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TNO-report
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R 2004/002 T +31 55 549 34 93

F +31 55 541 98 37
The Determination of Selected Additives info@mep.tno.nl

in Consumer Products

Date December 2003

Authors Ruud J.B. Peters

Order no. 34986-004

Keywords consumer products, additives, hazardous chemicals, alkylphenols and

ethoxylates, phthalates, flame retardants, organotin compounds

Intended for Mrs. M. Harthoorn

Greenpeace Nederland
Veemkade 18-20
1019 GZ Amsterdam

All rights reserved.

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any other means without the previous written consent of TNO. TESTING
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subject to either the Standard Conditions for Research Instructions given to TNO, or the relevant
agreement concluded between the contracting parties.
Submitting the report for inspection to parties who have a direct interest is permitted.

© 2004 TNO
TNO-report

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Summary

That hazardous chemicals are present in our environment is confirmed by several

studies and is becoming increasingly well documented. Such chemicals are not
only found outdoors, but also in ordinary house dust from virtually every home.
Among these chemicals are additives that are nowadays used in many consumer
goods we buy and use in our home everyday. Following a previous study that fo-
cused on textiles, toys, cosmetic and cleaning products, this study focuses on an
additional number of consumer products found in many homes, e.g. electronic
equipment, sport shoes, mattresses, some food packaging materials and vinyl floor-
ing. Selected products were tested for alkylphenols and alkylphenol ethoxylates,
phthalates, brominated flame retardants and organotin compounds.

The results show that with the exception of the vinyl flooring and the electronic
equipment, the amount of the listed additives identified in the tested products was
limited. With the exception of one of the television sets, all electronic equipment
contained high amounts of tetrabromobisphenol-A, in most cases mainly in the po-
lymerised form. It was surprising that in two of the computers tetrabromobisphe-
nol-A was also used as an additive flame retardant, resulting in concentrations up
to 20% by weight of tetrabromobisphenol-A monomer in the product. Two of the
three sport shoes and the vinyl flooring both contained phthalates. The sport shoes
contained up to 3,300 mg/kg DEHP while the total phthalate content of the vinyl
flooring was over 40% by weight. The sport shoes also contained nonylphenol eth-
oxylates and limited amounts of nonylphenol and organotin compounds. The
cheese packaging material did contain low amounts of nonylphenol and in one case
bisphenol-A. Finally, the mattresses only contained low amounts of phthalates,
some nonylphenol ethoxylates and only traces of organotin compounds.
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Contents

Summary...................................................................................................................... 2

1. Introduction.................................................................................................. 4

2. Study objective and approach ..................................................................... 5

2.1 Objective of the Greenpeace study.............................................. 5
2.2 Chemical parameters ................................................................... 5
2.3 Samples ........................................................................................ 5

3. Methods and materials................................................................................. 8

3.1 Sample pre-treatment................................................................... 8
3.2 Analytical procedures .................................................................. 8
3.2.1 Sample extraction......................................................... 8
3.2.2 Instrumental analysis ................................................... 9
3.2.3 Calculation of results ................................................. 10

4. Results........................................................................................................ 11
4.1 Bisphenol-A ............................................................................... 11
4.1.1 General information ................................................... 11
4.1.2 Results for bisphenol-A in this study ........................ 11
4.2 Alkylphenol and alkylphenol ethoxylates ................................. 12
4.2.1 General information ................................................... 12
4.2.2 Results for alkylphenols and alkylphenol
ethoxylates in this study.................................................. 12
4.3 Phthalates ................................................................................... 13
4.3.1 General information ................................................... 13
4.3.2 Results for phthalates in this study............................ 14
4.4 Brominated flame retardants ..................................................... 14
4.4.1 General information ................................................... 14
4.4.2 Results for brominated flame retardants in this study.... 15
4.5 Organotin compounds................................................................ 17
4.5.1 General information ................................................... 17
4.5.2 Results for organotin compounds in this study ......... 17
4.6 Quality control measurements................................................... 18
4.6.1 Method validation parameters ................................... 18
4.6.2 Recovery of extraction standard ................................ 18
4.6.3 Blank samples ............................................................ 19

5. Conclusions................................................................................................ 20

6. QA/QC statement ...................................................................................... 21

7. Authentication............................................................................................ 22

Appendix: Full results of all product analysis

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1. Introduction

The progress of the chemical industry in the past century has supplied the world
with a vast amount of chemicals. At present roughly 100,000 chemicals are used
and more than 500 new chemicals are introduced annually1. From these, several are
known to cause adverse effects to man and animal life. The best documented are
probably the persistent organic pollutants (POPs), such as the polychlorinated bi-
phenyls (PCB) and the pesticide DDT. Although the use of chemicals as PCBs and
DDT is forbidden for some time, it is still possible to measure these compounds in
the environment worldwide due to their use in the past. Meanwhile, new chemicals
have replaced these compounds, and some of these chemicals, like phthalates, al-
kylphenols (AP) and alkylphenol ethoxylates (APEO) and flame retardants are
produced and used in huge amounts. As a result, these compounds can be found in
all environmental compartments and for instance in house dust2,3. A recent TNO
study showed that phthalates, alkylphenols and alkylphenol ethoxylates and bromi-
nated flame retardants were present in precipitation samples4. Another study
showed that these compounds are also present in typical consumer products like
textiles, cosmetic products and toys5.

Only few people are aware that many of these chemicals are used as additives in
consumer goods we buy and use in our home everyday. Of course, these additives
are there for a reason, for example, phthalates are added to soften plastics and
flame retardants are used in electronic equipment to reduce the risk of fire in the
case of overheating of equipment. However, a consequence of their presence in
consumer products is that the user is constantly exposed to these chemicals and that
they will enter the environment during, or after use of the products. This study fo-
cuses on the determination of the presence of a number of additives, alkylphenols
and alkylphenol ethoxylates, phthalates and brominated flame retardants and or-
ganotin compounds in a number of typical consumer products.

