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

CONTENTS

page SUMMARY and KEYWORDS SAMENVATTING en TREFWOORDEN 1. INTRODUCTION 1.1 N-Nitrosamines and N-nitrosatable substances in balloons 1.2 Legal aspects 1.3 Previous market surveillance 1.4 Research aim EXPERIMENTAL 2.1 Sampling 2.2 Migration of N-nitrosamines and N-nitrosatable substances RESULTS AND DISCUSSION 3.1 Migration of N-nitrosamines and N-nitrosatable substances 3.2 Distribution in release of N-nitrosamines and N-nitrosatable substances 3.3 Warning on the labels 3.4 Comparison to test reports acquired from importers 3.5 Age indication 3.6 Comparison to previous market surveillance CONCLUSIONS ACKNOWLEGDEMENT LITERATURE ANNEX I: Overview of sampled balloons ANNEX II: Migration of N-nitrosamines and N-nitrosatable substances ANNEX III: Validation of migration method 1 1 1 2 2 3 3 3 4 4 5 6 6 8 8 11 11 12

2.

3.

4. 5. 6.

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

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; nitrosatable substances 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) and nitrosatable 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<0.01). Due to these results it can be concluded that the importers probably send a just fabricated balloon to the test institutions. In time the level of nitrosatable substances declines, due to a reaction with nitrite to nitrosamines. This can be seen from the results of the RIVM where probably older balloons were measured. Regardless of this, it is still not desirable to have these compounds in child articles as balloons. When compared to the results of 2002 a shift in the distribution of both nitrosamines and nitrosatable substances to a lower release of these compounds is noticeable. Thus, the results indicate an improvement, but the majority of the balloons still does not comply with the migration limits set by Germany or with the limits of teats and soothers. Keywords: balloons, migration, nitrosamines, nitrosatable substances

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

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 0,1 mg/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 in juni 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<0,01). Dit verschil zou kunnen worden verklaard doordat de importeurs waarschijnlijk een net gefabriceerde ballon als monster hebben opgestuurd naar de testinstituten. Na verloop van tijd zal het niveau van nitroseerbare verbindingen dalen doordat het reageert met nitriet tot nitrosamines. Dat verklaart de resultaten van het RIVM die aan oudere ballonnen heeft gemeten. Ondanks dit is het nog steeds niet gewenst dat deze verbindingen zich bevinden in kinderwaren als ballonnen. Vergeleken met de resultaten van 2002 is de gemiddelde concentratie van zowel nitrosamines als nitroseerbare verbindingen lager. De resultaten vertonen weliswaar een verbetering, het grootste deel van de ballonnen voldoet nog altijd niet aan de migratielimieten van Duitsland of de limieten van spenen en fopspenen. Trefwoorden: ballonnen, migratie, nitrosamines, nitroseerbare verbindingen.

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

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 to 0.42 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 and Commodities 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

1.3 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 hour instead 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 1st 2004: WAARSCHUWING! OM VEILIGHEIDSREDENEN NIET IN DE MOND NEMEN EN UITSLUITEND OPBLAZEN MET 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 nitrosatable substances 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).

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

2. EXPERIMENTAL 2.1 Sampling Sampling took place at the importers in June and July 2004 in the regions East, Northwest and Southwest of the Netherlands. In total 58 bags with balloons were collected. The importers were asked to supply recent test reports of their balloons. The labels of the packages were checked for the above-mentioned warning. A summary of the data of the sampled balloons is given in Annex I, Table 4. 2.2 Migration of N-nitrosamines and N-nitrosatable substances The RIVM (National Institute of Public Health and the Environment, Bilthoven) measured the migration of nitrosamines and nitrosatable substances. For the determination of the migration of N-nitrosamines and nitrosatable substances from balloons Standard Operation Procedure (SOP) ARO/008 was used, which is similar to EN 12868 [6.5]. All the balloons in a bag were cut into pieces of approximately 1 cm2. From the bag with snippings a representative sub sample was taken. The migration was performed in the prescribed, nitrite containing saliva simulator, during 1 hour at 40C. For teats and soothers it is prescribed on the packaging that they must be boiled prior to use. As this is not the case for balloons, in deviation of EN 12868, the rubber materials were not boiled for 10 minutes prior to the start of the migration experiment. In addition the migration time was shortened from 24 to 1 hour, as the exposure of children to balloons is much shorter as compared to teats and soothers. The rest of the migration experiment was carried out as prescribed in EN 12868. The release of the following nitrosamines and corresponding nitrosatable substances was determined:

N-nitrosodimethylamine N-nitrosodiethylamine N-nitrosodi-n-propylamine N-nitrosodi-n-butylamine N-nitrosopiperidine N-nitrosopyrrolidine N-nitrosomorpholine N-nitrosomethylphenylamine N-nitrosoethylphenylamine N-nitrosodibenzylamine N-nitrosodiisononylamine N-nitrosodiisodecylamine N-nitrosodibutylamine

A summary of the validation of this method is described in Annex III.

