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Analysis of selected groups of endocrine disruptors REPORT M-590 | 2016 Survey of endocrine disruptors in toys and articles for children
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Page 1: Survey of endocrine disruptors in toys and articles …...Survey of endocrine disruptors in toys and articles for children | M-590 6 5. Results and discussion In total, 58 samples

Analysis of selected groups of endocrine disruptors

REPORT

M-590 | 2016

Survey of endocrine disruptors in

toys and articles for children

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1

COLOPHON

Executive institution

ALS Laboratory Group Norway AS

Project manager for the contractor Contact person in the Norwegian Environment Agency

Ingrid Håøy Nygård

M-no Year Pages Contract number

M-590 2016 13 [Contract number]

Publisher The project is funded by

Norwegian Environment Agency Norwegian Environment Agency

Author(s)

Trine-Lise Torgersen

Title – Norwegian and English

Survey of endocrine disruptors in toys and articles for children

Undersøkelse av hormonforstyrrende stoffer i leker og barneprodukter

Summary – sammendrag

58 samples of toys and other articles for children were analysed for phthalates, bisphenols,

alkylphenols and –etoxilates, and/or chlorinated parafins. Some of the substances were detected in

few samples, but in most of the samples analysed, none of the substances were found. The most

noticeable finding was significant amounts of bisphenol A in many of the samples of soft polymer

analysed.

58 prøver av leker og andre barneprodukter ble analysert for ftalater, bisfenoler, alkylfenoler og –

etoksilater, og/eller klorparafiner. Noen an stoffene ble funnet i noen av prøvene, men i en stor del

av de undersøkte prøvene ble ingen av stoffene påvist. Det mest påfallende funnet var betydelige

nivåer av bisfenol A i mange av prøvene av myk plast som ble undersøkt for bisfenoler.

4 emneord 4 subject words

hormonforstyrrende leker produkter barn Endocrine toys articles children

Front page photo

John Petter Reinertsen

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Content

1. Summary and conclusion .................................................................................. 3

2. Sammendrag og konklusjon ............................................................................... 3

3. Background and aim of the project ..................................................................... 3

4. Materials and methods ..................................................................................... 4

5. Results and discussion ..................................................................................... 6

6. Concluding remarks ........................................................................................ 7

7. Appendices ................................................................................................... 8

7.1 Appendix 1 – Results presented in a table format .............................................. 8

7.2 Appendix 2 – Abbreviations ....................................................................... 12

7.3 References ........................................................................................... 12

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1. Summary and conclusion

A screening survey of selected groups of endocrine disruptors (EDCs) was conducted with 58

samples of toys and other articles for children. The majority of the articles examined were

made from soft polymer (PVC or PU), but some articles made from other materials were also

included in the survey. Samples were analysed for one or several of the following; phthalates,

bisphenols, chlorinated paraffins and alkylphenols/alkylphenol etoxilates. Only some of the

compounds analysed were detected in the samples, but the majority of samples did not

contain any of the substances analysed. Levels varied from traces to relatively high amounts.

The detection of bisphenol A in more than half of the samples where bisphenols were

examined give rice to some concern, especially since some parts of articles that children are

likely to place in their mouths had relatively high levels. However, since migration was not

measured for any of the detected substances, it was not possible to estimate risk of exposure

of any of the substances from the articles in questions.

2. Sammendrag og konklusjon

Utvalgte grupper hormonforstyrrende stoffer ble undersøkt i 58 leker og andre

barneprodukter. De fleste av produktene var laget av myk plast (PVC eller PU), men også

noen produkter av andre materialer ble undersøkt. Prøvene ble undersøkt for en eller flere av

følgende grupper: ftalater, bisfenoler, klorparafiner og alkylfenoler/alkylfenolektoksilater.

Kun noen få av stoffene ble påvist i prøvene, og nivåene varierte fra spormengder til relativt

høye konsentrasjoner. De fleste produktene inneholdt ingen av de undersøkte stoffene.

Bisfenol A ble funnet i over halvparten av prøvene som ble analysert for bisfenoler, i noen

tilfeller i relativt høye konsentrasjoner i deler av produktene som det er sannsynlig at barn vil

putte i munnen. Dette gir grunn til bekymring. Imidlertid ble det ikke utført

utlekkingsanalyser for noen av de stoffene som ble påvist, så det er ikke mulig å estimere

eksponeringsrisiko for noen av stoffene fra de produktene det er snakk om.

3. Background and aim of the project

Chemicals are an essential component of our daily lives, and are important for function and

properties of the articles we use and need every day. Some chemicals, however, can be

harmful for humans and/or for the environment. Some chemicals can interfere with the

endocrine (hormone) systems of humans and wildlife, with potentially adverse effects. These

chemicals are referred to as endocrine disrupters (ECDs).

