants.
The Danish Environmental Protection Agency / Survey and risk assessment of chemical substances in bicycle helmets 47
Table 6: Analysis results – Determination of elements (SEM-EDS) in the strap on the purchased bicycle helmets
Content of element in %
Strap on bicy-
cle helmet
Carbon
Nitrogen
Oxygen
Aluminium
Silicon
Calcium
Sulphur
Titanium
Sum
C1
64.33
35.67
100.00
C2
89.98
9.84
0.18
100.00
C3
63.73
35.92
0.11
0.24
100.00
C4
69.70
9.62
19.76
0.81
0.11
100.00
C5
72.51
9.40
17.95
0.14
100.00
C6
64.29
35.71
100.00
C7
64.68
35.14
0.18
100.00
C8
74.78
25.04
0.18
100.00
C9
67.88
11.09
21.03
100.00
C10
90.22
9.17
0.17
0.44
100.00
C11
64.54
35.46
100.00
C12
89.74
10.26
100.00
C13
85.25
14.75
100.00
C14
69.59
10.80
19.48
0.13
100.00
C15
91.68
8.32
100.00
C16
92.89
7.11
100.00
Table 7. Analysis results – Determination of elements (SEM-EDS) in the padding/foam material inside the purchased bicycle helmets
Content of elements in %
Foam in pad
in bicycle
helmet
Carbon
Nitrogen
Oxygen
Aluminium
Silicon
Calcium
Sulphur
Phosphorus
Chlorine
Barium
Magnesium
Sum*
C1
69.29
5.49
25.05
0.17
100.00
C2
68.95
5.33
25.58
0.14
100.00
C3
61.93
4.20
33.88
100.01
C4
61.19
5.41
33.22
0.17
99.99
C5
70.62
28.58
0.11
0.13
0.38
0.17
99.99
C6
69.05
5.55
24.68
0.22
0.50
100.00
C7
67.23
5.05
26.81
0.11
0.23
0.57
100.00
C8
68.33
5.15
25.56
0.22
0.16
0.14
0.44
100.00
C9
64.55
5.78
29.20
0.20
0.16
0.11
100.00
C10
66.57
3.14
29.22
0.19
0.29
0.60
100.01
C11
60.83
5.57
33.60
100.00
C12
67.20
3.85
28.95
100.00
C13
67.38
5.97
26.52
0.13
100.00
C14
69.40
4.48
25.15
0.35
0.18
0.44
100.00
C15
67.29
5.92
26.03
0.18
0.38
0.20
100.00
C16
62.72
4.87
32.41
100.00
* A sum higher or smaller than 100 is due to round-off.
5.2.2 Analysis results – Determination of fluorine
The analysis results for the determination of fluorine of the straps are stated in Table 8 below.
The analysis results are stated as the average of the two results from the duplicate determina-
tion.
Table 8: Analysis results for determination of fluorine
Bicycle helmet
Content of fluorine in straps
mg F/kg strap (ppm)
C1
< 5
C2
5
C3
< 5
C4
92
C5
< 5
C6
6.3
C7
< 5
C8
< 5
C9
< 5
C10
7.7
C11
< 5
C12
< 5
C13
< 5
C14
< 5
C15
< 5
C16
< 5
5.2.3 Discussion of analysis results
From the results in both Table 6 and Table 7, it is seen that more than 99% of the elements in
both straps and pad material consist of the elements carbon (C), oxygen (O) and nitrogen (N).
In section 3.5.2 “Information about materials in bicycle helmets”, it is stated that straps typically
consist of nylon (contains C, O and N) or PP (polypropylene) (contains only C and O, but not
N) and that pad material typically consists of PU foam (polyurethane) (contains C, O and N) or
EPP (expanded polypropylene) (contains C and O). Based on this information, the screening
results together with visual observations could thus indicate that 4 out of 16 straps are of nylon
and the remaining of PP (polypropylene) whereas 15 out of 16 helmets probably have pad
material which consists of PU foam (polyurethane) and one single bicycle helmet has foam
material consisting of for instance EPP (expanded polypropylene). However, other analyses
which have not been carried out in this project must be performed to confirm the material
composition in the purchased bicycle helmets.
As described, no content of bromine above the detection limit of 0.1% was identified in any of
the samples. According to Janssen (2005), a content of brominated flame retardants in flame
retarded products will typically be between 5-30% and other sources state that concentration
of brominated flame retardants in plastic is typically in concentrations between 0.1-28%. This
means that concentrations of bromine under 0.1% does not indicate use of brominated flame
retardants.
Chlorine and phosphorus were only identified in amounts above 0.1% in one product (C10). It
concerns relatively small amounts of 0.6 and 0.29% respectively. In a previous survey report
from the Danish EPA (Nørgaard Andersen et al., 2014), a content of both chlorine and phos-
phorus at the screening is identified as a content of the flame retardants TDCP and TCPP in
foam material in furniture. Therefore, the identified content of chlorine and phosphorus respec-
tively might indicate a content of chlorinated phosphorus-based flame retardants such as
TDCP and/or TCPP in bicycle helmet C10. For that reason, bicycle helmet C10 was selected
for quantitative analysis for a content of chlorinated phosphorus-based flame retardants. The
result of the quantitative analysis is stated in chapter 6.
The results of the fluorine determination in the straps show that fluorine was identified in four
of the bicycle helmets (C2, C4, C6 and C10). However, concerning C2, the duplicate determi-
nation only identified a content of fluorine above the detection limit in one of the two samples.
The results of the two samples are thus 5.2 ppm fluorine and < 5 ppm respectively. The con-
tent of fluorine in C6 and C10 is just above the detection limit with 6.3 and 7.7 ppm fluorine
respectively whereas the value of the content of fluorine in C4 is somewhat higher at 92 ppm.
The content of fluorine in C4 (and possibly C6 and C10) could thus indicate a content of poten-
tial polyfluoroalkyl substances (PFASs) whereas the content of fluorine is so low in the other
products that they either contain no fluorinated compounds or have a very low content of po-
tential PFASs.
Regarding other elements, small amounts of aluminium (AI), silicon (Si), calcium (Ca), sulphur
(S) and titan (Ti) were identified in the straps. Identification of titanium is most likely due to use
of titanium dioxide (white colourant) whereas identification of the other elements might be due
to use of filler, such as for instance aluminium oxide, calcium carbonate and silicon oxide.
However, other analyses, not carried out in this project, must be made to confirm the type of
potential fillers.
In the foam material, aluminium (AI), silicon (Si), calcium (Ca), sulphur (S), barium (Ba) and
magnesium (Mg) were also identified in small amounts. Here the finding is probably also due
to use of fillers, such as aluminium oxide, calcium carbonate, silicon oxide and barium sul-
phate or possible use of (residues of) the flame retardant aluminium hydroxide. However,
other analyses, not carried out in this project, must be made to confirm the type of various
other potential substances.
However, common to these elements is that they are identified in small amounts (< 1%).
6. Quantitative analyses
A quantitative analysis of the foam material in the pads in bicycle helmet C10 was performed
to examine whether the identified content of chlorine and phosphorus is due to a content of
chlorinated phosphorus-based flame retardants. Furthermore, quantitative content analyses in
the straps of C4, C6 and C10 for content of PFASs were performed.
6.1 Analysis methods
Analysis methods for quantification of chlorinated phosphorus-based flame retardants in the
pad material and quantification of PFASs in bicycle helmet straps are described further below.
These analyses were performed by Eurofins.
6.1.1 Quantitative analysis of chlorinated phosphorus-based flame
retardants
Quantitative analysis of chlorinated phosphorus-based flame retardants on bicycle helmet C10
was undertaken at Eurofins (Eurofins, Germany). The specific chlorinated phosphorus-based
flame retardants which were a part of the analyses are listed in Table 9.
As the foam material weighs very little in a bicycle helmet in relation to the sample amount
which is needed for the analysis, an extra identical bicycle helmet (with the same batch num-
ber and production date) was purchased for the use of the duplicate determination. The bicy-
cle helmet which was used for screening analyses is named C10A and the identical new bicy-
cle helmet is named C10B. Thus, quantitative analysis of chlorinated phosphorus-based flame
retardants is made on the foam material in the two identical bicycle helmets C10A and C10B.
The results are stated in Table 9.