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

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 N-nitrosamines Present (%) 95 93 2 3 12 Mean (mg/kg) 0.045 0.028 0.047 0.0073 0.022 Median (mg/kg) 0.010 0.014 0.047 0.0073 0.0012 Standard deviation (mg/kg) 0.11 0.041 0.0019 0.052 Maximum (mg/kg) 0.75 0.23 0.047 0.0087 0.14 nitrosatable substances Present (%) 97 83 0 0 21 Mean (mg/kg) 0.27 0.47 0.040 Median (mg/kg) 0.12 0.18 0.030 Standard deviation (mg/kg) 0.34 0.63 0.046 Maximum (mg/kg) 1.5 2.9 0.15
NDMA: NDBA: NMPhA: NDBzA: NDEA: N-nitrosodimethylamine N-nitrosodibutylamine N-nitrosomethylphenylamine N-nitrosodibenzylamine N-nitrosodiethylamine

total 0.072 0.041 0.13 0.75 0.65 0.41 0.66 3.2

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. The precursors 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].

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

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.

30 25

frequency

20 15 10 5 0 n.d. <0.01 0.01-0.05 0.05-0.1 0.1-0.2 0.2-0.3

NDMA NDBA Total

0.3-0.4

more

release of nitrosamines (mg/kg) Figure 1: The distribution in release of NDMA, NDBA and total nitrosamines from latex balloons (n=58) The precursor of NDMA was found in 97% of the balloons and the precursor of NDBA in 83%. In Figure 2 the distribution of these two precursors and the total release of nitrosatable substances is given. In most balloons the release of these two precursors does not exceed 0.5 mg/kg. There is more spread in the results for the precursor of NDBA. The peak in release of total nitrosatable substances is in the class 0.1 to 0.5 mg/kg. The highest value measured was 3.2 mg/kg.

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30 25

frequency

20 15 10 5 0 n.d. <0.1 0.1-0.5 0.5-1.0 1.0-1.5 1.5-2.0

NDMA NDBA Total

2.0-4.0

more

release of nitrosatable substances (mg/kg) Figure 2: The distribution in release of the nitrosatable substances from latex balloons (n=58) 3.3 Warning on the labels The Ministry of Health, Welfare and Sports, and the suppliers or importers of balloons in the Netherlands made an agreement to put a warning on the labels [see also section 1.3]. This warning should be present on the labels from May 1st 2004. Samples were taken at importers if possible, so the warning should be present on the labels of the sampled balloons in June and July 2004. 17 of the 58 samples (29%) complied with this agreement. 4 out of 16 importers (25%) put the warning on all their products. 2 out of 16 (13%) importers included this warning on a few of their products. Thus it can be concluded that not all the importers kept the agreement. The importers of the samples that lacked the right warning sentence received an official warning (41 samples, 71%). 3.4 Comparison to test reports acquired of importers The importers were asked to take responsibility for their products, for example by testing it for nitrosamines and nitrosatable compounds. 6 importers (38%) supplied a test report with their products. The tests were done by institutions such as Institut Fresenius (Germany), Chemisches Laboratorium Lbeck (Germany), and Pollock and Pool (UK). All the test results from these reports are given in Annex I, Table 4. Two test results of these reports did not comply with the German Standard. To convert the found migration into release per unit of area, the RIVM determined a conversion rate (kg/dm2). In Annex II, Table 5 the release per unit area for nitrosamines and nitrosatable substances for each sample is given. This figure for nitrosatable substances was used to compare the results of the RIVM with the obtained test results. In Table 2 the values obtained from the test reports are compared with the results of the RIVM.

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Table 2: Comparison between results from the test reports and the results from the RIVM. Nitrosamines Nitrosatable substances Sample nr. Test reports (mg/kg) RIVM (mg/kg) Test reports (g/dm2) RIVM (g/dm2) 45109283 0.002 0.039 0.350 0.03 45109291 0.002 0.048 0.350 0.07 45109305 0.002 0.047 0.350 0.02 45109313 0.010b 0.061 0.165b 0.07 45109321 0.010b 0.041 0.165b 0.01 45109348 0.003 0.014 0.757 0.17 45109356 0.003 0.006 0.757 0.03 45109364 0.010b 0.170 0.165b 0.28 45109429 0.008 0.079 0.091 mg/kgc 0.077 mg/kgc 45109437 0.005 0.079 0.071 0.17 45109445 0.013 0.027 0.164 mg/kgc 0.260 mg/kgc 45109453 0.009 0.358 0.106 -a c 45109461 0.008 0.051 0.131 mg/kg 1.14 mg/kgc 45109488 0.010 0.016 0.081 mg/kgc 1.04 mg/kgc 46521234 0.012b 0.091 0.5b 0.19 b b 46521242 0.012 0.069 0.5 0.04 46521269 0.012b 0.003 0.5b 0.21 46521277 0.012b 0.009 0.5b 0.05 46521285 0.012b 0.053 0.5b 0.46 46521404 0.001 0.004 0.519 0.02 46521412 0.001 0.013 0.519 0.07 46521439 0.001 0.018 0.519 0.05 46521455 0.0009 0.084 0.351 0.10 46521463 0.0009 0.576 0.351 0.13 46521471 0.0009 0.043 0.351 0.05 46521501 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. To compare 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<0.01) and nitrosatable substances (p<0.00001). The validation of the migration method used by the RIVM can be found in Annex III. The average nitrosamine concentration as measured by the RIVM is significantly higher as compared to the average concentration from the test reports. On the other hand, the concentration of nitrosatable substances from the test reports is significantly higher. The importers probably send a newly fabricated balloon to the test institution. In such a balloon the level of nitrosatable substances will be high. In time these nitrosatable substances will react with nitrite to nitrosamines. The level of nitrosatable substances will decline and the level of nitrosamines will rise as can be seen in the results of the RIVM. These results show a higher release of nitrosamines and a lower release of nitrosatable substances.