1
Jackson T. In: Material Concerns. Pollution, profit and quality of life. Routledge,
London, ISBN 0-415-13248-7, 40, 1996.
2
Vethaak A.D., Rijs G.B.J., Schrap S.M., Ruiter H., Gerritsen A., Lahr J. In: Estro-
gens and xeno-estrogens in the aquatic environment of the Netherlands.
RIZA/RIKZ-report no. 2002.001, February 2002.
3
Santillo D, Labunska I, Davidson H, Johnston P, Strutt M and Knowles O. Con-
suming Chemicals, Greenpeace Research Laboratories Technical Note 01/2003
(GRL-TN-01-2003), 2003.
4
Peters R.J.B. Hazardous Chemicals in Precipitation. TNO report R 2003/198, May
2003.
5
Peters R.J.B. Hazardous Chemicals in Consumer Productrs. TNO report R
2003/370, September 2003.
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2. Study objective and approach

2.1 Objective of the Greenpeace study

A recent TNO study revealed the presence of a number of hazardous chemicals in

consumer products5. The consumer products tested in that study were mainly tex-
tiles, cosmetic and cleaning products. The objective of this study is to determine
whether these compounds are also present in other consumer products like elec-
tronic equipment and mattresses. Their presence in these products may explain the
detection of these compounds in the dust in common homes3. This study presents
the results for the presence and concentrations of compounds in additional con-
sumer products like computers, television sets, mattresses and sport shoes.

2.2 Chemical parameters

In this study the decision was made to concentrate on compounds similar to those
that were analysed in the previous study in precipitation. The following chemical
parameters were selected for this study:
− Bisphenol-A
− Alkylphenols and alkylphenol ethoxylates
− Phthalates
− Brominated flame retardants
− Organotin compounds

The individual chemicals are listed in table 1. Some additional information about
the use of these compounds can be found in chapter 4.

2.3 Samples

In total 19 samples were received from Greenpeace in The Netherlands. The sam-
ples are common consumer products, including television sets, computers, cell
phones, sport shoes, mattresses and vinyl flooring. All samples were purchased by
Greenpeace in common shops in October 2003 and coded. Table 2 provides an
overview of the received samples.
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Table 1 Compound groups and specific compounds included in this study.

Group Specific compounds Acronym

Phthalates dimethyl phthalate DMP

diethyl phthalate DEP
di-iso-butyl phthalate DIBP
di-n-butyl phthalate DBP
benzylbutyl phthalate BBP
dicyclohexyl phthalate DCHP
di-(2-ethylhexyl) phthalate DEHP
di-n-octyl phthalate DOP
di-iso-nonylphthalate DINP
di-iso-decyl phthalate DIDP

Flame retardants 2,2',4,4'-tetrabromo diphenylether BDE 47

2,2',4,4',5-pentabromo diphenylether BDE 99
2,2',4,4',6-pentabromo diphenylether BDE 100
2,2',4,4',5,5'-hexabromo diphenylether BDE 153
2,2',3,4,4',5',6-heptabromo diphenylether BDE 183
octabromo diphenylether BDE octa
decabromo diphenylether BDE 209
hexabromo cyclododecane HBCD
tetrabromo bisphenol-A TBBA

Bisphenol-A Bisphenol-A BPA

Alkylphenols and
alkylphenol ethoxylates octylphenol OP
nonylphenol NP
octylphenol ethoxylates OPEO
nonylphenol ethoxylates NPEO

Organotins monobutyltin MBT

dibutyltin DBT
tributyltin TBT
tetrabutyltin TeBT
monooctyltin MOT
dioctyltin DOT
triphenyltin TPT
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Table 2 Overview of samples and chemical parameters to be determined.

TNO Code Greenpeace Product Description Chemical parameters to be

Code determined

BpA

AP/APEO

Phthal

BFR

O-Tin
52003305-001 GP-1 Television: Philips Real Flat: 21PT 5507/01 X
52003305-002 GP-2 Television: Samsung Plano: CW21A083NXXEC X
52003305-003 GP-3 Television: Panasonic TX: 21CK1C X

52003305-004 GP-4 Cell phone: Sony/Ericson T610: 35126300-200751-5 X X

52003305-005 GP-5 Cell phone: Samsung SGH-A800: 351004/26/634004/8 X X
52003305-006 GP-6 Cell phone: Siemens A55: 351855002740670 X X

52003305-007 GP-7 Computer: HP Pavilion A250 NL: NLD 33135B4 X

52003305-008 GP-8 Computer: Dell Optiflex GX240: FJ01G0J X
52003305-009 GP-9 Computer: IBM NetVista: 68233KG KBDALYN X

52003305-010 GP-10 Shoes: Nike Air Max Plus: 604133 161 X AP X X

52003305-011 GP-11 Shoes: Puma Torceira IT: 100287 05 X AP X X
52003305-012 GP-12 Shoes: Adidas Gammanova 2 IN: 382429 X AP X X

52003305-013 GP-13 Cheese: Unie kaas Goudse belegen ugd 24/12/03 X X

52003305-014 GP-14 Cheese: Royal Gouda Jonge kaas 48+ ugd 17/12/03 X X
52003305-015 GP-15 Cheese: Frico Kollumer ugd 19/12/03 X X

52003305-016 GP-16 Mattasses: Auping Inizio WH Pocket soepel: AB1512 X X X X X

52003305-017 GP-17 Mattasses: Springfield Ravanna X X X X X
52003305-018 GP-18 Mattasses: Ubica Atlanta X X X X X

52003305-019 GP-19 Vinyl flooring: Forbo X X X

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3. Methods and materials

3.1 Sample pre-treatment

Samples were stored at room temperature until analysis. All electronic equipment
was disassembled and all glass (television tubes), metal parts and electric wiring
removed. All plastic materials and printed circuit boards were broken in small
pieces. From these and from the other samples proportional sub-samples, with re-
spect to the different parts, were collected. Parts from electronic equipment were
grinded into small pieces of <1 mm. Sub-samples of the other samples were cut
into pieces smaller than 5 mm with clean scissors or a surgical knife for all other
samples. Following homogenisation of each sub-sample, an analytical sample of 1,
2 or 5 grams was collected, depending on the type of analysis.

