20050610 ND04o063 02 Nitrosamines in Ballonnen

8/12/2019 20050610 ND04o063 02 Nitrosamines in Ballonnen

1/21

MIGRATION OF N-NITROSAMINES AND N-NITROSATABLE

SUBSTANCES FROM LATEX BALLOONS

Report nr. ND04o063/02

VOEDSEL EN WAREN AUTORITEIT

internetsite www.vwa.nl

January 2005

VWA/KvW Noord, report ND04o063/02, January 2005


2/21

CONTENTS

page

SUMMARY and KEYWORDS

SAMENVATTING en TREFWOORDEN

1. INTRODUCTION 1

1.1 N-Nitrosamines and N-nitrosatable substances in balloons 1

1.2 Legal aspects 1

1.3 Previous market surveillance 2

1.4 Research aim 2

2. EXPERIMENTAL 3

2.1 Sampling 3

2.2 Migration of N-nitrosamines and N-nitrosatable substances 3

3. RESULTS AND DISCUSSION 4

3.1 Migration of N-nitrosamines and N-nitrosatable substances 4

3.2 Distribution in release of N-nitrosamines and N-nitrosatable substances 5

3.3 Warning on the labels 6

3.4 Comparison to test reports acquired from importers 6

3.5 Age indication 8

3.6 Comparison to previous market surveillance 8

4. CONCLUSIONS 11

5. ACKNOWLEGDEMENT 11

6. LITERATURE 12

ANNEX I: Overview of sampled balloons

ANNEX II: Migration of N-nitrosamines and N-nitrosatable substances

ANNEX III: Validation of migration method

VWA/KvW Noord, report ND04o063/02, January 2005


3/21

SUMMARY AND KEYWORDS

As a result of a German report on high release of nitrosamines and nitrosatable substances from balloons of a

Dutch supplier, the Dutch Inspectorate for Health Protection and Veterinary Public Health (VWA/KvW) initiated in

2002 a market surveillance on the chemical safety of balloons. 57 different balloons were sampled and only one

balloon complied with the migration limits as set for teats and soothers (nitrosamines 0.01 mg/kg; nitrosatablesubstances 0.1 mg/kg).

Due to these results, agreements have been made between the Inspectorate for Health Protection and Veterinary

Public Health, the minister of Health, Welfare and Sports, and the suppliers or importers of balloons in the

Netherlands (Regulier Overleg Warenwet (ROW)). An agreement has been made on putting a warning on the

labels: Warning! For safety reasons do not take balloons into the mouth and only inflate with a balloon pump.

Furthermore it was agreed upon in this ROW that on a short term the balloons had to comply with the German

limits (nitrosamines 0.01 mg/kg; nitrosatable substances 5 g/dm2) and on a long term the nitrosamines and the

nitrosatable substances would be phased out.

To investigate whether the market of balloons has been improved in 2 years of time and if the agreements were

kept, 58 balloons were sampled at the importers of the balloons in June and July 2004. The release of

nitrosamine and nitrosatable substances was determined by the RIVM according to EN 12868 (standard for teats

and soothers). The migration experiment was carried out for 1 hour instead of 24 hours, to compensate for the

fact that balloons are not mouthed as much as teats and soothers.

N-nitrosodimethylamine (NDMA) and N-nitrosodibutylamine (NDBA) and their precursors were the most

frequently found nitrosamines in the balloons. NDMA was found in 95% of the cases and NDBA in 93%. In

addition, other nitrosamines and nitrosatable substances were also found in the latex balloons.

8 balloons (14%) complied with the migration limits for teats and soothers for nitrosamines (0.01 mg/kg) andnitrosatable substances (0.1 mg/kg). On average, the migration limit for teats and soothers was exceeded by a

factor 7. The average releases of nitrosamines and nitrosatable substances were 0.072 mg/kg and 0.65 mg/kg,

respectively. The highest release of nitrosamines was 0.75 mg/kg, for nitrosatable substances was 3.2 mg/kg. 20

balloons (34%) complied with the German limits (nitrosamines 0.01 mg/kg; nitrosatable substances 5 g/dm2).

In 29% of the samples the warning which was agreed upon was included on the labels of the balloons.

6 importers (38%) supplied a test report with their products. Beforehand 2 test results did not comply with the

German standards. For nitrosamines the results of the RIVM were in most cases higher than the results from the

test reports. For nitrosatable substances the results of the RIVM were lower in most cases. This difference of

results is significantly (p


4/21

SAMENVATTING EN TREFWOORDEN

Naar aanleiding van een melding uit Duitsland over hoge afgiftes van nitrosamines en nitroseerbare verbindingen

uit ballonnen van een Nederlandse leverancier, heeft de VWA/KvW in 2002 een marktonderzoek gestart naar de

chemische veiligheid van ballonnen. 57 verschillende ballonnen zijn bemonsterd en slechts een ballon voldeed

aan de migratielimieten voor spenen en fopspenen (nitrosamines 0,01 mg/kg; nitroseerbare verbindingen 0,1mg/kg).