The quantitative analysis of chlorinated phosphorus-based flame retardants was carried out in
the following way: The sample was added quantification standards and prepared by ultrasonic
extraction with ethyl acetate. The extract was evaporated, cleaned-up by column chromatog-
raphy and recovery standards were added. The measurements were performed by gas chro-
matography with mass selective detection (GC/MS/MS-EI) on a 60-meter column. The quanti-
fication was performed by the method of isotope dilution/method of internal standard using 5
isotope-labelled standards.
6.1.2 Quantitative analysis of PFASs
Quantitative analysis of PFASs on bicycle helmet C4, C6 and C10 was performed at Eurofins.
The analyses were for two groups of PFASs. Each group of PFASs requires its own analysis
method.
1. Perfluorinated compounds (PFC) – in total 22 different compounds
2. Neutral fluorinated compounds (NPFC), also called neutral PFOA-based substances – in
total 11 compounds
As the bicycle helmet strap material weighs very little in a bicycle helmet in relation to the
sample amount which must be used for the analysis, two extra identical bicycle helmets (with
the same batch number and production date) were purchased to perform the duplicate deter-
mination.
The bicycle helmets on which screening analysis was performed are named C4A, C6A and
C10A and the identical new bicycle helmets are described with B and C respectively. For bicy-
cle helmet C4 it was not possible to provide two extra bicycle helmets with the same batch
number and production date like the helmet from the screening analysis. Therefore, three new
helmets with another production date were purchased (but all three with the same batch num-
ber and production date). These helmets were named C4newA, C4newB and C4newC respec-
tively.
In order to have material enough for a possible subsequent migration analysis, it was decided
to prepare a mixture sample of the three identical bicycle helmets A, B and C for each type of
bicycle helmet C4new, C6 and C10. For each mixture sample, material was selected to per-
form duplicate determination (described with 1 and 2 respectively). The in total six quantitative
analyses which were performed for content of PFASs were therefore performed on
C4newABC-1, C4newABC-2, C6ABC-1, C6ABC-2, C10ABC-1 and C10ABC-2. The results are
stated in Table 9.
The fundamental analysis steps are as follows:
Addition of internal isotope-labelled standards
Ultrasonic extraction of the homogenised sample material with matrix-dependent solvents
(multi)-step-sample clean-up (depending on matrix; e.g. SPE)
Analysis by liquid chromatography coupled with mass spectrometry (LC/MS-MS)
Identification via retention time and molecule or fragment ions
Quantification of the native PFC components via internal isotope-labelled standards
LOQ: 1-5 µg/kg dry mass dependent of the matrix
Reference method: DIN 38414-S14 modified to the matrix
6.2 Results of the quantitative analyses
The analysis results of the quantitative content analyses for chlorinated phosphorus-based
flame retardants and PFASs are stated below.
6.2.1 Analysis results for chlorinated phosphorus-based flame
retardants
The analysis results for the quantitative determination of the content of chlorinated phospho-
rus-based flame retardants of the foam material in C10 are stated in Table 9 below. The anal-
ysis results are stated separately for the two helmets C10A and C10B and as the average of
the two results from the duplicate determination. As previously mentioned, the two analyses in
the duplicate determination are performed on two bicycle helmets with identical batch number
and production date.
Table 9: Analysis results (content) for chlorinated phosphorus-based flame retardants
in foam material
Flame retardant
C10A
(mg/kg)
C10B
(mg/kg)
Average
(mg/kg)
Tri-o-cresyl phosphate
< 0.1
< 0.1
< 0.1
Tricresyl phosphate
< 0.4
< 0.4
< 0.4
Tris(2-chloroisopropyl) phosphate (TCPP)
20,400
18,700
19,550
Tris(1,3-dichloroisopropyl) phosphate
(TDCP)
6,320
8,020
7,170
Tris(2-butoxyethyl) phosphate (TBEP)
< 0.2
< 0.2
< 0.2
Tributyl phosphate (TBP)
< 0.2
< 0.2
< 0.2
Triisobutyl phosphate (TIBP)
2.6
2.4
2.5
(2-Ethylhexyl)-Diphenyl phosphate
< 0.5
< 0.39
< 0.5
Flame retardant
C10A
(mg/kg)
C10B
(mg/kg)
Average
(mg/kg)
(EHDP)
Tris(2-chloroethyl) phosphate (TCEP)
1.1
1.0
1.1
Tris(2-ethylhexyl) phosphate
< 0.52
< 0.63
< 0.63
Triphenyl phosphate (TPHP)
60
58
59
LOD (Limit of detection) = 0.1 – 0.5 mg/kg
< x = less than x, corresponding to LOD
From Table 9 it is seen that TCP and TDCP are identified in large amounts (19,550 ppm (2%)
and 7,170 ppm (0.7%) respectively) and that TIBP, TCEP and TPHP are identified in small
amounts (approx. 2 ppm (0.0002%), 1 ppm (0.0001%) and 60 ppm (0.006%) respectively).
By comparison, a limit value of 5 mg/kg (5 ppm) has been determined for TCPP, TDCP and
TCEP respectively (EU Directive 2014/79/EU, 2014) for toys intended for children below the
age of 3 years and toys intended to be put into the mouth. However, these limits do not apply
to bicycle helmets.
6.2.2 Analysis results for PFASs
The analysis results for the quantitative analysis of the content of PFASs in bicycle straps in
C4new, C6 and C10 are stated in Table 10 below. The analysis results are stated one by one
for each of the two analyses (duplicate determination) for each of the three helmets C4new,
C6 and C10. Furthermore, an average value for C4new is stated. It is the only helmet where
PFASs above the detection limit are identified. As mentioned earlier, the two analyses in the
duplicate determination are performed on a mixture sample of three bicycle helmets A, B and
C with identical batch number and production date.
From Table 10 it is seen that only a few PFASs are identified in C4 but no PFASs are identi-
fied in C6 and C10. This is consistent with the fact that according to the fluorine determination,
C4 had a far higher content of fluorine (approx. 92 ppm) in comparison with C6 and C10 where
the content was just above the detection limit of the 5 ppm (approx. 6-7 ppm).
The identified PFASs in C4 are perfluorooctanoic acid (PFOA), perfluorohexane sulphonate
(PFHxS) and perfluorohexanoic acid (PFHxA). PFHxS is identified in the highest concentration
of 11.6 ppb (µg/kg) in one of the two single determinations.
However, it must be noted that PFOA and PFHxA are only identified in one of the two single
determinations and that the concentration of PFHxS in the two single determinations has a
factor 10 of difference. This can partly be due to the general uncertainties at the analyses and
partly the fact that the measured values are close to the detection limit. Another uncertain
factor is that C4newABC is produced as a mixture sample of three different bicycle helmets.
Even if these “identical” bicycle helmets have the same production number and batch number
they are not necessarily identical. Finally, the proportion of the mixture between strap from
helmet A, B and C can be a little different in the two single determinations.
In Table 11 the values which are above the detection limit are converted to µg/m
2
based on
the measurements which were made of weight and area of the analysed samples. It must be
noted that especially for C4 which consists of round ropes as bicycle strap the calculation is
uncertain. Here the calculation of the surface area is performed by calculating the area of a
cylinder. In the calculations, an average of the values for weight per area unit, which were
measured for the two duplicate determinations for each bicycle helmet, was used.
The identified concentrations of PFASs in C4 are converted to µg/m
2
thus 1.02 µg/m
2
for per-
fluorooctanoic acid (PFOA), 6.26 µg/m
2
for perfluorohexane sulphonate (PFHxS), and 0.98
µg/m
2
for perfluorohexanoic acid (PFHxA).
By comparison, the limit value for PFOS and PFOS derivates in articles is 0.1% (1000 ppm) or
1 µg/m
2
for textiles. None of the detected PFASs falls under the description PFOS derivates.