3.2 Analytical procedures

3.2.1 Sample extraction

3.2.1.1 Bisphenol-A, alkylphenols and ethoxylates

The analytical sample was soxhlet extracted overnight with dichloromethane. The
extract was filtered if necessary and brought to a final volume of 100 ml with di-
chloromethane. A part of this extract was evaporated to dryness under nitrogen.
The residue was re-dissolved in a 50/50 mixture of HPLC water and methanol. Fi-
nally, the extract was filtered through a 0.45 µm filter and prepared for instrumen-
tal analyses.

3.2.1.2 Phthalates

The analytical sample was brought into a soxhlet thimble and extracted overnight
with dichloromethane. The extract was filtered if necessary and brought to a final
volume of 100 ml with dichloromethane. A part of this extract was concentrated,
filtered through 0.45 µm filter and brought to a final volume of 1 ml. Finally,
1,2,3,4-tetrachloronaphthalene was added as an injection standard.
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3.2.1.3 Flame retardants

The analytical sample was brought into a soxhlet thimble and extracted overnight
with dichloromethane. The extract was filtered if necessary and brought to a final
volume of 100 ml with dichloromethane. A part of this extract was concentrated
and filtered through 0.45 µm filter. Diazomethane was added for the derivatization
of any free tetrabromobisphenol-A in the sample extract. Finally, the extract was
concentrated to a volume of 1 ml and 1,2,3,4-tetrachloronaphthalene was added as
an injection standard.

For samples from electronic equipment an additional, and different, determination

is performed. Many of these materials do contain tetrabromobisphenol-A in a po-
lymerised, non-extractable, form. The presence of tetrabromobisphenol-A is con-
firmed using the extraction method described above, however, only the residual
monomer fraction is determined. The total tetrabromobisphenol-A content, the sum
of the monomer and polymer fraction, can only be determined after destruction to
bromine. Therefore, a sub-sample of the grinded sample material is collected and
digested in a Na/K carbonate melt at 900 ºC. The bromine content of the resulting
carbonate mix is determined with ion chromatography. The amount of bromine is
recalculated to tetrabromobisphenol-A, which than indicates the maximum amount
of tetrabromobisphenol-A in the sample (sum of monomer and polymer).

3.2.1.4 Organotin determination

A sub-sample was sonicated for 60 min in a sodium dithiocarbamate solution in

ethanol after the addition of tripropyltin chloride (TPrT) as an internal standard.
The extracts are left in the dark at room temperature overnight and sonicated a sec-
ond time for 60 min. Next, the extracts were centrifuged and the sample residue
removed. Two more internal standards, mono- and diheptyltin chloride (MHT and
DHT) were added to control the extraction and derivatization procedure. After the
addition of an acetate buffer (pH 4), HPLC water and a solution of sodium tetra-
ethylborate (the derivatization agent) in ethanol, the mixture was extracted twice
with hexane. The combined hexane fraction were dried and concentrated to a small
volume. After purification of the extract using column chromatography on alumina,
the extract is concentrated to a final volume of 1 ml and 1,2,3,4-tetrachloron-
aphthalene is added as an injection standard.

3.2.2 Instrumental analysis

Bisphenol-A, alkylphenols and alkylphenol ethoxylates are analysed using liquid

chromatography in combination with mass spectrometry (LC/MS). The LC/MS
was a Hewlett Packard 1100 LC/ESI/MS system equipped with a guard column
and a Waters Symmetry C18 analytical column, length 15 cm, 3.9 mm i.d., 5 µm
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particle size. For bisphenol-A and alkylphenols negative ionisation was used, for
alkylphenol ethoxylates positive ionisation. The mass spectrometer was used in the
selected ion monitoring mode and typically three ions were monitored for bisphe-
nol-A and alkylphenols. For alkylphenol ethoxylates fifteen ions (for n=1 to n=15,
each separated by 44 mass units) were monitored.

Phthalates, brominated flame retardants and organotin compounds were analysed

using gas chromatography in combination with mass spectrometry (GC/MS). The
GC/MS was a Hewlett Packard 6890 gas chromatograph equipped with HP-5MS
capillary column, length 30 m, 0.25 mm i.d., 0.25 µm film thickness, and inter-
faced to a Hewlett Packard 5973 mass spectrometer. The mass spectrometer was
used in the selected ion monitoring mode and typically two or three ions were
monitored for each compound.

3.2.3 Calculation of results

Identification of target compounds was based on retention time and qualifier ion ra-
tios. Quantification was based on external standards analysed within the same se-
ries as the sample extracts. The external standards were prepared from commer-
cially available pure substances. The number of ethoxy units in the commercial al-
kylphenol ethoxylate standards ranged from n=5 to n=15 with a maximum around
n=8-9. In all cases peak areas were used for calculations. The recovery of the added
extraction standards was calculated but only the organotin results were corrected
for this recovery. No correction for blank value was applied.

With the exception of the electronic equipment the results are expressed in mg/kg
product. For the electronic equipment all glass and metal parts, and all electric wir-
ing was removed prior to sub-sampling. This means that the results are expressed
in mg/kg for the sum of all polymer parts of the products and not in mg/kg product.
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4. Results

4.1 Bisphenol-A

4.1.1 General information

Bisphenol-A (BPA) is a widely used intermediate in the production of epoxy res-

ins, polycarbonate plastics and flame retardants, e.g. a substance used in an exten-
sive range of products. BPA is the most common monomer for polycarbonates in-
tended for food contact1. Not polymerised BPA may be released from the polycar-
bonate and thus enter the environment or food products. The chemical structure of
BPA is given in the figure below.