Vanwege deze resultaten is in Regulier Overleg Warenwet (ROW) verband overleg geweest tussen de Minister

van Volksgezondheid, Welzijn en Sport, de VWA en de importeurs van de ballonnen. Er is een afspraak gemaakt

over het plaatsen van een waarschuwingszin op het etiket: Waarschuwing! Om veiligheidsredenen niet in de

mond nemen en uitsluitend opblazen met een ballonnenpomp. Daarnaast is er afgesproken dat op korte termijn

de ballonnen zouden voldoen aan de Duitse norm (nitrosamines 0,01 mg/kg; nitroseerbare verbindingen

5 g/dm2) en dat deze verbindingen op de lange termijn zouden worden uitgefaseerd.

Om te onderzoeken of de markt in de afgelopen 2 jaar is verbeterd en of alle afspraken zijn nagekomen, zijn injuni en juli 2004 58 ballonnen bemonsterd bij de importeurs. De afgifte van nitrosamines en nitroseerbare

verbindingen is bepaald door het RIVM volgens EN 12868 (Norm voor spenen en fopspenen). De migratie is

daarbij uitgevoerd gedurende 1 uur in plaats van 24 uur om te compenseren voor het feit dat ballonnen niet zo

veel in de mond worden genomen als spenen en fopspenen.

N-nitrosodimethylamine (NDMA) and N-nitrosodibutylamine (NDBA) en zijn voorlopers werden het meest

gevonden in de ballonnen. NDMA werd in 95% van de gevallen gevonden, NDBA in 93%. Daarnaast zijn er nog

verschillende andere nitrosamines en nitroseerbare verbindingen gevonden.

8 ballonnen (14%) voldeden aan de migratielimiet van nitrosamines (0,01 mg/kg) en nitroseerbare verbindingen

(0,1 mg/kg) voor spenen en fopspenen. De migratielimieten werden gemiddeld met een factor 7 overschreden.De gemiddelde afgifte van nitrosamines en nitroseerbare verbindingen was respectievelijk 0,072 mg/kg en

0,65 mg/kg. De hoogste afgifte van nitrosamines was 0,75 mg/kg en voor nitroseerbare verbindigen was dit

3,2 mg/kg. 20 ballonnen (34%) voldeden aan de Duitse norm (nitrosamines 0,01 mg/kg; nitroseerbare

verbindingen 5 g/dm2).

Op 29% van de monsters was de afgesproken waarschuwingszin aanwezig. 6 importeurs (38%) konden een

testrapport bij hun ballonnen overhandigen. Op voorhand voldeden twee testresultaten niet aan de Duitse limiet.

Voor de nitrosamines vielen de resultaten gevonden door het RIVM in de meeste gevallen hoger uit dan de

resultaten uit de testrapporten. Voor de nitroseerbare verbindingen vielen de resultaten van het RIVM lager uit.

Het verschil in de resultaten is significant (p


5/21

1. INTRODUCTION

1.1 N-nitrosamines and N-nitrosatable substances in balloons

In July 2002 Germany (Landesanstalt fr Arbeitsschutz) notified the Inspectorate for Health Protection of the high

release of nitrosamines from a balloon of a Dutch toy supplier. The migration of N-nitrosodimethylamine (NDMA)

from this balloon was 0.69 mg/kg, the migration of the nitrosatable substance (precursor of NDMA) amounted to0.42 mg/dm2. The Dutch supplier took these balloons from the German market.

Nitrosamines comprise a class of compounds that have exhibited carcinogenic activity in several laboratory animals.

Nitrosatable substances can be converted into nitrosamines and therefore may form a cancer risk too. In

toxicology, it is presumed that humans are at least as sensitive as laboratory animals to develop cancer due to

exposure to nitrosamines in foodstuffs or consumer products. The nitrosamines and nitrosatable substances

originate from certain accelerators (carbamates) used for the vulcanisation of rubber.

1.2 Legal aspects

Balloons are a child article and therefore must comply with the requirements of the Decree on Toys (Food andCommodities Act) [6.1].In Appendix 2, article 10, part A (general requirements for child articles and toys) it is

required for toys and child articles not to impose any danger on the child's health or to form a danger to physical

injuries by swallowing, inhalation or contact with the skin, mucous membranes or eyes, arising from the chemical

composition.