The Danish Environmental Protection Agency / Survey and risk assessment of chemical substances in bicycle helmets 55
Table 10: Analyses results (content) of PFASs in bicycle straps – unit: µg/kg (ppb)
PFAS compound
C4newABC-1
µg/kg (ppb)
C4newABC-2
µg/kg (ppb)
C4newABC
Average
µg/kg (ppb)
C6ABC-1
µg/kg (ppb)
C6ABC-2
µg/kg (ppb)
C10ABC-1
µg/kg (ppb)
C10ABC-2
µg/kg (ppb)
NPFC, neutral PFOA derivatives (*, #1)
4:2 Fluorotelomer alcohol (4:2 FTOH)
< 485
< 463
< 474
< 289
< 265
< 493
< 513
6:2 Fluorotelomer alcohol (6:2 FTOH)
< 485
< 463
< 474
< 289
< 265
< 493
< 513
8:2 Fluorotelomer alcohol (8:2 FTOH)
< 485
< 463
< 474
< 289
< 265
< 493
< 513
10:2 Fluorotelomer alcohol (10:2 FTOH)
< 485
< 463
< 474
< 289
< 265
< 493
< 513
6:2 Fluorotelomer acrylate (6:2 FTAc)
< 194
< 185
< 190
< 116
< 106
< 197
< 205
8:2 Fluorotelomer acrylate (8:2 FTAc)
< 194
< 185
< 190
< 116
< 106
< 197
< 205
10:2 Fluorotelomer acrylate (10:2 FTAc)
< 194
< 185
< 190
< 116
< 106
< 197
< 205
N-methylperfluorooctane sulfonamide (MeFOSA)
< 97.1
< 92.6
< 94.9
< 57.8
< 53.1
< 98.5
< 103
N-ethylperfluorooctane sulfonamide (EtFOSA)
< 97.1
< 92.6
< 94.9
< 57.8
< 53.1
< 98.5
< 103
N-methylperfluorooctane sulfonamide-ethanol
(MeFOSE)
< 97.1
< 92.6
< 94.9
< 57.8
< 53.1
< 98.5
< 103
N-ethyl-perfluorooctansulfonamide-ethanol (EtFOSE)
< 97.1
< 92.6
< 94.9
< 57.8
< 53.1
< 98.5
< 103
PFC. perfluorinated substances (*. #2)
Perfluorooctane sulfonate (PFOS)
< 0.505
< 0.543
< 0.524
< 0.498
< 0.518
< 0.459
< 0.513
Perfluorooctanic acid (PFOA)
1.60
< 0.543
1.07
< 0.498
< 0.518
< 0.459
< 0.513
Total PFOS/PFOA excl. LOQ
1.60
ND
1.07
ND
ND
ND
ND
Total PFOS/PFOA incl. LOQ
2.10
1.09
1.60
0.995
1.04
0.917
1.03
Perfluorobutane sulphonate (PFBS)
<0.758
< 0.815
< 0.787
< 0.746
< 0.777
< 0.688
< 0.769
Perfluorobutanoic acid (PFBA)
< 0.505
< 0.543
< 0.524
< 0.498
< 0.518
< 0.459
< 0.513
Perfluoropentane acid (PFPeA)
< 0.505
< 0.543
< 0.524
< 0.498
< 0.518
< 0.459
< 0.513
Perfluorohexane sulphonate (PFHxS)
11.6
1.60
6.60
< 0.746
< 0.777
< 0.688
< 0.769
Perfluorohexanoic acid (PFHxA)
1.52
< 0.543
1.03
< 0.498
< 0.518
< 0.459
< 0.513
Perfluoroheptan sulphonate (PFHpS)
<0.758
< 0.815
< 0.787
< 0.746
< 0.777
< 0.688
< 0.769
Perfluoroheptanoic acid (PFHpA)
< 0.505
< 0.543
< 0.524
< 0.498
< 0.518
< 0.459
< 0.513
Perfluorooctane sulfonamide (PFOSA)
< 0.505
< 0.543
< 0.524
< 0.498
< 0.518
< 0.459
< 0.513
Perfluorononanoic acid (PFNA)
< 0.505
< 0.543
< 0.524
< 0.498
< 0.518
< 0.459
< 0.513
PFAS compound
C4newABC-1
µg/kg (ppb)
C4newABC-2
µg/kg (ppb)
C4newABC
Average
µg/kg (ppb)
C6ABC-1
µg/kg (ppb)
C6ABC-2
µg/kg (ppb)
C10ABC-1
µg/kg (ppb)
C10ABC-2
µg/kg (ppb)
Perfluorodecane sulphonate (PFDS)
<0.758
< 0.815
< 0.79
< 0.746
< 0.777
< 0.688
< 0.769
Perfluorodecanoic acid (PFDA)
< 0.505
< 0.543
< 0.524
< 0.498
< 0.518
< 0.459
< 0.513
Perfluoroundecanoic acid (PFUnA)
< 0.505
< 0.543
< 0.524
< 0.498
< 0.518
< 0.459
< 0.513
Perfluorododecane acid (PFDoA)
< 0.505
< 0.543
< 0.524
< 0.498
< 0.518
< 0.459
< 0.513
Perfluorotridecane acid (PFTrA)
< 0.505
< 0.543
< 0.524
< 0.498
< 0.518
< 0.459
< 0.513
Perfluorotetradecane acid (PFTA)
< 0.505
< 0.543
< 0.524
< 0.498
< 0.518
< 0.459
< 0.513
Perfluor-3.7-dimethyloctane acid (PF-3.7-DMOA)
< 1.01
< 1.09
< 1.05
< 0.995
< 1.04
< 0.917
< 1.03
7H-Dodecafluoroheptanoic acid (HPFHpA)
< 1.01
< 1.09
< 1.05
< 0.995
< 1.04
< 0.917
< 1.03
6:2 Fluorotelomer sulphonate (6:2 FTS) (H4PFOS)
< 0.758
< 0.815
< 0.787
< 0.746
< 0.777
< 0.688
< 0.769
4:2 Fluorotelomer sulphonate (4:2 FTS) (H4PFHxS)
< 1.01
< 1.09
< 1.05
< 0.995
< 1.04
< 0.917
< 1.03
8:2 Fluorotelomer sulphonate (8:2 FTS) (H4PFDS)
< 1.01
< 1.09
< 1.05
< 0.995
< 1.04
< 0.917
< 1.03
Total PFC excl. LOQ
14.7
1.60
8.15
ND
ND
ND
ND
Total PFC incl. LOQ
27.3
16.3
21.80
14.2
14.8
13.1
14.6
* = not accredited
#1 = Internal test method GC-MS
#2 = Internal testmethod GLS OC 400, LC-MS/MS
LOQ (Limit of quantification) for the individual substances is listed with < x, for the substances
ND = not detected
Table 11: Analysis results (content) for PFASs in bicycle straps
PFASs
C4newABC
Average
µg/kg (ppb)
C4newABC
Average
µg/m
2
Perfluorooctanoic acid (PFOA)
1.07
1.02
Perfluorohexane sulphonate (PFHxS)
6.6
6.26
Perfluorohexanoic acid (PFHxA)
1.03
0.98
Total PFC excl. LOQ
8.15
7.73
6.2.3 Summary of analysis results
The results from the screening showed a content of chlorine and phosphorus in the pad mate-
rial in C10 (which might indicate a content of chlorinated phosphorus-based flame retardants)
as well as a content of fluorine in the straps in C4, C6 and C10 (which might indicate a content
of fluorinated compounds). Therefore, pad material in C10 was analysed quantitatively for a
content of chlorinated phosphorus-based flame retardants and the straps in C4, C6 and C10
were analysed quantitatively for a content of fluorinated compounds.
The result was that TCPP and TDCP were identified in the pad material in C10 in large
amounts (19,550 ppm (2%) and 7,170 ppm (0.7%) respectively) and TIBP, TCEP and TPHP
were identified in small amounts (approx. 2 ppm (0.0002%), 1 ppm (0.0001%) and 60 ppm
(0.006%) respectively).
A few PFASs were identified in the strap in C4 but no PFASs above the detection limit in the
straps in C6 and C10. This corresponds with the fact that according to the fluorine determina-
tion C4 had a far higher content of fluorine in comparison with C6 and C10. The identified
PFASs in C4 are perfluorooctanoic acid (PFOA), perfluorohexane sulphonate (PFHxS) and
perfluorohexanoic acid (PFHxA). PFHxS is identified in the highest concentration of 6.6 ppb
(µg/kg) as an average of the two single determinations.
Due to identification of chlorinated phosphorus-based flame retardants in the pad material in
C10 and PFASs in the strap in C4, migration analysis to water for both the pad material in C10
and the strap in C4 was subsequently performed.
7. Migration analyses
Based on findings of chlorinated phosphorus-based flame retardants in the foam material in
the bicycle helmet C10 and PFASs in the bicycle strap in bicycle helmet C4, migration anal-
yses were performed for these substances in the two bicycle helmets where these substances
were identified at the quantitative analyses.