4.1.2 Results for bisphenol-A in this study

BPA was determined in the samples 52003305-010 to -019, e.g. sport shoes, pack-
aging foil of cheese, mattresses and vinyl flooring. BPA was found in only one of
the cheese packaging foils (52003305-015) at a level of 1.2 mg/kg. BPA has been
found previously in similar concentrations in the polymer coating of food cans2. In
two of the three sport shoes traces of bisphenol-A was identified, but these were
below the quantification limit of the method used in this study, 0.5 mg/kg.

The results for BPA are presented in table A.1 in the appendix.

1
Mountfort KA, Kelly J, Jickels SM, Castle L. Food Additives and Contamina-
tions, 56-63, 14, 1997.
2
Goodson A, Summerfield W, Cooper I. Food Additives and Contaminants. 1-12,
19, 2002.
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4.2 Alkylphenol and alkylphenol ethoxylates

4.2.1 General information

Alkylphenols (APs) and alkylphenol ethoxylates (APEOs) are used in plastics as

additives and as surface-active ingredients in industrial detergents and emulsifiers.
APs commonly used are nonylphenol (NP) and to a lesser extent octylphenol (OP),
in both cases pre-dominantly the para-substituted isomers (>90%). APEOs are used
as emulsifiers in textile and carpet cleaning products, and as emulsifiers in solvents
and agricultural pesticides1. As with the APs, nonylphenol ethoxylate (NPEO) is
more used than octylphenol ethoxylate (OPEO). The chemical structure of n-
nonylphenol and octylphenol-mono-ethoxylate (better known as Triton X-100) are
presented below.

4.2.2 Results for alkylphenols and alkylphenol ethoxylates in this study

In total 10 products were analysed for APs and APEOs. These included sport
shoes, the packaging foil of cheese, mattresses and vinyl flooring. APs or APEOs,
or both were detected in all samples, however in very different amounts. The sport
shoes (52003305-010 to -012) mainly contain NPEO and NP in concentrations up
to 2100 mg/kg for NPEO and 290 mg/kg for NP. The sample containing the high-
est amounts NP and NPEO (52003305-010) in addition contained some OPEO,
probably as an impurity in the NPEO used in the production of the base materials.

The cheese packaging foil samples all contained low amounts of NP, ranging from
1.3 to 3.4 mg/kg. This is in agreement with the results from another presently con-
ducted study where similar concentrations of NP are found in wrapping foils for
food packaging.
All mattresses contained NPEO in concentrations ranging from 25 to 190 mg/kg.
The sample with the highest concentration of NPEO in addition contained low con-

1
Maguire R.J. Water Qual. Res. J. Canada 34, 37-78, 1999.
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centrations of NP and OPEO, again probably as an impurity in the NPEO used in

the production of the base materials.
The vinyl flooring sample contained NPEO in a concentration of 460 mg/kg. As in
the mattresses samples NP and OPEO were identified also, however, in much
lower concentrations.

The complete results for AP and APEO are presented in table A.1 in the appendix.

4.3 Phthalates

4.3.1 General information

Phthalates are commonly found in soft plastics, cosmetic and personal care prod-
ucts. In general phthalates are used as plasticizers to increase the flexibility of high
molecular weight polymers. In some soft plastics phthalates may comprise up to
50% of the total weight. Major phthalates used are di-(2-ethylhexyl) phthalate
(DEHP) and di-iso-nonyl phthalate (DINP). In food packaging materials a similar
type of compound, di-iso-octyl adipate, the di-iso-octyl ester of hexanedioic acid, is
often used instead of phthalates.

Due to the presence of phthalates in common household products, cosmetics and

toys, the potential for human exposure is very high. The EU has imposed an emer-
gency restriction for 6 phthalates (DBP, BBP, DEHP, DOP, DINP and DIDP) in
articles for children in the age of 0-3 years1. The chemical structure of DEHP and
DEP is presented below.

1
Rastogi SC, Worsoe IM. Danisch National Environmental Research Institute.
NERI Technical Report No. 373, 2001.
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4.3.2 Results for phthalates in this study

In total 10 products were analysed for phthalates. These include cell phones, sport
shoes, mattresses and the vinyl flooring material. Only low concentrations of
phthalates were found in the cell phones and the mattresses, the highest concentra-
tion being 120 mg/kg DEHP in one of the cell phones. This indicates that these
phthalates are probably not true additions, but more likely residues resulting from
the raw production materials or otherwise. In two of the sport shoes higher concen-
trations of DIBP, sample 52003305-010 concentration 1700 mg/kg, and DEHP,
sample 52003305-011 concentration 3300 mg/kg were found. The third type of
sport shoe showed only low concentrations of phthalates up to 35 mg/kg for DEHP.
In the mattresses only low amounts of various phthalates were found that were
probably residues resulting from the raw production materials. As expected the vi-
nyl flooring material contained the highest concentrations of phthalates, especially
BBP and another phthalate that was identified as di-iso-heptyl phthalate. The con-
centration of BBP was 150,000 mg/kg while the concentration of di-iso-heptyl
phthalate (based on the response factor of BBP) was estimated to be 270,000
mg/kg. This means that the total phthalate content of this material is over 40% by
weight.

The complete results of the phthalate analysis are presented in table A.2 in the ap-
pendix.

4.4 Brominated flame retardants

4.4.1 General information

Flame retardants are added to polymers used in a wide range of materials such as
electric and electronic equipment, paint, textiles and in carts and aircraft to prevent
them from catching fire. Within the group of the brominated flame retardants two
types of flame retardants can be distinguished.
Polybrominated diphenyl ethers (PBDE) are so-called additive flame retardants.
PBDEs are used as commercial mixtures such as Bromkal, with different degrees
of bromination. Typically, PBDEs may comprise up to 5% to 20% of the total
weight of a product to which they are added. Since these chemicals are not chemi-
cally bound they may “leak” from the polymer product, thus entering the environ-
ment. Hexabromocyclododecane (HBCD) is a cyclo-aliphatic brominated chemical
meant to partially replace PBDEs because of their known toxicity. HBCD is also an
additive flame retardant and can enter the environment in much the same way.