In a European directive (93/11/EEC) the migration of nitrosamines and nitrosatable substances from teats and

soothers is regulated [6.2].This directive is incorporated in the Dutch Packaging and Food-Utensils Regulation

(Food and Commodities Act) [6.3].In Part A, Chapter III (Rubber products) the following migration limits are

imposed on the migration of nitrosamines and nitrosatable substances from rubber teats and soothers:

N-nitrosamines, in total 0.01 mg/kg rubber

Nitrosatable substances, in total, determined as N-nitrosamines 0.1 mg/kg rubber

These migration limits are based on detection limits and not on a toxicological evaluation, as for (suspected)

carcinogenic substances it is presumed that no safe contact exists. Although balloons are not intended to be put

in the mouth by babies or young children, this is considered to be very likely. According to the Decree on toys

[6.1]the chemical composition of child articles shall not impose a danger on the child's health. The migration

limits for nitrosamines and nitrosatable substances from rubber teats and soothers are therefore used to evaluate

the actual migration values from balloons.

Germany has set specific limits for the migration of nitrosamines and nitrosatable sustances from balloons [6.4].

For nitrosamines the limits are the same as in Directive 93/11/EEC [6.2], for nitrosatable substances the limits is

changed into release per unit of area:

N-nitrosamines, in total 0.01 mg/kg rubber

Nitrosatable substances, in total, determined as N-nitrosamines 5 g/dm2

The migration of nitrosamines and nitrosatable substances from teats and soothers must be determined

according to EN 12868 [6.5].In the German study and also in other test reports for the testing of balloons, the

migration time is shortened from 24 hours to 1 hour, as for children the exposure to balloons is expected to be

much shorter than the exposure to teats and soothers. In our experiments, therefore, the migration time is set at

1 hour also. All comparisons made in this report are based on a 1-hour migration test for balloons and a 24-hour

migration test for teats and soothers.

VWA/KvW Noord, report ND04o063/02, January 2005 1


6/21

1.3 Previous market surveillance

As a result of this German notification, the Inspectorate for Health Protection and Veterinary Public Health

initiated a market surveillance on the migration of nitrosamines and nitrosatable substances from balloons [6.6].

In July 2002 57 different balloons were sampled on the Dutch market. The release of nitrosamines and

nitrosatable substances was determined in a nitrite containing saliva simulator according to EN 12868 (standard

for teats and soothers) [6.5]. In deviation of this standard, the migration experiment was carried out during 1 hourinstead of 24 hours, to compensate for the fact that balloons are not mouthed as frequently and long as is the

case for teats and soothers.

N-nitrosodimethylamine (NDMA) and its precursor were detected in almost all balloons. In more than 60% of the

balloons N-nitrosodibutylamine (NDBA) and its precursor were present. In addition, other nitrosamines and

nitrosatable substances were detected, also. Of the 57 balloons, only 1 balloon complied after one hour of

migration with the migration limits imposed on teats and soothers for nitrosamines (0.01 mg/kg rubber) and

nitrosatable substances (0.1 mg/kg rubber). On average the limit for nitrosamines and nitrosatable substances

was exceeded by a factor 15. The highest values found for the release of nitrosamines and nitrosatable

substances were 0.63 and 5.7 mg/kg rubber, respectively.

The migration was also studied as a function of time. At low exposure times (5 minutes) already a considerable

amount had migrated. Within these 5 minutes, the release of nitrosamines and nitrosatable substances had

exceeded the limits of Directive 93/11/EEC [6.2].

Due to these results, discussion took place between the Inspectorate for Health Protection and Veterinary Public

Health, the Ministry of Health, Welfare and Sports, and the suppliers or importers of balloons in the Netherlands

in the Regulier Overleg Warenwet (ROW) [6.7]. There are no producers of balloons in the Netherlands. On this

consultation it was agreed upon to put the following warning on the labels before May 1st2004:

WAARSCHUWING! OM VEILIGHEIDSREDENEN NIET IN DE MOND NEMEN EN UITSLUITEND OPBLAZENMET EEN BALLONNENPOMP

(Warning! For safety reasons do not take balloons into the mouth and only inflate with a balloon pump).

Due to a certain amount of time between production and sale, there is a transition period. After several months

this warning should be present on all labels. Furthermore it was agreed that these balloons should on a short

term comply with the German limits. But the intention is to phase out the nitrosamines and nitrosatable

substances on the long term (several years).

1.4 Research aim

The aim of this project is to investigate whether the market for balloons has improved in 2 years of time.

Therefore 58 balloons were sampled at the importers of balloons. The release of nitrosamines and nitrosatablesubstances was determined by the RIVM and compared with the limit for teats and soothers as well as the

German limit. Furthermore it was checked if the warning has been put on the labels of the balloons. The results

were compared to the test results supplied by the importers (if present).