7.1 Migration conditions
The following migration conditions were applied:
1 hour
37 °C
Static conditions, i.e. no stirring
Migration to water
The exposure time for a child below 3 years was set to 1 hour per day as worst-case corre-
sponding to 30 minutes of transport each way. A temperature of 37 °C corresponding to a
general body temperature was used. No stirring was used at the migration but static conditions
in order to simulate the practical use as far as possible.
For the chlorinated phosphorus-based flame retardants, the special condition was that these
were identified in the foam material inside the pads on the inner side of the bicycle helmet. In
most of the bicycle helmets (and also in C10), the foam material was encircled by a layer of
textile on all sides, i.e. no direct contact between skin and the foam material takes place.
Therefore, the entire pads were put into the migration liquid to simulate the real situation when
the bicycle helmet is worn.
Regarding the migration analyses, the migration was performed to water and not to artificial
sweat for two reasons: According EN 71-10:2005 it is stated that analytical tests have shown
that for the organic substances for which analyses are performed in EN 71-10 and EN 71-11
(i.e. among other things these chlorinated phosphorus-based flame retardants), water is as
good a simulant as other typically used simulants, such as artificial sweat. In addition to this,
the analysis results for migration to water can be used for both the calculation of the theoreti-
cal dermal and oral exposure.
7.2 Analysis methods
Analysis methods for migration of chlorinated phosphorus-based flame retardants in pad mate-
rial and migration of PFASs in bicycle strap are described closer below. These analyses were
performed by Eurofins.
7.2.1 Migration analysis for chlorinated phosphorus-based flame
retardants
Migration analysis for chlorinated phosphorus-based flame retardants was performed for the
foam material in the bicycle helmet C10. As the foam material weighs very little in a bicycle
helmet in relation to the sample amount which is needed for the analysis, the duplicate deter-
mination was carried out by means of purchase of an extra identical bicycle helmet (with the
same batch number and production date). The bicycle helmet on which screening analyses
were performed is named C10A and the identical new bicycle helmet is named C10B. Thus,
both quantitative analysis and migration analysis of chlorinated phosphorus-based flame re-
tardants are performed on the foam material in the two identical bicycle helmets C10A and
C10B.
The migration analysis for chlorinated phosphorus-based flame retardants in C10 was per-
formed in the following way:
Addition of quantification standards.
Ultrasonic extraction with ethylacetate, evaporation of the extract, addition of recovery
standard.
Measurement: GC/MS/MS-EI on 60 m VFXms.
Quantification by method of isotope dilution/method of internal standard using 5 isotope-
labelled standards.
3.7 g sample material and 75 mL simulant (water) for the migration analysis were applied.
The migration was performed at 37 °C for 1 hour.
The results are stated in Table 12 below.
The 3.7 g sample material corresponded to approx. half of the pad material which was in the
bicycle helmet.
7.2.2 Migration analysis of PFASs
Migration analysis for PFASs was performed for the strap in bicycle helmet C4, however, not
on the very same bicycle helmet on which the screening analyses were performed but on
three new helmets (C4new) with another production date as it was impossible to buy more
bicycle helmets with the same production date.
The strap material from the three new bicycle helmets, named C4newA, C4newB and C4newC
respectively, was mixed to two mixture samples C4newABC-1 and C4newABC-2 which consti-
tuted the duplicate determination as the strap weighs very little in a bicycle helmet compared
to the sample amount which is needed for the analysis. Thus, both quantitative determination
of content of PFASs as well as migration of PFASs on sample material from the same bicycle
helmets (mixture sample of material from three identical bicycle helmets) were performed.
The migration analysis for PFASs in C4newABC was performed in the following way:
Addition of internal isotope-labelled standards and ultrasonic extraction of the homogenised
sample material with matrix-dependent solvents (multi)-step-sample clean-up (depending on
matrix; e.g. SPE).
The analysis is performed by liquid chromatography coupled with mass spectrometry
(LC/MS-MS) with identification via retention time and molecule or fragment ions. The quanti-
fication of the native PFC components is performed via internal isotope-labelled standards.
The quantification limit LOQ is 50-100 ng/L simulant or 0.3-0.7 µg/kg bicycle strap depend-
ent of the substance.
Reference method: DIN 38414-S14 modified to the matrix.
12.4 and 11.9 g sample material respectively was used and 75 mL simulant (water) for the
migration analysis. The migration was performed at 37 °C for 1 hour.
The results are stated in Table 13.
7.3 Results of the migration analyses
The analysis results of the migration analyses for chlorinated phosphorus-based flame retard-
ants and PFASs are stated below.
7.3.1 Analysis results for chlorinated phosphorus-based flame
retardants
The analysis results for the migration analysis for chlorinated phosphorus-based flame retard-
ants of the foam material in C10 are stated in Fejl! Henvisningskilde ikke fundet. below. The
analysis results are stated individually for the two helmets C10A and C10B and as the average
of the two results from the duplicate determination. As earlier mentioned, the two analyses in
the duplicate determination are performed on two bicycle helmets with identical batch number
and production date. Differences in the analysis result can thus be due to both common
measurement uncertainty and individual differences in two bicycle helmets from the same
production date.
The analysis results are stated both as amount of substance per litre of simulant (µg/l) and
amount of substance per amount of sample material (µg/kg). The migration analysis was per-
formed for one hour so the real units are µg/l/hour and µg/kg/hour respectively.
Table 12: Analysis results (migration) for chlorinated phosphorus-based flame retard-
ants in foam material
Flame retardants
C10A
(µg/l/
hour)
C10A
(µg/kg/
hour)
C10B
(µg/l/
hour)
C10B
(µg/kg/
hour)
Aver-
age
(µg/l/
hour)
Aver-
age
(µg/kg/
hour)
Tri-o-cresyl phosphate
< 0.2
< 4
< 0.2
<4
< 0.2
<4
Tricresyl phosphate
< 0.8
<16
< 0.8
<16
< 0.8
<16
Tris(2-chloroisopropyl) phosphate (TCPP)
26,000
530,000
17,500
350,000
21,750
440,000
Tris(1,3-dichloroisopropyl) phosphate
(TDCP)
545
11,000
450
9,100
498
10,050
Tris(2-butoxyethyl) phosphate (TBEP)
< 0.4
<8
< 0.4
<8
< 0.4
<8
Tributyl phosphate (TBP)
< 0.4
<8
< 0.4
<8
< 0.4
<8
Triisobutyl phosphate (TIBP)
1.26
26
1.19
24
1.23
25
(2-Ethylhexyl)-Diphenyl phosphate
(EHDP)
< 0.4
<8
< 0.4
<8
< 0.4
<8
Tris(2-chloroethyl) phosphate (TCEP)
7.79
160
6.11
120
6.95
140
Tris(2-ethylhexyl) phosphate
< 1.1
<23
< 0.518
<11
<0.81
<17
Triphenyl phosphate (TPHP)
0.659
14
0.663
13
0.661
14
< x = less than x, corresponding to the detection limit. As the detection limit depends on the amount of
sample material the detection limit can vary for the same substance in different samples.
From Table 12 it is seen that in the migration liquid the same chlorinated phosphorus-based
flame retardants are identified as those which were identified in the analysis with regard to
content (Table 9), i.e. TCPP, TDCP, TIBP, TCEP and TPHP.
TCPP and TDCP are identified in the largest amounts in the migration liquid 440,000 and
10,050 µg/kg/hour respectively, corresponding to 440 µg/g/hour and 10 µg/g/hour respectively.
TIBP, TCEP and TPHP are identified in smaller amounts in the migration liquid (approx. 0.025
µg/g/hour, 0.140 µg/g/hour and 0.014 µg/g/hour respectively).
7.3.2 Analysis results for PFASs
The analysis results for the migration analysis for PFASs in the bicycle helmet in C4new are
stated in Table 13 below. The analysis results are stated individually for the two samples
C4newABC-1 and C4newABC-2 and as the average of the two results from the duplicate de-
termination. As earlier mentioned, the two analyses in the duplicate determination are per-
formed on a mixture sample of three different bicycle helmets with identical batch number and
production date.
The analysis results are stated as both amount of substance per litre of simulant (ng/l) and
amount of substance per amount of sample material (µg/kg). The migration analysis was per-
formed for one hour so the real units are ng/l/hour and µg/kg/hour respectively.
In general, no PFASs are identified above the detection limit of between 0.3-0.7 µg/kg/hour of
bicycle strap. In Table 13, only the analysis results for the three PFASs which were identified
at the quantitative analysis are stated.