Tetrabromobisphenol-A (TBBA) can be used as both a reactive and an additive

flame retardant. In its more common reactive use, it is added to materials as a co-
polymer, which means that it is chemically bound to, and part of, the polymer ma-
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terial itself. TBBA is used in this way in epoxy polymers such as printed circuit
boards in electronic equipment like computers and television sets. Even when used
in this manner, small amounts of the TBBA monomer will not be polymerized and
can “leak” into the environment. In other cases, mostly in ABS plastics, TBBA is
used as an additive flame retardant in concentrations up to 16% by weight1,2. Its use
in this additive mode can result in proportionately much higher losses to the envi-
ronment from products during use than when used reactively.
The chemical structure of decabromodiphenylether (BDE-209), HBCD and TBBA
are presented below.

4.4.2 Results for brominated flame retardants in this study

A number of relevant PBDE, HBCD and TBBA were determined in the electronic
equipment samples in this study, e.g. television sets, computers and cell phones,
and in mattresses. For the interpretation of the data, especially those of the elec-
tronic equipment, it is necessary to understand how the final sample is prepared.
For the electronic equipment all metal parts and glass parts, e.g. the television tube
itself, and all electrical wiring were removed. From all remaining parts that could

1
Luijk R. PhD dissertation “Formation of polyhalogenated dibenzo-p-dioxins and
benzofurans during thermal degradation processes” University of Amsterdam,
may 1993.
2
Danish Environmental Protection Agency, Environmental Project no. 494 1999,
“Brominated Flame Retardants”, www.mst.dk/udgiv/Publications/1999/87-7909-
416-3/html/default_eng.htm. 1999.
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be differentiated visually, proportional sub-samples were collected. No differentia-

tion has been made between printed circuit boards and other polymers. The
amounts of these sub-samples were based on the estimated total amount of that par-
ticular part or material in the product. This means that only small sub-samples are
collected from small parts while large sub-samples are collected from, for instance,
the outside material of the product.

The results for the brominated flame retardants are presented in table A.3 in the
appendix. In general, only small amounts of PBDE were found in three of the sam-
ples, one cell phone (52003305-004) and two computers (52003305-007 and
52003305-009). In the mattresses no brominated flame retardants were found at all.
The relative amounts of the PBDE found in one of the computers clearly show the
signature of the commercially available Octa-mix that consists mainly of hexa-,
hepta- and octa-BDE. HBCD was identified in one of the computers (52003305-
009) in a concentration of 70 mg/kg. The low concentrations of these brominated
flame retardants indicate that these are not a true addition if they originate from a
main polymer part of the product. More likely, they originate from a smaller sub-
sample, e.g. from a small polymer part in the computer or cell phone.

For TBBA two different determinations, a specific extraction and destruction to

bromine, are performed. As pointed out earlier TBBA is often used as a copolymer
in the epoxy material of printed circuit boards. An extraction of the sample will
only reveal the amount of monomer TBBA still present in the sample (column
“TBBA-monomer” in table A.3). The polymerised TBBA can only be determined
by destruction to bromine and recalculation of the bromine content to TBBA. Note
that such a determination will produce a result that represents the maximum TBBA
amount in the product (column “TBBA-maximum” in table A.3). The TBBA
amount may even be overestimated if other bromine sources are present in the
sample.

The results in table A.3 show that all electronic equipment contains TBBA in
monomer or polymer form. Taking into account that only non-polymerised TBBA
is available for extraction, and that the printed circuit board generally is not the ma-
jor part of the polymer material in these products, only low or medium TBBA-
monomer concentrations up to 100 mg/kg are expected to result from the printed
circuit boards. This means that with the exception of samples 52003305-002, -007
and -009, TBBA results most likely from the printed circuit boards or minor parts
of the electronic product. For the computers with TNO codes 52003305-007 and -
009 the maximum- and monomer-TBBA concentrations are of the same order of
magnitude, indicating that in these products TBBA is also used as an additive
flame retardant. Sample 52003305-007 contains TBBA in its monomer form up to
20% by weight, probably originating from the computer monitor since the casing
of the computer itself is mainly made of metal.
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The complete results of the brominated flame retardants are presented in table A.3
in the appendix.

4.5 Organotin compounds

4.5.1 General information

There are three major applications for organotin compounds. First, the use of tribu-
tyltin (TBT) in anti-fouling paints for ships, secondly, the use of triphenyltin (TPT)
as a pesticide, and third, the use of butyl- and octyltin compounds as stabilisers in
polymers. Therefore, many textile products containing polymer parts, like T-shirts
with prints, sanitary bandages, plasters and diapers, can contain organotin com-
pounds1. In some occasions organotin compounds are used as fungicides on textiles
that are exposed to extreme whether conditions, such as canvas. The structures of
TBT and TPT are presented below.

Until a few years ago mainly TBT and its degradation products dibutyltin (DBT)
and monobutyltin (MBT) were found. Nowadays, it is more often di-octyltin
(DOT) and mono-octyltin (MOT) that are found, always in the polymer parts
(foam, plastic or adhesives) used in these of products2. Concentrations range from
0.01 mg/kg up to more than 2 mg/kg for textile products, and up to more than 50
mg/kg for polymer parts of products.

4.5.2 Results for organotin compounds in this study

In this study six samples, sport shoes and mattresses were analysed for seven indi-
vidual organotin compounds. The organotin compounds MBT, DBT, MOT and
DOT where found in the sport shoes in concentrations ranging from 0.05 to 2.0

1
Gaikema F.J., Alberts P.J. Gaschromatografische bepaling van residuen van or-
ganotinverbindingen in textielproducten. De Ware(n)-Chemicus 1999, 23-33.
2
Observations of over four years of organotin determinations in materials by TNO
TNO-report

TNO-MEP − R 2004/002 18 of 22

mg/kg product for the individual compounds. Since all parts of the shoes were sub-
sampled it is not clear from which part the organotin compounds originate.
In the mattresses only low amounts of the organotin compounds DBT, TeBT and
DOT were found with a maximum concentration of 0.07 mg/kg. These concentra-
tions may be impurities in one of the base materials of the mattresses, but it is more
likely that one of the base materials, present as a minor part of the entire sample,
contains these organotins.