7/21


8/21

3. RESULTS AND DISCUSSION

3.1 Migration of N-nitrosamines and N-nitrosatable substances

In Annex II, Table 5 the results are given of the migration of nitrosamines and nitrosatable substances for the 58

samples. In Table 1 the average values, the median, the standard deviation and the maximum value are given for

the migration of nitrosamines and nitrosatable substances.

Table 1: Migration of nitrosamines and nitrosatable substances of latex balloons (n=58)

NDMA NDBA NMPhA NDBzA NDEA total

N-nitrosamines

Present (%) 95 93 2 3 12Mean (mg/kg) 0.045 0.028 0.047 0.0073 0.022 0.072Median (mg/kg) 0.010 0.014 0.047 0.0073 0.0012 0.041Standard deviation (mg/kg) 0.11 0.041 0.0019 0.052 0.13Maximum (mg/kg) 0.75 0.23 0.047 0.0087 0.14 0.75

nitrosatable substances

Present (%) 97 83 0 0 21Mean (mg/kg) 0.27 0.47 0.040 0.65Median (mg/kg) 0.12 0.18 0.030 0.41Standard deviation (mg/kg) 0.34 0.63 0.046 0.66Maximum (mg/kg) 1.5 2.9 0.15 3.2

NDMA: N-nitrosodimethylamineNDBA: N-nitrosodibutylamineNMPhA: N-nitrosomethylphenylamineNDBzA: N-nitrosodibenzylamineNDEA: N-nitrosodiethylamine

NDMA and NDBA were found most frequently. NDMA was found in 95% of the balloons, NDBA in 93%. This also

applies to its precursors. NMPhA, NDBzA and NDEA were also found, although in a lower frequency. Theprecursors of NMPhA and NDBzA were not found, the precursor of NDEA was found in 21% of the balloons.

In 20 balloons (34%) the value of nitrosamines did not exceed the limit for teats and soothers, including the

analytical tolerance (0.02 mg/kg). In 18 balloons (31%) the value of nitrosatable substances was under the limit

for teats and soothers. In total, 9 balloons (16%) complied with both migration limits.

The German limit for nitrosamines is 0.01 mg/kg [6.4], thus 20 balloons (34%) comply with this limit, including the

analytical tolerance (100%). The German limit for nitrosatable substances is 5 g/dm2. All the balloons (100%)

comply with this limit. In total, 20 balloons (34%) complied with the German standard.

The mean migration of nitrosamines was 0.072 mg/kg. For nitrosatable substances the mean migration was

0.65 mg/kg. This exceeded the migration of nitrosamines by a factor 9. Compared to the migration limit for teats

and soothers, the limit for nitrosamines and for nitrosatable substances were exceeded by a factor of 7 on

average.

To correct for the fact that balloons are not intended to be taken into the mouth, the migration test was performed

during 1 hour instead of 24 hours. Nitrosamines are suspected to be carcinogen (NDMA is a category II

carcinogen), and nitrosatable substances can react to form these nitrosamines. Therefore it is desirable to phase

out all the nitrosamines and nitrosatable substances. In the ROW [6.7] the agreement has been made with the

branch of trade and the companies that the balloons are considered to be in compliance with article 3 of the

Decree on Toys [6.1], when they comply with the German limits [6.4].



9/21

On the long term it was agreed upon to phase out all the nitrosamines and nitrosatable substances. In that case

the balloons have to comply with the migration limits for teats and soothers.

The balloons which did not comply with both the German limits [6.4] and the limits on teats and soothers [6.2]

received an official warning (38 samples, 66%). A notification with a covering letter was send to the importers

whose balloons complied with the German limits, but not with the limits for teats and soothers (12 samples, 21%).

3.2 Distribution in release N-nitrosamines and N-nitrosatable substances

In Figure 1 the distribution in release of NDMA, NDBA and the total nitrosamines is given. The values of each

single nitrosamine were added up for this last category. It appeared that for most balloons the release of NDMA

and NDBA did not exceed 0.05 mg/kg. For NDBA the values of migration are slightly higher. The highest value

measured was 0.75 mg/kg (for NDMA). The peak in release of total nitrosamines is in the class 0.01 to 0.05

mg/kg. The release for most balloons does not exceed 0.1 mg/kg. The highest release of nitrosamines is 0.75

mg/kg.

0

5

10

15

20

25

30

n.d.


10/21

0

5

10

15

20

25

30

n.d.


11/21

Table 2: Comparison between results from the test reports and the results from the RIVM.