Table 13: Analysis results (migration) for PFASs in bicycle strap
PFASs
C4newABC-1
(ng/l/hour)
C4newABC-1
(µg/kg/hour)
C4newABC-2
(ng/l/hour)
C4newABC-2
(µg/kg/hour)
Perfluorooctanoic acid (PFOA)
< 50
< 0.3
< 50
< 0.4
Perfluorohexane sulphonate (PFHxS)
< 75
< 0.5
< 75
< 0.5
Perfluorohexanoic acid (PFHxA)
< 50
< 0.3
< 50
< 0.4
< x = less than end x, corresponding to the detection limit. As the detection limit depends on the amount of
sample material the detection limit can vary for the same substance in different samples.
7.3.3 Summary of results for the migration analyses
The following migration analyses were performed:
Migration of chlorinated phosphorus-based flame retardants in bicycle helmet C10
Migration of PFASs in bicycle helmet C4
The results of the migration analyses on the pads inside the bicycle helmet show that the
same chlorinated phosphorus-based flame retardants are identified in the migration liquid as
those which were identified in the analysis with regard to content in C10. TCPP and TDCP are
identified in the largest amounts in the migration liquid, 0.044% and 0.001% respectively for
migration for 1 hour, corresponding to 440 ppm and 10 ppm respectively for one hour of mi-
gration. TIBP, TCEP and TPHP are identified in smaller amounts in the migration liquid (ap-
prox. 0.025 ppm, 0.140 ppm and 0.014 ppm respectively for one hour of migration).
The results from the migration analyses of the bicycle strap on C4new show that no PFASs
migrate above the detection limit of between 0.3 and 0.7 µg/kg/hour of bicycle strap dependent
on the individual PFAS.
8. Hazard assessment
A summary (in the form of a table) of the most important data for use in the risk assessment
for the substances which migrate from the bicycle helmets for the two types of migration anal-
ysis in this project (i.e. chlorinated phosphorus-based flame retardants and PFAS compounds)
has been prepared.
Data identified for the substances which migrate from the bicycle helmets is summarised in
Table 14. The reference for the data is stated in the outermost right column and is briefly de-
scribed below. The identified data, i.e. DNEL value (Derived No Effect Level), and values for
skin and oral absorption are used directly in the risk assessment.
It should be noticed that risk assessments have formerly been performed in one or more of the
‘chemicals in consumer products’ surveys carried out for the Danish EPA for the flame retard-
ants TCPP, TDCP and TCEP. The DNEL values and values for skin and oral absorption used
in these projects are used directly in this project. Both Nørgaard Andersen et al. (2014) and
Kjølholt et al. (2015) list dermal and oral absorption values for TCPP of 40% and 80% respec-
tively, and values for TDCP of 30% and 100% for dermal and oral absorption respectively.
Kjølholt et al. (2015) uses an absorption of 100% for TCEP for both dermal and oral absorp-
tion. These values are listed in an EU risk assessment of the substance (EU RAR, 2009). The
former projects used as references are from 2014 and 2015 respectively. For this reason, it is
assumed that the used DNEL values not necessarily have been changed since then.
For the flame retardants TIBP and TPHP, the DNEL values as listed in the ECHA database of
registered substances are used well aware that these values are assessed by the producers
and are not validated by impartial experts. In general, the DNEL values for skin and oral ab-
sorption for the general population are used. As no data for skin and oral absorption is listed
for these two substances, an absorption of 100% is used as a worst-case.
For the PFASs, risk assessments have also been performed in a couple of the former ‘chemi-
cals in consumer products’ surveys carried out for the Danish EPA. Furthermore, an environ-
mental project (Larsen & Giovalle, 2015) has been prepared. In this former project, a health
assessment of PFOA, PFOS and PFOSA has been carried out. This health assessment was
used as a basis of determination of limit values for these substances in drinking water
amongst other things. The survey project Klinke et al. (2016) uses DNEL values from this
environmental project whereas a former survey project (Lassen et al., 2015) states DNEL
values from other literature as the environmental project was prepared simultaneously.
The used DNEL values for PFOA from the different projects are more or less at the same
level. However, the DNEL value for serum (blood fluid), which is stated by RAC in an opinion
on PFOA (ECHA, 2016a), cannot be used directly in the calculations in this project as we do
not have information about serum values when using bicycle helmets with PFASs in the bicy-
cle straps. Larsen & Giovalle (2015) calculates a TDI value (Tolerable Daily Intake) of 0.1
µg/kg bw/day for PFOA. This value is listed as a DNEL value for PFOA in Klinke et al. (2016)
whereas Lassen et al. (2015) lists a DNEL value of 0.08-0.17 µg/kg bw/day based on earlier
literature.
The information available on DNEL values for other PFASs is limited. These are therefore
often assumed on the basis of knowledge of PFOA and PFOS. In Larsen & Giovalle (2015),
they calculate a TDI value of 0.03 µg/kg bw/day for PFOS. In Klinke et al. (2016), they de-
scribe that the Danish EPA decided to use this TDI value for PFOS as a worst-case limit value
for a total sum of 12 PFASs, including PFOA, PFHxS and PFHxA, which have been identified
in a bicycle strap in this project. This DNEL value of 0.03 µg/kg bw/day is therefore used as
DNEL value for the total sum of PFASs in Klinke et al. (2016).
The same choice has been made in this project on bicycle helmets. This means that the DNEL
value of 0.03 µg/kg bw/day is used as the worst-case value for the sum of PFOA, PFHxS and
PFHxA. It is a worst-case value as PFHxS and PFHxA probably are far less toxic than PFOA
(based on knowledge of NOAEL values (No Observed Adverse Effect Level) for PFHxA of
100,000 µg/kg bw/day (Iwai & Hoberman, 2014), for PFHxS of 20,000 µg/kg bw/day (Loveless
et al, 2009) and for PFOA of 60 µg/kg bw/day (Lassen & Giovalle, 2015)).
A value for skin absorption of 2% is used for all PFASs as stated in Lassen et al. (2015). In
Lassen et al. (2015), it is stated that the skin absorption of PFASs is < 2%. A value for oral
absorption of 90% is used as stated in Lassen et al. (2015).
Values used in the risk assessment are marked in bold in Table 14.
Table 14: Data hazard assessment of identified substances by migration analysis
Name of substance
CAS no.
Harmonised classification
DNEL dermal
(µg/kg bw/day)
DNEL oral
(µg/kg bw/day)
Critical effect
Skin / oral
absorption
Reference
Tris(2-chloroisopropyl) phos-
phate (TCPP)
13674-84-5
Harmonised classification:
None
Notified classification:
Acute Tox. 4 H302 (568)
Aquatic Chronic 3 H412 (35)
Eye Irrit. 2 H319 (4)
Skin Irrit. 2 H315 (1)
720*
70
No data
70
Liver damage
40% (derm)
80% (oral)
ECHA registration
dossier
Nørgaard Andersen
et al., 2014
Kjølholt et al., 2015
Tris(1,3-dichloroisopropyl)
phosphate (TDCP)
13674-87-8
Harmonised classification:
Carc. 2 H351
17
5
17
5
Kidney damage
30% (derm)
100% (oral)
ECHA registration
dossier
Nørgaard Andersen
et al., 2014
Kjølholt et al., 2015
Triisobutyl phosphate (TIBP)
126-71-6
Harmonised classification:
None
Notified classification:
Skin Sens. 1 H317 (244)
Aquatic Chronic 3 H412 (134)
Eye Irrit. 2 H319 (30)
Skin Irrit. 2 H315 (39)
Resp. Sens. 1 H334 (23)
2,130
2,130
-
-
ECHA registration
dossier
Tris(2-chloroethyl) phosphate
(TCEP)
115-96-8
Harmonised classification:
Acute Tox. 4 H302
Carc. 2 H351
Aquatic Chronic 2 H411
Repr. 1B H360F
No data
13
No data
13
Kidney damage
100% (derm)
100% (oral)
ECHA registration
dossier
Kjølholt et al., 2015
EU RAR, 2009
Triphenyl phosphate (TPHP)
115-86-6
-
1,980
500
Liver damage
-
ECHA registration
dosier
The Danish Environmental Protection Agency / Survey and risk assessment of chemical substances in bicycle helmets 65
Name of substance
CAS no.