4.6 Quality control measurements

4.6.1 Method validation parameters

All methods applied were already used in earlier studies and were validated in ac-
cording to research and development protocols. The linearity of the instrumental
analysis is known but in this case the linearity of the complete method is not a very
useful parameter since the concentrations in the products can be so far apart that
extracts have to be concentrated or diluted for the result to fall in the linear range of
the instrumental analysis.

The repeatability for each of the methods is determined by replicate analyses of the
same sample. For homogenous samples, like the cheese packaging material, the re-
peatability is better than 15%. For non homogenous samples, like television sets,
the repeatability within the collected sub-sample is comparable with the previous
one, but the repeatability for the complete method, e.g. analysis including all sam-
ple pre-treatment, sub-sampling and analysis, is estimated to be no better than 50%.

The quantification limits are given in the result tables in the appendix and generally
vary between 0.01 mg/kg and 1 mg/kg, depending on the type of analyses and ex-
pected result.

4.6.2 Recovery of extraction standard

Internal (extraction) standards were added for the determination of the organotin
compounds. In all cases the recovery was above 70% and the results for the or-
ganotin compounds are corrected for this recovery. For the other compounds the
addition of an extraction standard to a solid product sample, finely cut or grinded to
small pieces, does not say much about the quality of the extraction. For the phtha-
lates and flame retardants the quality of the extraction was tested additionally by
extracting the same sample three times. Analyses showed that 100% of the analytes
were found in the first extract.
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4.6.3 Blank samples

With each series blank samples were included. These blank consisted of a complete
analysis in the same series as the samples, however, without the addition of sample
material. With the exception of the phthalate DEHP no blank values were ob-
served.
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5. Conclusions

In this study 19 consumer products have been tested for the presence various addi-
tives. A selected number of these 19 products were analysed for bisphenol-A, al-
kylphenols and ethoxylates, phthalates, flame retardants and organotin compounds.

− From the electronic equipment tested in this study, two of the computers con-
tained high amounts of TBBA used as an additive flame retardant, in one sam-
ple up to 20% by weight. Six out of nine samples contained high amounts of
polymerised TBBA probably originating from the printed circuit boards. Only
traces of PBDEs and HBCD were found in the samples, mainly in the com-
puters. In addition the cell phones were tested for the presence of phthalates.
These were found, however, only in low concentrations.

− Two of the three sport shoes did contain phthalates, DIBP in a concentration of
1,700 mg/kg and DEHP in a concentration of 3,300 mg/kg. In addition all
shoes contained NPEO with a maximum concentration of 2,100 mg/kg. In that
latter sample NP was also found in a concentration of 290 mg/kg. Finally all
sport shoes were found to contain organotin compounds. The total amounts or-
ganotin ranged from 1.5 to 2.8 mg/kg, mainly DBT and DOT.

− The foil packaging of the cheese products were tested for BPA, APs and
APEOs. Only one of them did contain low amounts of BPA while all contained
NP in concentrations up to 3.4 mg/kg.

− The mattresses were analysed for all chemicals that were part of this study. In
general they only contained traces of APs, APEOs, phthalates and organotin
compounds. Brominated flame retardants were not identified in these samples.
The most prominent compound identified was NPEO in concentrations ranging
from 25 to 190 mg/kg.

− As expected by the nature of the product, the vinyl flooring material contained
high amounts of phthalates, in total up to 40% by weight. Apart from the
phthalates originally involved in this study, di-iso-heptyl phthalate was identi-
fied as the major phthalate in this material. In addition the vinyl material con-
tained NPEO in a concentration of 460 mg/kg and low amounts of OPEO and
NP.
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6. QA/QC statement

The analytical determinations in this study are performed in compliance with NEN-
EN-ISO/IEC 17025 and RvA accreditation no. 54, “The development and applica-
tion of methods for the determination of organic contaminants in environmental
matrices, wastes and materials”. TNO Environment, Energy and Process Innova-
tion is listed in the RvA register under no. L 026. The Dutch Council for Accredita-
tion (RvA) and is a member of the European co-operation for Accreditation (EA)
and the International Laboratory Accreditation Co-operation (ILAC). TNO Envi-
ronment, Energy and Process Innovation operates in compliance with the Quality
System standard ISO 9001 (certificate no. 00680-97-AQ-ROT-RvA).
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TNO-MEP − R 2004/002 22 of 22

7. Authentication

Name and address of the principal:

Greenpeace Nederland
Veemkade 18-20
1019 GZ Amsterdam

Names and functions of the cooperators:

Dr. R.J.B. Peters Project Leader
Ing. R. Geenen Technician
Drs. R.J. van Delft Technician
Ing. H. Beeltje Technician

Date upon which, or period in which, the research took place:

November 2003 – December 2003

Signature: Approved by:

R.J.B. Peters Dr. M.P. Keuken

Project leader MA Head of Department MA
TNO-report

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Appendix

Appendix Full results of all product analysis

In the result tables the following acronyms are being used:

Group Specific compounds Acronym

Phthalates dimethyl phthalate DMP

diethyl phthalate DEP
di-iso-butyl phthalate DIBP
di-n-butyl phthalate DBP
benzylbutyl phthalate BBP
dicyclohexyl phthalate DCHP
di-(2-ethylhexyl) phthalate DEHP
di-n-octyl phthalate DOP
di-iso-nonylphthalate DINP
di-iso-decyl phthalate DIDP