Nitrosamines Nitrosatable substancesSample nr. Test reports (mg/kg) RIVM (mg/kg) Test reports (g/dm2) RIVM (g/dm2)

45109283 0.002 0.039 0.350 0.0345109291 0.002 0.048 0.350 0.07

45109305 0.002 0.047 0.350 0.0245109313 0.010b 0.061 0.165b 0.0745109321 0.010b 0.041 0.165b 0.0145109348 0.003 0.014 0.757 0.1745109356 0.003 0.006 0.757 0.0345109364 0.010b 0.170 0.165b 0.2845109429 0.008 0.079 0.091 mg/kgc 0.077 mg/kgc45109437 0.005 0.079 0.071 0.1745109445 0.013 0.027 0.164 mg/kgc 0.260 mg/kgc45109453 0.009 0.358 0.106 -a45109461 0.008 0.051 0.131 mg/kgc 1.14 mg/kgc45109488 0.010 0.016 0.081 mg/kgc 1.04 mg/kgc

46521234 0.012b 0.091 0.5b 0.1946521242 0.012b 0.069 0.5b 0.0446521269 0.012b 0.003 0.5b 0.2146521277 0.012b 0.009 0.5b 0.0546521285 0.012b 0.053 0.5b 0.4646521404 0.001 0.004 0.519 0.0246521412 0.001 0.013 0.519 0.0746521439 0.001 0.018 0.519 0.0546521455 0.0009 0.084 0.351 0.1046521463 0.0009 0.576 0.351 0.1346521471 0.0009 0.043 0.351 0.0546521501 0.001 0.003 0.519 0.02

(a) no conversion rate determined (b) Average value of various samples (c) Values given in mg/kg, quality allowed 0.1 mg/kg

There are some drawbacks to these test results. For some test reports it is not very likely that the tests were done

with the same batch balloons from which the samples were obtained. In addition, some test reports seemed to

represent more than one sample taken by the VWA (or the other way around). Therefore for some samples

average values of the test results were given in Annex I, Table 4. For some other samples it is assumed that the

tests were done on the same batch. The importers probably did not send a representative sample to the test

institutions.

For nitrosamines, in most cases the value obtained by the RIVM is higher than the results from the test reports.

For nitrosatable substances the values from the test reports are higher than the results obtained by the RIVM. Tocompare these results a t-test - paired two-sample for means - was performed. The values of nitrosatable

substances that are given in mg/kg are left out of this t-test. As can be seen from the data the results from the test

reports differ significantly from the results from the RIVM for both nitrosamines (p


12/21

Regardless of this effect it is still not desirable to have these compounds in child articles and toys. Furthermore,

the producers of the balloons are able to produce balloons without nitrosamines and nitrosatable substances,

which can also be concluded from the data in this report.

3.5 Age indication

In Annex I, Table 4 the age indication mentioned on the labels of the balloons is given. This is summarized inFigure 3. In 45% of the cases supervision of an adult on children under 8 years is recommended. In 36% of the

cases there was no age indication given on the label. 7 samples (12%), on which no age indication was given,

were not intended for consumers, which might be the reason for the absence. Thus, in most cases the warning /

instruction sentences comply with the prescribed sentencefrom prCEN/TR 15071[6.8] Other age indications (>3

and > 5 years) were given also (Figure 3).

36% 45%

5%2%7%5%

supervision < 8 years

> 8 years

>5 years

none

supervision < 6 years

> 3 years

Figure 3: Age indication on labels of the balloons (n=58)

In 22% of the cases a symbol, which indicates that the product is not suitable for children under 3 years, was

printed on the label. This was always in combination with a written age indication, mostly the one that advises

supervision of an adult on children under 8 years. Due to the danger of suffocation, balloons are not suitable for

young children. However when the balloons are inflated, they are often given to young children to play with.

3.6 Comparison to previous market surveillance (2002)

There is a shift in the kind of nitrosamines found. In Table 3 the proportion of each nitrosamine and precursor

found in 2002 and in 2004 is given. In the survey of 2002 N-nitrosodiisononylamine (NDiNA),

N-nitrosodiisodecylamine (NdiDA) and N-morfoline (NMOR) were found together with NDMA, NDBA, NDEA and

NDBzA. NMPhA was not found in the survey of 2002. In 2004 it was found in 2% of the balloons. The number of

balloons, which contain NDBA and its precursor, is increased.

Warning! Children under eight years can choke or suffocate on uninflated or broken balloons. Adult supervision

required. Keep uninflated balloons from children. Discard broken balloons at once. Made of natural rubber latex.



13/21

Table 3: Proportion of each nitrosamine and precursor found for 2002 (n=57) and 2004 (n=58).

Nitrosamines (%) Nitrosatable substances (%)2002 2004 2002 2004

NDMA 96 95 96 97NDEA 9 12 9 21

NDBA 61 93 66 83NDBzA 7 3 4 0NDiNA 16 0 4 0NDiDA 5 0 20 0NMOR 2 0 0 0NMPhA 0 2 0 0

When the distribution in total release of nitrosamines is compared for both surveys (Figure 4),it can be seen that

the total release is shifted to lower values. For 2004 the peak in release of nitrosamines is in the class 0.01 to

0.05 mg/kg. In 2002 most balloons had a migration between 0.05 and 0.3 mg/kg.