Harmonised classification
DNEL dermal
(µg/kg bw/day)
DNEL oral
(µg/kg bw/day)
Critical effect
Skin / oral
absorption
Reference
Perfluorooctanoic acid (PFOA)
335-67-1
Harmonised classification:
Acute Tox. 4 H302
Eye Dam. 1 H318
Acute Tox. 4 H332
Carc. 2 H351
Lact. H362
STOT RE 1 H372
Repr. 1B H360D
0.08 – 0.17
0.1
0.03
(total PFAS)
0.8 µg/ml serum
0.08 – 0.17
0.1
0.03
(samlet PFAS)
0.8 µg/ml serum
Liver damage
Reprotoxic
effects
2% (derm)
90% (oral)
Lassen et al., 2015
Larsen & Giovalle,
2015
Klinke et al., 2016
RAC opinion, 2016
Perfluorohexane sulfonate
(PFHxS)
355-46-4
Harmonised classification:
None
Notified classification:
None
0.08 – 0.17
0.03
(total PFAS)
0.08 – 0.17
0.03
(total PFAS)
Liver damage
2% (derm)
90% (oral)
Lassen et al., 2015
Klinke et al., 2016
Larsen & Giovalle,
2015
Perfluorohexane sulfonic acid
(PFHxA)
307-24-4
Harmonised classification:
None
Notified classification:
Skin Corr. 1B H314 (29)
Resp. Sens. 2 H335 (3)
Met. Corr. 1 H290 (1)
Eye Dam. 1 H318 (1)
Acute Tox. 3 H301 (1)
Acute Tox. 3 H311 (1)
Acute Tox. 2 H330 (1)
0.08 – 0.17
0.03
(total PFAS)
0.08 – 0.17
0.03
(total PFAS)
Liver damage
2% (derm)
90% (oral)
Lassen et al., 2015
Klinke et al., 2016
Larsen & Giovalle,
2015
* No DNEL value is listed. The value is a DMEL value (Derived Minimum Effect Level). The listed value is for workers and not for the general population.
Values in bold are used in the risk assessment.
9. Exposure calculations
In this chapter exposure calculations are carried out, i.e. calculation of the amount of chlorine
phosphorus-based flame retardants and PFASs which children below the age of 3 years will
be exposed to during use of bicycle helmet C4 and C10 respectively. Exposure calculations
are carried out for the following scenarios:
Dermal exposure for chlorine phosphorus-based flame retardants in pad materials in C10
Dermal exposure for PFASs in bicycle straps in C4
Oral exposure for PFASs in bicycle straps in C4 (if the child sucks on a piece of the strap)
Even though no migration of PFASs from the strap in the bicycle helmet C4 was identified in
the migration analysis to water, an exposure calculation has been performed and the detection
limit has been used as the value for the amount migrating.
It is not considered to be likely that a child will suck on the pads fastened inside the bicycle
helmet. The pads must be taken out of the helmet for this scenario to be possible as the pads
are fastened with Velcro. At normal use of the bicycle helmet C4, it is not possible to get a
piece of the strap which has been analysed in this project into the mouth. This part of the bicy-
cle helmet is two pieces of rope which are situated around both ears and not under the chin.
On these two pieces of robe around the ears, a strap is attached and this strap is fastened
under the chin. The strap which goes under the chin (it looks like the straps from other bicycle
helmets) has not been analysed in this project.
A worst-case scenario for oral exposure for the PFASs which migrate from the rope is calcu-
lated if a child should suck on this part of the strap, e.g. if the child sits with the bicycle helmet
in its hand before departure/transport by bicycle with the bicycle helmet on the head.
9.1 Method for calculation of dermal exposure
As a basis for calculation of the dermal exposure, which young children will be exposed to by
use of bicycle helmets, the model for calculation of dermal exposure stated by ECHA is used.
According to the REACH Guidance on consumer exposure assessment (ECHA, 2016b), the
exposure for a substance migrating from a product can be described by the formula below
(appendix R.15.5).






   

where
D
der
Dermal dose, i.e. the amount of substance, which potentially
can be absorbed per kg body weight. Later in the calculations
the dermal absorption rate of the substance is considered
mg/kg bw/day
Q
prod
Amount of product used
g
F
prod
Weight fraction of substance in the product
g/g product
F
migr
Rate (fraction) of substance migrating to skin per unit time
(hours)
g/g/hours
F
contact
Fraction of contact area for skin, to account for the fact that the
product is only partially in contact with the skin (default value =
1)
cm
2
/cm
2
T
contact
Contact duration between product and skin
hours
n
Mean number of events per day
/day
BW
Body weight
kg
In this project, where migration analyses have been carried out, the result from the migration
analyses can be used directly instead of the weight fraction of the substances in the product
(F
prod
). In this case, this means that the analysis result from the migration (migrated substance
per g product per time) multiplied with the total weight of the pad material in C10 (Q
prod
) corre-
sponds to the total amount of substance that can migrate from the pads in the bicycle helmet.
Furthermore, it is not the entire amount of the migrated chlorine phosphorus-based flame
retardants that are absorbed through the skin. In the calculations, the actual possible fraction
which can be absorbed is accounted for. The modified formula used for calculation of the ex-
posure in this report is therefore:







 

where
D
der
Dermal dose, i.e. the amount of substance, which potentially
can be absorbed per kg body weight. By use of F
abs
the dermal
absorption rate of the substance is considered
µg/kg bw/day
Q
prod
Amount of product used
g
MG
prod
Amount of substance, which migrates per amount of product
per unit time (here: migration time is 1 hour)
µg/g/hours
F
contact
Fraction of contact area for skin, to account for the fact that the
product is only partially in contact with the skin (default value =
1)
-
T
contact
Contact duration between product and skin
hours
F
abs
Fraction of substance absorbed through skin
-
n
Mean number of events per day
/day
BW
Body weight
kg
As the point of departure, the calculations are carried out for a worst-case scenario, which
afterwards can be refined, if the calculations result in a risk. As part of this worst-case scenario
it is assumed that e.g. the measured migrations are constant over the used exposure time.
9.2 Method for calculation of oral exposure
As the point of departure, for the calculation of the oral exposure, which young children will be
exposed to by use of bicycle helmets, the formula as listed above for dermal exposure is used,
but modified for oral exposure.









where
D
oral
Oral dose, i.e. the amount of substance, which potentially can
be absorbed per kg body weight. By use of F
abs
the oral ab-
sorption rate of the substance is considered
µg/kg bw/day
Q
prod
Amount of product used
g
MG
prod
Amount of substance, which migrates per amount of product
per unit time (here: migration time is 1 hour)
µg/g/hours
F
contact
Fraction of product in the mouth, to account for the case where
the product is only partially in contact with the mouth (default
value = 1)
-
T
contact
Contact duration between product and mouth
hours
F
abs
Fraction of substance absorbed orally
-
n
Mean number of events per day
/day
BW
Body weight
kg
9.3 Used exposure values
The following values are used for the exposure calculations in this project:
Dermal (D
der
) / Oral (D
oral
) exposure
D
der
and D
oral
are the calculated dermal and oral exposure respectively of a specific substance.
This exposure is used in the risk assessment. The dermal exposure illustrates the exposure
when the bicycle helmet is worn at transport on bike. The oral exposure illustrates the expo-
sure when the child sucks on parts of the bicycle helmet, e.g. right before departure/transport
on bike. It is not possible to put the parts, of which a risk assessment is carried out, into the
mouth during transport where it is assumed that the bicycle helmet will be worn correctly on
the head.
Amount of product (Q
prod
)
Q
prod
is the total weight of pads inside the bicycle helmet C10 where a migration of chlorine
phosphorus-based flame retardants has been identified and the total weight of strap in the
bicycle helmet C4 where a migration of PFASs is identified.
For C10 the total weight of all pads in the bicycle helmet of 7.45 g is used even though not all
pads in the bicycle helmet are in direct contact with the skin. C10 consists of a total of four
pads inside where one pad is situated in the forehead (probably with direct skin contact), two
pads are situated in each side of the helmet and the last pad is situated in the top of the hel-
met. The two pads in the sides of the helmet as well as the pad in the top of the helmet proba-
bly do not have any direct skin contact as the hair of the child will be between the pads and the
scalp. In the winter where the child carries a knitted hat under the bicycle helmet the skin con-
tact will be even smaller.
Similar for C4, the total weight of in all 2 x 13 cm bicycle strap, i.e. 7.0 g strap corresponding to
the strap going from the edge of the helmet and around the ears is used for the calculation of
the dermal exposure. C4 is constructed with two different types of straps where fluorine has
been identified in the strap (rope) going around the ears. It is the total weight of this rope that
is used in the calculations.