Flame retardants 2,2',4,4'-tetrabromo diphenylether BDE 47

2,2',4,4',5-pentabromo diphenylether BDE 99
2,2',4,4',6-pentabromo diphenylether BDE 100
2,2',4,4',5,5'-hexabromo diphenylether BDE 153
2,2',3,4,4',5',6-heptabromo diphenylether BDE 183
octabromo diphenylether BDE octa
decabromo diphenylether BDE 209
hexabromo cyclododecane HBCD
tetrabromo bisphenol-A TBBA

Bisphenol-A Bisphenol-A BPA

Alkylphenols and
alkylphenol ethoxylates octylphenol OP
nonylphenol NP
octylphenol ethoxylates OPEO
nonylphenol ethoxylates NPEO

Organotins monobutyltin MBT

dibutyltin DBT
tributyltin TBT
tetrabutyltin TeBT
monooctyltin MOT
dioctyltin DOT
triphenyltin TPT

Note: With the exception of the electronic equipment the results are expressed in
mg/kg product. For the electronic equipment all glass and metal parts, and all elec-
tric wiring was removed prior to sub-sampling. This means that the results are ex-
pressed in mg/kg for the sum of all polymer parts of the products and not in mg/kg
product.
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Appendix

Table A.1 Concentrations of bisphenol-A, alkylphenols and ethoxylates in consumer products

TNO Code Greenpeace Product Description Bisphenol-A, alkylphenols and alkylphenol ethoxylates
Code
BpA mg/kg OP NP OPEO NPEO
mg/kg mg/kg mg/kg mg/kg

52003305-010 GP-10 Sport shoes: Nike Air Max Plus: 604133 161 <0.5 <0.5 290 11 2100
52003305-011 GP-11 Sport shoes: Puma Torceira IT: 100287 05 <0.5 <0.5 21 <0.5 200
52003305-012 GP-12 Sport shoes: Adidas Gammanova 2 IN: 382429 <0.5 <0.5 34 <0.5 480

52003305-013 GP-13 Cheese: Unie kaas Goudse belegen ugd 24/12/03 <0.5 <0.5 3.4 <0.5 <0.5
52003305-014 GP-14 Cheese: Royal Gouda Jonge kaas 48+ ugd 17/12/03 <0.5 <0.5 2.3 <0.5 <0.5
52003305-015 GP-15 Cheese: Frico Kollumer ugd 19/12/03 1.2 <0.5 1.3 <0.5 <0.5

52003305-016 GP-16 Mattrasses: Auping Inizio WH Pocket soepel: AB1512 <0.5 <0.5 <0.5 <0.5 73
52003305-017 GP-17 Mattrasses: Springfield Ravanna <0.5 <0.5 1.4 1.1 190
52003305-018 GP-18 Mattrasses: Ubica Atlanta <0.5 <0.5 <0.5 <0.5 25

52003305-019 GP-19 Vinyl flooring: Forbo <0.5 <0.5 10 3.1 460

Table A.2 Concentrations of phthalates in consumer products

TNO Code Greenpeace Product Description Phthalates
Code DMP DEP DIBP DBP BBP
mg/kg mg/kg mg/kg mg/kg mg/kg
52003305-004 GP-4 Cell phone: Sony/Ericson T610: 35126300-200751-5 1.6 1.7 13 35 63
52003305-005 GP-5 Cell phone: Samsung SGH-A800: 351004/26/634004/8 1.5 1.0 13 37 <0.1
52003305-006 GP-6 Cell phone: Siemens A55: 351855002740670 0.2 0.4 16 <0.1 0.2
52003305-010 GP-10 Sport shoes: Nike Air Max Plus: 604133 161 0.2 140 1700 4.6 2.8
52003305-011 GP-11 Sport shoes: Puma Torceira IT: 100287 05 <0.1 23 23 5.5 0.6
52003305-012 GP-12 Sport shoes: Adidas Gammanova 2 IN: 382429 0.2 19 7.4 3.3 5.0
52003305-016 GP-16 Mattrasses: Auping Inizio WH Pocket soepel: AB1512 <1 0.7 11 2.8 0.8
52003305-017 GP-17 Mattrasses: Springfield Ravanna 0.2 1.9 15 4.0 0.7
52003305-018 GP-18 Mattrasses: Ubica Atlanta <0.1 0.7 14 3.8 9.7
52003305-019 GP-19 Vinyl flooring: Forbo* 0.1 13 24 130 150000

TNO Code Greenpeace Product Description Phthalates

Code DCHP DEHP DOP DINP DIDP
mg/kg mg/kg mg/kg mg/kg mg/kg
52003305-004 GP-4 Cell phone: Sony/Ericson T610: 35126300-200751-5 <0.1 <0.1 <0.1 <1 <1
52003305-005 GP-5 Cell phone: Samsung SGH-A800: 351004/26/634004/8 <0.1 <0.1 0.3 <1 <1
52003305-006 GP-6 Cell phone: Siemens A55: 351855002740670 0.2 120 <0.1 <1 <1
52003305-010 GP-10 Sport shoes: Nike Air Max Plus: 604133 161 <0.1 14 11 <1 <1
52003305-011 GP-11 Sport shoes: Puma Torceira IT: 100287 05 <0.1 3300 <0.1 <1 <1
52003305-012 GP-12 Sport shoes: Adidas Gammanova 2 IN: 382429 <0.1 35 <0.1 <1 <1
52003305-016 GP-16 Mattrasses: Auping Inizio WH Pocket soepel: AB1512 <0.1 3.1 <0.1 <1 <1
52003305-017 GP-17 Mattrasses: Springfield Ravanna 0.2 30 <0.1 <1 <1
52003305-018 GP-18 Mattrasses: Ubica Atlanta 0.1 8.5 <0.1 <1 <1
52003305-019 GP-19 Vinyl flooring: Forbo* <1 620 <1 <1 <1
* An additional phthalate in this sample was di-iso-heptyl phthalate with an estimated concentration of 270,000 mg/kg
TNO-report