0

5

10

15

20

25

30


14/21

As a result of the market surveillance in 2002, in the ROW agreements have been made to improve this situation

[see section 1.3]. One of these agreements was that on a short term balloons would comply with the German

limits. In this surveillance 20 balloons (34%) complied with the German limits. On the long term the intention is to

phase out all nitrosamines and nitrosatable substances. When compared with the migration limits for teats and

soothers, in 2002 only one balloon complied. In 2004, 9 balloons comply with the limits for teats and soothers.

Thus, the results indicate an improvement, but the majority of the balloons still do not comply with the migrationlimits set by Germany or with the limits of teats and soothers.



15/21

4. CONCLUSIONS

The nitrosamines and nitrosatable substances that were found most frequently in balloons were

N-nitrosodimethylamine (NDMA) and N-nitrosodibutylamine (NDBA) and their precursors. NDMA was found in

95% of the cases and NDBA in 93%. In addition, three other nitrosamines were found in the latex balloons as

well, namely N-nitrosomethylphenylamine (NMPhA) N-nitrosodibenzylamine (NDBzA) and N-nitrosodiethylamine(NDEA).

The average release of nitrosamines and nitrosatable substances was 0.072 mg/kg and 0.65 mg/kg, respectively,

mainly from NDBA and NDMA. The migration limit for teats and soothers was exceeded by a factor 7 on average.

The highest release of nitrosamines was 0.75 mg/kg, for nitrosatable substances it was 3.2 mg/kg.

9 balloons (16%) complied with the migration limits for teats and soothers including the analytical tolerance.

20 balloons (34%) complied with the German limits. The samples that did not comply with the German limits

received an official warning (38 samples, 66%). A notification with a covering letter was send to the importers

whose balloons complied with the German limits, but not with the limits for teats and soothers (12 samples, 21%).

In 29% of the samples the warning was included on the labels of the packaging of the balloons. This shows that

the agreements made with the importers were not kept by everyone. The importers, who did not put the warning

on the labels, received an official warning (41 samples, 71%). In 36% of the samples no age indication was

present on the label. In 45% of the cases supervision of an adult on children under 8 years was recommended.

6 importers (38%) supplied a test report with their products. Beforehand 2 test results did not comply with the

German standards. For nitrosamines the results of the RIVM were in most cases higher than the results from the

test reports. For nitrosatable substances the results of the RIVM were lower in most cases. This difference of

results is highly significant (p


16/21

6. LITERATURE

6.1 Warenwetbesluit Speelgoed (Warenwet) van 15 mei 1991. Staatsblad 1991, 269.

6.2 Commission Directive 93/11/EEC of 15 March 1993 concerning the release of the N-nitrosamines and N-

nitrosatable substances from elastomer of rubber teats and soothers. Official Journal L 093, 17/04/1993 P.

6.3 Regeling Verpakkingen en gebruiksartikelen (Warenwet) van 20 november 1979. Staatscourant 1980, 18.

6.4 Datenbank Stoffenempfehlungen, Hoofdstuk XXI, nr. 2.5 en 3.

6.5 EN 12868. 1999. Child use and care articles. Methods for determining the release of N-nitrosamines and N-

nitrosatable substances from elastomer or rubber teats and soothers.

6.6 Bouma, K. November 2002. Migratie van nitrosamines en nitroseerbare verbindingen uit ballonnen. Rapport

ND1TOY01/01, Keuringsdienst van Waren Noord.

6.7 Website Regulier Overleg Warenwet (ROW): http://www.row.minvws.nl/content.aspx?cid=106

6.8 prCEN/TR 15071: safety of toys; national translations of warnings and instructions for use in EN-71,

august 2004 (D).

http://www.row.minvws.nl/content.aspx?cid=106http://www.row.minvws.nl/content.aspx?cid=106


17/21

ANNEX I: OVERVIEW OF SAMPLED BALLOONS

Table 4: Information on sampled balloons

sample nr. Description age indication warning test reports complianceGerman Standard