Endocrine disrupters interfere with natural hormone systems, and health effects can appear

long after the exposure has stopped. Exposure to ECDs in critical developmental stages can

interfere with sexual development in both humans and animals. Exposure to endocrine

disrupters in the womb can have life-long effects and can even have consequences for the

next generation. Babies and young children are also especially vulnerable to exposure from

ECDs, both because their bodies and organs are not fully developed and are changing rapidly,

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and because their intake of substances relative to their body weight is high compared to

adults.

Children spend a lot of time interacting with their toys, and toys are subject to close body

contact as well as being sucked on, bitten into and licked. There is a huge potential for

exposure of harmful substances to children from toys through the skin or via oral intake. It is

important to minimize children’s risk of exposure to harmful chemicals via their toys, and

toys in Europe are strictly regulated with respect to harmful chemicals. There is, however, a

lack of specific regulations concerning ECDs in toys, and to how to handle substances with

known or suspected endocrine disrupting properties at low concentration. There is also a lack

of knowledge regarding the potential for occurrence of ECDs in toys. The present survey was

conducted as a screening of the presence of selected ECDs in toys and other children’s

articles on the Norwegian market.

The chemicals measured was selected by cross-referencing the EU list of ECDs or suspected

ECDs with substances categorised as ECDs on the SIN-list* and the Norwegian list of priority

substances. From the resulting list of substances, a further selection was made from those

considered likely to be present in the type of materials often used in toys. This lead to the

following list of chemicals to be measured in selected types of toys or other children's articles

made from selected materials:

Phthalates

Nonyl- and octylphenol and their etoxilates

Short- and medium chained chlorinated paraffins

Bisphenols

4. Materials and methods

Children are particularly vulnerable to endocrine disrupters. Hence, the current project is

focused on articles for children, and more specifically the parts of the articles that can (and

are likely to) be put in the mouth by a child. The type of articles were not limited to articles

for very young children, who are generally more inclined to mouthing of toys and other items,

but were selected from items that also older children may be likely to suck, chew or lick on.

In addition to oral exposure, the potential for dermal exposure or leaking of chemicals into

children’s indoor environment was considered when selecting articles.

A total of 58 toys and other articles for children were purchased for the project. The articles

were predominantly made from hard and soft plastics/polymers and rubber/silicone. In

addition, a number of outdoor clothing items made from water and/or wind repellant

material, and some appendages and accessories to the clothes, were obtained. Articles were

purchased in toy stores, bookstores and sports shops in the period April – June 2014. Not all

samples were analyzed for all chemicals. Details of samples and analysis are given in

appendix 1.

The samples were analyzed by ALS Laboratory Group Norway AS or their sub-contractors, in

the period September – November 2014.

* SIN-list: Substitute It Now: http://chemsec.org/what-we-do/sin-list

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Phthalates were extracted with an organic solvent in an ultrasound bath, and determined by

GC-MS according to DIN-19742:2012-04, with a limit of quantification (LOQ) at 0.05 % (w/w).

Details of which substances were determined in the analysis are given in table 1.

Short- and medium-chained chlorinated paraffins were determined by GC-NCI/MS according to

ISO 12010, with an LOQ at 0.10 mg/kg. Short-chained chlorinated paraffins (SCCP) have 10-13

carbon chain lengths, while medium-chained chlorinated paraffins (MCCP) have 14-17 carbon

chain lengths. Individual compounds in each group were not quantified. Results were given as

sum SCCP or sum MCCP.

Nonylphenol (NP), octylphenol (OP), and their etoxilates (NPe and OPe, respectively), were

determined using GC-MS according to EN ISO 18857-2. Individual substances were not

quantified. Results are given as sum NP, sum OP, sum NPe and sum OPe.

Bishpenol A was extracted with an organic solvent in an ultrasound bath, and determined by

GC-MS according to EN ISO 22032:2009-07, while other bisphenols were determined by GC-MS

according to ASTM D7574:2009. LOQ for all bisphenols were 1 mg/kg. Details of which

substances were determined are listed in table 1.

In the methods for phthalates and bisphenols, the following substances were determined:

Table 1: List of substances measured in the determination of phthalates and bisphenol