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Appendix

Table A.3 Concentrations of brominated flame retardants in consumer products

TNO Code Greenpeace Product Description Brominated flame retardants
Code BDE 47 BDE 99 BDE 100 BDE 153 BDE 183
mg/kg mg/kg mg/kg mg/kg mg/kg
52003305-001 GP-1 Television: Philips Real Flat: 21PT 5507/01 <0.1 <0.1 <0.1 <0.1 <0.1
52003305-002 GP-2 Television: Samsung Plano: CW21A083NXXEC <0.1 <0.1 <0.1 <0.1 <0.1
52003305-003 GP-3 Television: Panasonic TX: 21CK1C <0.1 <0.1 <0.1 <0.1 <0.1
52003305-004 GP-4 Cell phone: Sony/Ericson T610: 35126300-200751-5 <0.1 0.2 <0.1 <0.1 <0.1
52003305-005 GP-5 Cell phone: Samsung SGH-A800: 351004/26/634004/8 <0.1 <0.1 <0.1 <0.1 <0.1
52003305-006 GP-6 Cell phone: Siemens A55: 351855002740670 <0.1 <0.1 <0.1 <0.1 <0.1
52003305-007 GP-7 Computer: HP Pavilion A250 NL: NLD 33135B4 <0.1 <0.1 <0.1 0.4 1.6
52003305-008 GP-8 Computer: Dell Optiflex GX240: FJ01G0J <0.1 <0.1 <0.1 <0.1 <0.1
52003305-009 GP-9 Computer: IBM NetVista: 68233KG KBDALYN <0.1 <0.1 <0.1 <0.1 0.4

52003305-016 GP-16 Mattrasses: Auping Inizio WH Pocket soepel: AB1512 <0.1 <0.1 <0.1 <0.1 <0.1
52003305-017 GP-17 Mattrasses: Springfield Ravanna <0.1 <0.1 <0.1 <0.1 <0.1
52003305-018 GP-18 Mattrasses: Ubica Atlanta <0.1 <0.1 <0.1 <0.1 <0.1

TNO Code Greenpeace Product Description Brominated flame retardants

Code BDE octa BDE 209 HBCD 1 2
TBBA TBBA sum
monomer monomer
and polymer

52003305-001 GP-1 Television: Philips Real Flat: 21PT 5507/01 <0.1 <0.1 <0.1 2.1 130
52003305-002 GP-2 Television: Samsung Plano: CW21A083NXXEC <0.1 <0.1 <0.1 210 34000
52003305-003 GP-3 Television: Panasonic TX: 21CK1C <0.1 <0.1 <0.1 5 8300
52003305-004 GP-4 Cell phone: Sony/Ericson T610: 35126300-200751-5 <0.1 <0.1 <0.1 <0.1 6500
52003305-005 GP-5 Cell phone: Samsung SGH-A800: 351004/26/634004/8 <0.1 <0.1 <0.1 <0.1 12000
52003305-006 GP-6 Cell phone: Siemens A55: 351855002740670 <0.1 <0.1 <0.1 0.6 14000
52003305-007 GP-7 Computer: HP Pavilion A250 NL: NLD 33135B4 1.0 <0.1 <0.1 200000 190000
52003305-008 GP-8 Computer: Dell Optiflex GX240: FJ01G0J <0.1 <0.1 <0.1 31 15000
52003305-009 GP-9 Computer: IBM NetVista: 68233KG KBDALYN <0.1 <0.1 70 21000 57000
52003305-016 GP-16 Mattrasses: Auping Inizio WH Pocket soepel: AB1512 <0.1 <0.1 <0.1 <0.1 <100
52003305-017 GP-17 Mattrasses: Springfield Ravanna <0.1 <0.1 <0.1 <0.1 <100
52003305-018 GP-18 Mattrasses: Ubica Atlanta <0.1 <0.1 <0.1 <0.1 <100
1
: TBBA monomer is free extractable TBBA content, determined specifically as TBBA
2
: TBBA is an estimate of the sum of monomer and polymer TBBA, determined by a very different method than TBBA monomer (see section 3.2.1.3)

Table A.4 Concentrations of organotin compounds in consumer products

TNO Code Greenpeace Product Description Organotin compounds
Code MBT DBT TBT TeBT
mg/kg mg/kg mg/kg mg/kg
52003305-010 GP-10 Sport shoes: Nike Air Max Plus: 604133 161 0.05 0.82 <0.01 <0.01
52003305-011 GP-11 Sport shoes: Puma Torceira IT: 100287 05 0.20 2.0 <0.01 <0.01
52003305-012 GP-12 Sport shoes: Adidas Gammanova 2 IN: 382429 0.13 1.7 <0.01 <0.01
52003305-016 GP-16 Mattrasses: Auping Inizio WH Pocket soepel: AB1512 <0.01 0.03 <0.01 0.03
52003305-017 GP-17 Mattrasses: Springfield Ravanna <0.01 <0.01 <0.01 <0.01
52003305-018 GP-18 Mattrasses: Ubica Atlanta <0.01 <0.01 <0.01 <0.01

TNO Code Greenpeace Product Description Organotin compounds

Code MOT DOT TPT
mg/kg mg/kg mg/kg
52003305-010 GP-10 Sport shoes: Nike Air Max Plus: 604133 161 0.16 0.47 <0.01
52003305-011 GP-11 Sport shoes: Puma Torceira IT: 100287 05 <0.01 0.10 <0.01
52003305-012 GP-12 Sport shoes: Adidas Gammanova 2 IN: 382429 0.19 0.81 <0.01
52003305-016 GP-16 Mattrasses: Auping Inizio WH Pocket soepel: AB1512 <0.01 <0.01 <0.01
52003305-017 GP-17 Mattrasses: Springfield Ravanna <0.01 0.07 <0.01
52003305-018 GP-18 Mattrasses: Ubica Atlanta <0.01 <0.01 <0.01