N-nitr(mg/k

45109283 Orange balloons none nob yes yes 0.00245109291 Pink balloons none nob yes yes 0.00245109305 Green balloons none nob yes yes 0.00245109313 White balloons none nob yes yes 0.01045109321 blue balloons none nob yes yes 0.01045109348 white balloons none nob yes yes 0.00345109356 dark green balloons none nob yes yes 0.00345109364 mac donalds balloons supervision < 8 year nob yes yes 0.01045109429 50 balloons pearl symbola+ supervision < 8 year no yes yes 0.00845109437 50 balloons supervision < 8 year yes yes yes 0.00545109445 6 music balloons symbola+ < 3 year no yes no 0.01345109453 modeling balloons symbola+ supervision < 8 year yes yes yes 0.00945109461 water bombs symbola+ supervision < 8 year no yes no 0.00845109488 giant balloons symbola+ supervision < 8 year yes yes yes 0.01045109526 white plain balloons none nob no unknown45109534 round star topprint none nob no unknown45109542 ruby red plain latex none nob no unknown46521234 metallic blue supervision < 8 year yes yes no 0.01246521242 pastel lime green supervision < 8 year yes yes no 0.01246521269 professional latex balloons symbola+ supervision < 8 year yes yes no 0.01246521277 giant balloons supervision < 8 year yes yes no 0.01246521285 sarah balloons supervision < 8 year yes yes no 0.01246521293 100 balloons symbola+ supervision < 8 year no no unknown

46521307 blue balloons symbola

+ supervision < 8 year no no unknown46521315 top quality decoration balloons > 8 year no no unknown46521323 baby balloons symbola+ supervision < 8 year yes no unknown46521404 blue balloons none no yes yes 0.00146521412 yellow balloons none no yes yes 0.00146521439 balloons boebies > 3 year no yes yes 0.00146521447 8 balloons symbola+ supervision < 8 year no no unknown

VWA/KvWNoord,repo

rtND04o063/02,January2005

AnnexI


18/21

sample nr. Description age indication warning test reports complianceGerman Standard

N-nitr(mg/k

VWA/KvWNoord,repo


AnnexI

46521455 balloons pastel supervision < 8 year yes yes yes 0.00046521463 10 balloons symbola+ supervision < 8 year yes yes yes 0.00046521471 8 balloons symbola+ supervision < 8 year yes yes yes 0.000

46521498 balloons none no no unknown46521501 balloons with text none no yes yes 0.00147783267 10 balloons > 3 year no no unknown47783275 6 balloons supervision < 8 year yes no unknown47783305 balloons amazing supervision < 8 year no no unknown47784131 balloons very bestf supervision < 8 year no no unknown47784158 balloons 7years supervision < 8 year yes no unknown47885183 24 balloons helium supervision < 8 year yes no unknown47885191 8 giant balloons helium supervision < 8 year yes no unknown47885205 metallic balloons helium supervision < 8 year yes no unknown47885213 birthday balloons helium supervision < 8 year yes no unknown47885361 round balloons 7 stars none no no unknown

47885388 standard balloons none no no unknown47885396 round balloons soccer none no no unknown47885418 round balloons smile none no no unknown47885426 pink balloons hearts none no no unknown47885434 round balloons ivory silk none no no unknown47885442 round balloons yellow none no no unknown48048625 red balloons > 5 year no no unknown48048633 cobalt blue balloons > 5 year no no unknown48048641 lemon yellow balloons > 5 year no no unknown48048668 5 pink balloons supervision < 6 year no no unknown48048684 apple green balloons supervision < 6 year no no unknown48048692 orange balloons supervision < 6 year no no unknown

48048706 10 balloons symbola+ > 3 year no no unknown(a) Symbol: not suitable for children under 3 years. (d) Average value of various samples.

(b) Not intended for consumers. (e) Values given in mg/kg, quality allowed 0.1 mg/kg

(c) Value according to test report. (f) Labeling not in Dutch


19/21

ANNEX II: MIGRATION OF NITROSAMINES AND NITROSATABLE SUBSTANCES

Table 5: Migration of nitrosamines and nitrosatable substances from latex balloons

N-nitrosamines (mg/kg) nitrosa

Sample nr.

NDMA NDBA NDBzA NMPhA NDEA total total

(g/dm2)

NDMA NDBA

45109283 0.011 0.028 0.039 0.009 0.115 0.01645109291 0.003 0.045 0.048 0.007 0.013 0.45445109305 0.003 0.044 0.047 0.009 0.096 0.03045109313 0.057 0.002 0.001 0.061 0.017 0.065 0.18045109321 0.006 0.033 0.002 0.041 0.014 0.033 0.00745109348 0.005 0.009 0.014 0.004 0.208 0.411 45109356 0.004 0.001 0.006 0.002 0.067 0.02745109364 0.162 0.008 0.170 0.041 1.140 n.d.45109429 0.028 0.042 0.009 0.079 0.020 0.075 0.00345109437 0.048 0.031 0.079 0.016 0.689 0.14545109445 0.004 0.017 0.006 0.027 0.008 0.199 0.06145109453 0.339 0.019 0.0004 0.358 - 1.493 0.02745109461 0.014 0.036 n.d. 0.051 0.009 0.771 0.26945109488 0.003 0.012 0.0007 0.016 0.005 0.198 0.83345109526 0.003 0.028 0.031 0.010 0.251 0.198 45109534 n.d. 0.001 0.001 0.0003 0.042 0.16845109542 0.002 0.062 n.d. 0.063 0.020 0.083 1.20446521234 0.087 0.004 0.091 0.020 0.844 0.003 duplicate 0.043 n.d. 0.043 0.012 0.331 0.01246521242 0.067 0.002 0.069 0.017 0.167 n.d.46521269 0.003 n.d. 0.003 0.001 0.153 0.77246521277 0.001 0.008 n.d. 0.009 0.002 0.027 0.143