List of substances measured – phthalates and bisphenols

PHTHALATES BISPHENOLS

Substance Cas no Substance Cas no

DEHP 117-81-7 BPA 80-05-7

DBP 84-74-2 BPAF 1478-61-1

BBP 85-68-7 BPAP 1571-75-1

DINP 28553-12-0 BPB 77-40-7

DIDP 26761-40-0 BPBP 1844-01-5

DNOP 117-84-0 BPC 79-97-0

DIPP 605-50-5 BPC2 14868-03-2

DnHP 84-75-3 BPE 2081-08-5

PIPP 776297-69-9 BPF 87139-40-0

BMEP 117-82-8 BPFL 3236-71-3

DIBP 84-69-5 BPG 127-54-8

DEP 84-66-2 BPM/P 13595-25-0/2167-51-3

DCHP 84-61-7 BPPH 24038-68-4

MEHP 4376-20-9 BPS 80-09-1

MBP 131-70-4 BPT

DPrP 131-16-8 BPZ 843-55-0

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5. Results and discussion

In total, 58 samples of toys or other articles for children were analysed for one or more of the

groups of substances described above. Of these, 28 samples were made from “soft polymer”,

several of which were most likely PVC. Ten samples were wet weather clothes made from

polyurethane. The rest of the samples were made of rubber/latex/elastan, textiles/synthetic

fibres or other polymers (hard polymers), and there were a few samples of modelling clay and

slime.

Details of samples, analysis and results are presented in appendix 2.

Phthalates were only detected in six of the 50 samples where this was examined. In three of

the samples only trace amounts were found, 0.11 % DIBP, 0.17 % DEP and 0.29 % DEHP,

respectively. In the remaining three samples, DEHP was found in concentrations of 3.5 %, 15 %

and 19 %. All of the phthalates were found in samples of “soft polymer”, most likely PVC. All

articles where phthalates were detected fall outside the scope of the restriction of phthalates

in toys and childcare articles (REACH annex XVII, entries 51 and 52). However, some of the

articles (pendants and fabric of outdoor clothing), are articles that children can put in their

mouth and chew or suck on for longer periods. The risk of exposure from these articles have,

however, not been estimated.

Short-chained chlorinated paraffins (SCCPs) were detected in three of 41 analysed samples. A

pencil case was found to contain 1600 mg/kg (0.16 %), the fabric of a rain jacket contained

5100 mg/kg (0.51 %) and 66 000 mg/kg (6.6 %) was found in the zipper pendant of another

rain jacket. In the first two samples, medium-chained chlorinated paraffins (MCCPs) were also

measured, at levels of 3400 mg/kg and 7600 mg/kg, respectively. SCCPs are prohibited in

articles through the POPs regulation (regulation (EC) no 850/2004). Accordingly, the two rain

jackets were non-compliant articles, and was withdrawn from the market. The 0.16 % SCCPs

found in the pencil case, was considered an unintentional trace contaminant, hence the

pencil case was not considered a non-compliant article. The content of 66 000 mg/kg (6.6 %

by weight) in the zipper pendant of one of the rain jackets, is of particular concern, as this is

a part of the jacket that children may put in their mouth, increasing the risk of oral exposure

to SCCPs from this article.

In addition to the above-described findings of chlorinated paraffins, trace amounts of MCCPs

were detected in zipper pendant from a third rain jacket. The same zipper pendant also

contained trace amounts (0.29 %) of DEHP.

Nonylphenols (NFs) were found in three of 16 samples analysed, in concentrations from

23 mg/kg to 670 mg/kg. All samples were soft polymer (possibly PVC). In a fourth sample of a

soft polymer, 12 mg/kg nonylphenol etoxilates (NPEs) were detected. At the time of testing,

there were no restrictions for these compounds in the samples were they were detected.

A surprisingly high number of the samples that were analysed for bisphenols came out positive

for bisphenol A (BPA). Bisphenols were only measured in 16 samples, and BPA was found in

nine of them. Of these, eight of the samples were made from soft polymer, most likely PVC.

In the PVC samples, trace amounts (2.6 mg/kg) was detected in one item, in the remaining

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seven articles, levels of BPA was between 16 mg/kg and 160 mg/kg. In one sample made from

hard polymer, 1.1 mg/kg BPA was measured. This level was just above the detection limit of

1 mg/kg. No other bisphenols were found in any of the samples analysed.

At the time of purchase of the samples, BPA was restricted in toys if the under the general

ban on CMR-substances in toys. However, the ban in not applicable if the content of the

substance is below the classification limit for substances, in this case the limit for

classification at the time was 5 %. The detected levels were well below this limit. Hence, the

articles in question were compliant with relevant legislation.

Some of the samples where the highest levels of BPA were detected were pendants or

appendages of such size and shape that children can, and most likely will, put them in the

mouth. If BPA were to migrate from these articles, there is a risk of oral exposure of BPA

from these articles. However, as migration analysis were not conducted as part of this

project, the risk of BPA exposure, cannot be estimated.

6. Concluding remarks

Of the 58 samples analysed in this survey, only a few of the selected EDCs were found in

significant levels in relatively few of the samples. Two articles were withdrawn from the

market due to content of SCCPs. In the remaining cases where substances were detected,

either the articles were outside the scope of a regulation, or levels detected were below

regulatory limits. Still, some findings give rise to concern. In particular, the detection of BPA

in more than half of the samples analysed may initiate further investigations of the presence

of BPA/other bisphenols in articles for children.