A calculation of oral exposure is also carried out if a young child should suck on this rope.
However, it must be emphasised that it is not possible to put this rope into the mouth, when
the child wears the helmet correctly, but only when for example the child sits with the bicycle
helmet in its hands or plays with the helmet. Here as worst-case it is decided to use an amount
of 4 cm of rope, corresponding to the part of the rope that is possible for the child to get into
the mouth because the rope is attached in both ends to the edge of the bicycle helmet.
Migration (MG
prod
)
MG
prod
is the amount of substance which at chemical analysis has shown to migrate out of the
product to water at 37 °C for 1 hour (is equal to the result of the migration analysis).
Fraction of area in contact with skin/mouth (F
contact
)
F
contact
is the fraction of the product which is in contact with the skin or the mouth.
A value of 0.5 is used for skin contact for the pads inside the helmet of C10 and for the strap of
C4 because it is only the one side of the pads and the strap which is in contact with the skin.
The pads in C10 are about 0.5 to 1 cm thick and the strap of C4 is a round rope with a diame-
ter of about 1 cm.
A default value of 1 is used for contact with the mouth as it is assumed that the child has the
entire piece of strap with a diameter of about 1 cm in the mouth.
Contact time (T
contact
)
T
contact
is the time in hours which the bicycle helmet is worn by the child. In this project, a con-
tac time of 30 minuttes (0.5 hours) has been used as a worst-case contact time for dermal
contact each time the bicycle helmet is worn.
For the situation with oral exposure a contact time of 10 minutes is used corresponding to the
time it is assumed the child will have the bicycle helmet in its hands before departure/transport
on bike. It is not possible for the child to suck on the part of the strap where PFASs have been
identified when the helmet is worn correctly on the head.
Absorption (skin or oral (F
abs
))
F
abs
is the fraction of the substance which is absorbed through skin or via the mouth. The
fraction is listed in Table 14 and specific values are used if available. Otherwise 100% is used
as a worst-case when data is missing.
Events per day (n)
As mentioned earlier, the total exposure time is assumed to be 1 hour corresponding to 30
minutes of transport in each direction (e.g. to and from day care centre). The mean number of
events per day, n, where the young children wear the bicycle helmet is assumed to be 2 per
day, corresponding to transport to and from e.g. day care centre.
Body weight (BW)
Based on RIVM (2014), the value of 9.8 kg as the body weight of a child under 3 years has
been chosen. ECHA (2016b) refers to default values in RIVM (2014). Here it is stated that the
average weight for 1-2-year-old Dutch children is 9.8 kg and that the average weight for 2-3-
year-old Dutch children is 12.4 kg. As a worst-case value the lowest value, i.e. 9.8 kg is used,
which will result in the highest exposure (D
der
/D
oral
).
9.4 Exposure calculations
The different parameters and values which are used in the exposure calculation for C10 are
summarised in Table 15 where the dermal dose (D
der
) for the flame retardants also is calculat-
ed.
Table 15: Exposure calculation of dermal exposure to C10
Substance
TCPP
TDCP
TIBP
TCEP
TPHP
Q
prod
(g)
7.45
7.45
7.45
7.45
7.45
MG
prod
(µg/g/hour)
440
10.05
0.025
0.14
0.014
F
contact
(-)
0.5
0.5
0.5
0.5
0.5
T
contact
(hours)
0.5
0.5
0.5
0.5
0.5
F
abs
(-)
0.40
0.30
1
1
1
n (per day)
2
2
2
2
2
BW (kg)
9.8
9.8
9.8
9.8
9.8
D
der
(µg/kg bw/day)
66.898
1.146
0.010
0.053
0.005
Similar the different parameters and values used in the exposure calculation for C4 are sum-
marised in Table 16 and Table 17 where the dermal exposure (D
der
) for the PFASs is calculat-
ed when a child wears the bicycle helmet and the oral exposure (D
oral
) for the PFASs when a
child sucks on the strap of the bicycle helmet before departure/transport on bike. As men-
tioned earlier, the detection limit has been used as the value for the amount migrating, as no
migration of PFASs from the strap in the bicycle helmet C4 was identified in the migration
analysis. The calculation has been performed to ensure that no health risk exists from a possi-
ble migration below the values for which it is possible to analyse.
Table 16: Exposure calculation of dermal exposure to C4
Substance
PFOA
PFHxS
PFHxA
Q
prod
(g)
7
7
7
MG
prod
(µg/g/hour)
0.0004
0.0005
0.0004
F
contact
(-)
0.5
0.5
0.5
T
contact
(hours)
0.5
0.5
0.5
F
abs
(-)
0.02
0.02
0.02
n (per day)
2
2
2
BW (kg)
9.8
9.8
9.8
D
der
(µg/kg bw/day)
2.9 E-06
3.6 E-06
2.9 E-06
Table 17: Exposure calculation of oral exposure to C4
Substance
PFOA
PFHxS
PFHxA
Q
prod
(g)
7
7
7
MG
prod
(µg/g/hour)
0.0004
0.0005
0.0004
F
contact
(-)*
0.154
0.154
0.154
T
contact
(hours)**
0.167
0.167
0.167
F
abs
(-)
0.9
0.9
0.9
n (per day)
1
1
1
BW (kg)
9.8
9.8
9.8
D
oral
(µg/kg bw/day)
6.6 E-06
8.2 E-06
6.6 E-06
* Here a fraction of 4 cm out of 26 cm has been used
** Here a fraction of 1/6 hours has been used
10. Risk assessment
As described earlier, the purpose of this project has been to investigate whether the content of
the identified problematic chemical substances in bicycle helmets can be hazardous to health
for children.
The method used for calculating the risk is stated below. As described earlier, no hazard as-
sessment has been performed for the substances investigated in this project and migrating
from the bicycle helmets. However, the DNEL values which are used in the reports Nørgaard
Andersen et al. (2014), Kjølholt et al. (2015), Lassen et al. (2015) and Klinke et al. (2016) are
used in this report as well (see values marked in bold in Table 14).
10.1 Method for calculation of the risk
In principle, exposure to substances in bicycle helmets can happen through the different expo-
sure pathways – dermal, oral and by inhalation. Exposure to substances that evaporate from
the bicycle helmets is considered to be negligible and will moreover be considerably diluted in
outdoor air. Oral exposure, i.e. if the children sucks on the bicycle helmet, is assumed to be
irrelevant in the actual use situation as it is not possible to suck on either the pads inside the
helmet of C10 or the part of the strap that has been analysed for PFASs in C4. On the contra-
ry, it will be possible for a child to suck on the examined strap in C4 when the helmet is not
worn, but it is not considered to be likely that a child will suck on the pads inside the helmet as
these pads in that case will have to be taken out of the helmet first (they are attached with
Velcro). Therefore, a calculation of the exposure through skin (the dermal exposure D
der
) for
C10 and C4 as well as a calculation of the oral exposure (D
oral
) for C4 has been calculated in
this project. The oral and dermal exposure to PFASs in C4 are added up in order to get the
total exposure.
According to the REACH Guidance document on risk assessment (ECHA, 2016c), it should be
assessed in each single case whether a risk of health hazards exists by use of the following
formula. The risk is expressed as Risk Characterisation Ratio (RCR), which is calculated as
the ratio between the size of the exposure (D
der
or D
oral
) and the Derived No Effect Level
(DNEL):




If RCR > 1 (i.e. the exposure is higher than the DNEL) a risk exists. If RCR < 1, the exposure
is not considered to constitute a risk.
Exposure to different substances with the same effect (in this project several different flame
retardants or several different PFASs that result in liver damage) can be characterised as
cocktail effects. Cocktail effects from several substances with the same effect can be calculat-
ed as an additive effect by use of the dose-addition principle, which has also been in several of
the former survey projects from the Danish EPA.
Therefore, the total, i.e. additive risk is calculated by adding up the RCR values of the single
substances (1 to n):





  
It is only for substances from the same bicycle helmet with the same effects where the RCR
values are added up, as it is assumed that no children use more than one bicycle helmet (e.g.
C4 and C10) at the same time.
10.2 Risk assessment
In the risk assessment, the calculated exposure (the calculated dermal exposure D
der
or the
calculated oral exposure D
oral
) is compared with the DNEL value. The used DNEL values for
these substances which migrate from the bicycle helmets C4 and C10 in this project are listed
in Table 14.