46521285 0.028 0.025 0.053 0.015 0.300 1.327 46521293 0.056 0.013 0.070 0.014 0.337 0.06146521307 0.174 0.005 n.d. 0.179 0.040 1.233 0.01646521315 0.026 0.043 0.069 0.016 0.085 0.327 46521323 0.007 0.011 0.018 0.004 0.151 0.46946521404 0.002 0.001 0.004 0.001 0.030 0.035duplicate 0.003 0.021 0.024 0.007 0.179 n.d.

VWA/KvWNoord,repo


AnnexII


20/21

N-nitrosamines (mg/kg) nitrosa

Sample nr.NDMA NDBA NDBzANDBzA NMPhANMPhA NDEANDEA totaltotal total

(g/dm2)total(g/dm

NDMANDMA NDNDBABA 2)

46521412 0.004 0.009 0.013 0.004 0.083 0.144duplicate 0.006 0.014 0.020 0.004 0.441 n.d.

46521439 0.005 0.013 0.018 0.006 0.152 n.d.46521447 0.017 0.048 0.064 0.016 0.483 0.07446521455 0.073 0.011 0.084 0.022 0.342 0.02846521463 0.207 0.229 0.140 0.576 0.128 0.317 0.22346521471 0.010 0.033 0.043 0.010 0.085 0.145 46521498 0.001 0.004 0.005 0.001 0.018 0.00646521501 0.001 0.002 n.d. 0.003 0.001 0.058 n.d.47783267 0.747 n.d. 0.747 0.210 1.331 n.d. 47783275 0.011 0.012 0.022 0.005 0.763 0.00647783305 0.014 0.054 0.069 0.020 0.346 1.25347784131 0.019 0.031 0.050 0.015 0.061 0.18347784158 0.123 0.029 0.152 0.038 0.051 0.197

47885183 0.011 0.187 0.199 0.035 0.277 1.34047885191 0.007 0.007 0.014 0.004 0.092 0.68347885205 0.008 0.044 0.052 0.011 0.094 1.04647885213 0.001 0.030 0.031 0.009 0.040 1.72947885361 0.023 0.122 n.d. 0.144 0.044 0.421 1.67247885388 0.010 0.014 0.024 0.006 n.d. n.d. 47885396 0.001 0.015 0.016 0.004 0.044 1.10147885418 0.016 0.057 0.0003 0.073 - 0.248 2.92747885426 0.002 0.007 0.008 0.001 0.059 0.964 47885434 n.d. 0.004 0.004 0.001 0.107 1.70147885442 0.016 0.025 0.047 0.088 0.023 0.131 0.38248048625 0.009 0.002 0.011 0.003 0.043 n.d.

48048633 n.d. n.d. 0.008 0.008 0.002 0.117 n.d.48048641 0.005 0.003 0.008 0.002 0.025 0.003 48048668 0.021 0.008 0.029 0.012 0.015 0.17548048684 0.006 n.d. 0.006 0.001 0.018 0.00348048692 0.021 0.022 0.043 0.008 0.117 n.d.48048706 0.019 0.006 0.023 0.006 n.d. n.d.

VWA/KvWNoord,repo


AnnexII


21/21

ANNEX III: VALIDATION OF MIGRATION METHOD

Detection limit:

The detection limit varied between 0.5 and 1.7 g/kg for the different nitrosamines, depending of the nitrosamine.

For nitrosatable substances the detection limit varied between 3.2 and 10.8 g/kg, also depending on the

nitrosamine.

Recovery

The recovery was not determined since it was a migration test.

Reproducibility

The migration test was performed three times in 2 balloons. With these results, an indication is obtained of the

reproducibility of the measurement.

Table 6: Reproducibility migration nitrosamines and nitrosatable substances.

Balloon 1 Balloon 2NDMA NDBA NDMA NDBA

N-nitrosamines

X-gem (g/kg) 4.6 21.3 4.4 20.4St. dev. (g/kg) 1.1 1.8 0.5 1.5RSD (%) 23.4 8.7 10.4 7.4

Nitrosatable substances

X-gem (g/kg) 695 816 400 1772St. dev. (g/kg) 151 76 102 290RSD (%) 21.7 9.3 25.3 16.4

Documents

20050610 ND04o063 02 Nitrosamines in Ballonnen