*CMR = Carcinogenic, mutagenic or toxic to reproduction

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7. Appendices

7.1 Appendix 1 – Results presented in a table format

Overview of samples, which analysis were conducted and concentration of substances when detected

Article User group Analyses Findings

< 3

6 m

onth

s

> 3

6 m

onth

s

Phta

late

s

Chlo

ro-p

ara

fins

Alk

ylp

henols

and -

eto

xilate

s

Bis

phenols

DEH

P (

%)

DIB

P (

%)

DEP (

%)

SC

CP (

mg/k

g)

MC

CP (

mg/k

g)

sum

nonyl-

phenol

(mg/k

g)

sum

nonyl-

phenol

eto

xilate

s (m

g/k

g)

BPA

(m

g/k

g)

Foam figurines (PU/EVA) X X

Slime X X

Eraser X X X

Modelling clay X X X X

Modelling foam X X X 0.17

Modelling clay X X X X

Doll - hair X X X

Doll - head (soft polymer) X X X

Baby doll (soft polymer) X X X

Figurine (PVC/soft polymer) X X X

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Ballons X X X

Ballons X X X

Modelling clay X X X X

Slime X X

Balls (soft polymer) X X X

Case/container (PVC/soft polymer) X X X X X 3.5 57

Hot water bottle (soft polymer) X X X X

Cover for hot water bottle (textile) X X X

Iphone cover (soft polymer) X X X X X

Case/container (PVC/soft polymer) X X X

Case/container (PVC/soft polymer) X X X

Pinting apron (PVC/soft polymer) X X X X X 420 16

Bike horn (rubber/latex) X X X X 160

Pendant (soft polymer) X X X X X 19 23 160

Pencil case (textil + PVC/soft polymer) X X X X X 1600 3400 2.6

Pendant (soft polymer) X X X X X 12 140

Pencil case (PVC/soft polymer) X X X X X

Wallet (PVC/soft polymer) X X X X X 670 38

Hairbrush (hard polymer) X X X 1.1

Ball (PVC/soft polymer) X X X X X

Drawing mat (textile + PVC/soft polymer) X X X

Computer case - plastic buttons (foam) X X X

Computer case - textile X X

Figurine - hard polymer X X X

Rain mitten (soft polymer/PU) X X X X

Rain mitten (soft polymer/PU) X X X X

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Rain mitten (soft polymer/PU) X X X X

Rain mitten lining (soft polymer) X X X X

Rain mitten (soft polymer/PU) X X X X 7300

Rain mitten lining (soft polymer) X X X X

Rain mitten (soft polymer/PU) X X X X

Rain mitten lining (soft polymer) X X X

Rain jacket (soft polymer/PU) X X X X

Rain jacket (soft polymer/PU) X X X X

Wind jacket (textile/soft polymer) X X X X

Zipper pendant on wind jacket (PVC/soft polymer)

X X X 87

Rain jacket (soft polymer/elastan) X X X

Zipper pendant on rain jacket (PVC/soft polymer)

X X X X 66000

Zipper pendant on wind jacket (PVC/soft polymer)

X X X

Zipper pendant on rain jacket (PVC/soft polymer)

X X X X 0.29 1100

Rain jacket (soft polymer/PU) X X X X 15 5100 7600

Rain trousers (soft polymer/PU) X X X X

Suspenders on rain trousers (elastan) X X X X X 0.11

Rain trousers (soft polymer/PU) X X X

Suspenders on rain trousers (elastan) X X X X X

Doll - belt (polymer) X X X

Wallet (PVC/soft polymer) X X X

Slime X X

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7.2 Appendix 2 – Abbreviations

EDC Endocrine disruptor

PVC Polyvinyl chloride

PU Polyurethane

7.3 References

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The Norwegian Environment Agency is working for

a clean and diverse environment

The Norwegian Environment Agency is working for

a clean and diverse environment. Our primary

tasks are to reduce greenhouse gas emissions,

manage Norwegian nature, and prevent pollution.

We are a government agency under the Ministry

of Climate and Environment and have 700

employees at our two offices in Trondheim and

Oslo and at the Norwegian Nature Inspectorate’s

more than sixty local offices.

We implement and give advice on the

development of climate and environmental

policy. We are professionally independent. This

means that we act independently in the individual

cases that we decide and when we communicate

knowledge and information or give advice.

Our principal functions include collating and

communicating environmental information,

exercising regulatory authority, supervising and

guiding regional and local government level,

giving professional and technical advice, and

participating in international environmental

activities.

Norwegian Environment Agency

Telephone: +47 73 58 05 00 | Fax: +47 73 58 05 01

E-mail: [email protected]

Web: www.environmentagency.no

Postal address: Postboks 5672 Sluppen, N-7485 Trondheim

Visiting address Trondheim: Brattørkaia 15, 7010 Trondheim

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