The calculated RCR values for these flame retardants and PFASs are listed below for C10
(Table 18) and C4 (Table 19) respectively. The total sum of the RCR values (RCR total) for
TCPP and TPHP respectively, as well as TDCP and TCEP has been calculated as these sub-
stances according to Table 14 have the same critical effect, i.e. liver damage and kidney dam-
age. Correspondingly, the sum of the RCR values for PFASs has been calculated, as these
substances also have the same critical effect (liver damage).
Table 18: Risk assessment (calculation of RCR-values) for C10
Substance
D
der
(µg/kg bw/day)
DNEL
(µg/kg bw/day)
RCR
RCR
total
TCPP
66.898
70
0.96
0.96
TPHP
0.005
1,980
0.000003
TDCP
1.146
5
0.23
0.23
TCEP
0.053
13
0.004
TIBP
0.010
2,130
0.000004
-
It is evident from Table 18 that all calculated RCR values are below 1, with the highest RCR
value for TCPP of 0.96. The RCR value for TCPP of 0.96 is, however, close to 1 and is the
only value which is close to 1. However, several aspects of the calculation cause the calcula-
tion to be a worst-case calculation and therefore indicate that the actual exposure will be con-
siderable smaller:
A total exposure time of 1 hour has been used in the calculations. This is a long transporta-
tion time on bike for a little child, and this exposure time will probably be shorter for most
young children.
Moreover, the exposure has been calculated by use of the migration from all four pads in the
bicycle helmet, where it primarily is the pad placed in the forehead that will be in direct con-
tact with the skin. For most young children, the hair of the children will be in between the
pads inside the helmet and the scalp.
Finally, different conditions regarding the actual migration analysis are relevant for the calcu-
lations and lead to worst-case conditions for the calculations:
For the migration analysis, a total amount of migration fluid of 75 ml was used (in or-
der to be able to carry out the analysis in practice) and the intact pads were sub-
merged in the fluid. This means that in practice the pads were soaked with fluid. It is
not assumed that in practice a young child who rides on its parents’ bike or rides on
its own bike will sweat that much so such a large amount of the flame retardant will
migrate when the helmet is worn.
In C10 a total amount of TCPP of 19,550 µg/g and a migration of 440 µg/g/hour were
identified, i.e. in theory the total amount of TCPP will migrate out of the pads in about
44 hours (or 44 days with 1 hour of use/day) provided that the rate of migration is
constant and that the pads are soaked with sweat each time.
Therefore, the assessment is that there is no real health risk when a child carries the C10
bicycle helmet each day for a longer period – even though the highest RCR value (for TCPP)
is close to 1. Similar, there is no real health risk even though the RCR values for several of the
substances with the same critical effect are added up. The total RCR values for the same
critical effect are still below 1.
Table 19: Risk assessment (calculation of RCR values) for C4
Product (substance)
D
der
/ D
oral
(µg/kg bw/day)
DNEL
(µg/kg bw/day)
RCR
RCR
Total
(dermal and oral)
PFOA (dermal)
2.9 E-06
0.03
-
0.001
PFHxS (dermal)
3.6 E-06
PFHxA (dermal)
2.9 E-06
Total PFAS (dermal)
9.3 E-06
0.03
0.0003
PFOA (oral)
6.6 E-06
PFHxS (oral)
8.2 E-06
PFHxA (oral)
6.6 E-06
Total PFAS (oral)
2.1 E-05
0.03
0.0007
Table 19 illustrates that the total RCR values for the PFASs are well below 1. This means that
there is no health risk for a child to wear the bicycle helmet C4 each day for a longer period.
Even though a worst-case overall DNEL value has been used for all PFASs, no health risk
exists. The total RCR value for both dermal and oral exposure for all PFASs is still significantly
below 1 with regard to the chemical substances investigated in this project.
Furthermore, it should be emphasised that the analyses did not result in a migration of PFASs
from the strap in C4 but that the detection limit has been used for the calculations. This calcu-
lation has been made to ensure that a migration lower than the detection limit could constitute
a health risk.
10.3 Conclusion
In this project, chlorine phosphorus-based flame retardants have been identified in pads inside
one single bicycle helmet (out of 16) and PFASs have been identified in a strap in one single
bicycle helmet (out of 16). The flame retardants migrate from the pads, but no migration of
PFASs from the strap was identified.
Based on the risk assessment results calculated in this project, it can be concluded that even
though flame retardants have been identified inside the pads in a single bicycle helmet (out of
16) and even though these problematic substances migrate from the bicycle helmet and
thereby can be absorbed through the skin of the young children wearing these helmets, the
amounts are on a level that seen in isolation does not constitute a health risk for liver damage,
which is the critical effect of the flame retardant TCPP (with the highest RCR value). In addi-
tion, the amounts do not constitute a health risk even when adding up the amount of the differ-
ent flame retardants with the same health effect.
However, it should be noted that numerous PFASs exist and chemical analyses were only
carried out in this project for 33 selected PFASs. Therefore, it may be possible that other
PFASs are present in the bicycle helmets investigated in this project and that these com-
pounds may migrate but these chemical analyses have not been carried out in this project, as
they are not a part of the standard analyses for PFASs.
Former studies have shown that children are also exposed to the same flame retardants and
the same PFASs from other consumer products. A selection of the results from the latest sur-
veys from the Danish EPA is listed below:
Furniture (PFAS-compounds), RCR = 0.0026 (Klinke et al., 2016)
Snowsuit + contribution from indoor environment (PFASs), RCR = 0.008 (Lassen et al.,
2015)
Total contribution from indoor environment (TDCP), RCR = 0.65 (Nørgaard Andersen et al.,
2014)
Total contribution from indoor environment (TCPP), RCR = 0.07 (Nørgaard Andersen et al.,
2014)
In the Danish EPA survey about child safety seats and other children products with textiles
(Kjølholt et al., 2015), RCR values above 1 (corresponding to a possible health risk) were
identified for TDCP in one single child safety seat and baby mattress, and for TCEP and TCPP
in one single baby carrier. For the other investigated products, the RCR values were between
0.06 and 0.81. Overall, the flame retardants may constitute a health risk provided that the
same child is exposed to the specific investigated products at the same time. However, it
should be pointed out that in general worst-case assumptions have been used and that the
calculations contain uncertainties.
Even though the calculated RCR values are below 1 for the bicycle helmet C10 investigated in
this project, they contribute to the total exposure to these flame retardants in different children
products which children use daily.
Looking only at the bicycle helmets, none of the investigated helmets constitutes a health
problem with regard to the chemical substances investigated in this project. Moreover, it
should be emphasised that it was only in two bicycle helmets out of 16 analysed helmets
where either flame retardants were identified in the pads or where PFASs were identified in
the strap. Most of the examined bicycle helmets investigated in this project do not contain
neither the investigated chlorine phosphorus-based flame retardants nor PFASs.
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The Danish Environmental
Protection Agency
Haraldsgade 53
DK-2100 København Ø
www.mst.dk
Survey and risk assessment of chemical substances in bicycle helmets
The purpose of this project has been to examine whether the content of the possibly
problematic chemical substances in bicycle helmets can be hazardous to children’s
health. In total 16 different bicycle were purchased. The screening analyses showed
a small content of both chlorine and phosphorus in a single bicycle helmet (C10). A
content of fluorine just above the detection limit of 5 ppm was identified in C6 and
C10 as well as a high fluorine con-tent of 92 ppm in C4. Quantitative analyses of
certain chlorinated phosphorus-based flame retardants in the pad material in C10
were performed as well as of certain PFASs in bicycle straps on C4, C6 and C10.
The results showed that in the pad material in C10, the flame retardants TCPP and
TDCP were identified in large amounts and that TIBP, TCEP and TPHP were identi-
fied in small amounts. A few PFASs were identified in the strap in C4 in small
amounts but no PFASs above the detection limit were identified in the straps from C6
and C10. The results of the migration analyses on the pads inside the bicycle helmet
showed that the same chlorinated phosphorus-based flame retardants were identified
in the migration liquid as identified at the content analysis carried out on C10 (TCPP
TDCP,TIBP, TCEP and TPHP. The results of the migration analyses on the bicycle
strap on C4 showed that no PFASs migrate above the detection limit. Looking only at
the bicycle helmets, none of the investigated helmets constitutes a health problem
with regard to the chemical substances investigated in this report.