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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 in Figure 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 sentence from prCEN/TR 15071[6.8] Other age indications (>3 and > 5 years) were given also (Figure 3).

36%

45%

5%

7%

2% 5%

none supervision < 8 years supervision < 6 years > 8 years > 3 years >5 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.

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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 97 NDEA 9 12 9 21 NDBA 61 93 66 83 NDBzA 7 3 4 0 NDiNA 16 0 4 0 NDiDA 5 0 20 0 NMOR 2 0 0 0 NMPhA 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.
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20 15 10 5 0 <0.01 0.010.05

2004 2002

0.05-0.1 0.1-0.2 0.2-0.3 0.3-0.4 0.4-0.5 0.5-0.6

more

release of nitrosamines (mg/kg) Figure 4: The distribution in release of total nitrosamines for 2004 (n=58) and 2002 (n=57) In Figure 5 the same comparison as in Figure 4 has been made for the nitrosatable substances. Again, the total release of nitrosatable substances has been declined. In 2004 the peak in release is in the class 0.1 to 0.5 mg/kg, in 2002 this peak was in the class 1.5 to 2.0 mg/kg.
30 25

frequency

20 15 10 5 0 n.d. <0.1

2004 2002

0.1-0.5 0.5-1.0 1.0-1.5 1.5-2.0 2.0-2.5 2.5-3.0 3.0-3.5 more

release of nitrosatable substances (mg/kg) Figure 5: The distribution in release of nitrosatable substances for 2004 (n=58) and 2002 (n=57)

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

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 migration limits set by Germany or with the limits of teats and soothers.

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

10

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<0.01). Due to these results it can be concluded that the importers probably send a newly fabricated balloon to the test institutions. Newly fabricated balloons have a lower level of nitrosamines and a higher level of nitrosatable substances. In time the nitrosatable substances will react with nitrite to nitrosamines. This can be seen in the balloons measured by the RIVM. Most probably these balloons were older. Regardless of this, it is still not desirable to have the compounds in child articles and toys. Furthermore, the producers of the balloons are able to produce balloons without these compounds. The number of balloons that comply with the migration limit for teats and soothers is increased from 1 to 8 balloons. Some nitrosamines and precursors were not found in this survey. In the distribution of both nitrosamines and nitrosatable substances a shift to a lower release of these compounds is noticeable, when compared to 2002. Thus, the results indicate an improvement, but the majority of the balloons still do not comply with the migration limits set by the German standards or with the limits of teats and soothers. 5. ACKNOWLEDGEMENT Ronald Schothorst and his colleagues of the RIVM in Bilthoven are gratefully acknowledged for the analysis of the balloons.

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

11

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 Nnitrosatable 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 Nnitrosatable 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).

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

12

ANNEX I: OVERVIEW OF SAMPLED BALLOONS Table 4: Information on sampled balloons sample nr. Description age indication 45109283 45109291 45109305 45109313 45109321 45109348 45109356 45109364 45109429 45109437 45109445 45109453 45109461 45109488 45109526 45109534 45109542 46521234 46521242 46521269 46521277 46521285 46521293 46521307 46521315 46521323 46521404 46521412 46521439 46521447 Orange balloons Pink balloons Green balloons White balloons blue balloons white balloons dark green balloons mac donalds balloons 50 balloons pearl 50 balloons 6 music balloons modeling balloons water bombs giant balloons white plain balloons round star topprint ruby red plain latex metallic blue pastel lime green professional latex balloons giant balloons sarah balloons 100 balloons blue balloons top quality decoration balloons baby balloons blue balloons yellow balloons balloons boebies 8 balloons none none none none none none none supervision < 8 year symbola + supervision < 8 year supervision < 8 year symbola + < 3 year symbola + supervision < 8 year symbola + supervision < 8 year symbola + supervision < 8 year none none none supervision < 8 year supervision < 8 year symbola + supervision < 8 year supervision < 8 year supervision < 8 year symbola + supervision < 8 year symbola + supervision < 8 year > 8 year symbola + supervision < 8 year none none > 3 year symbola + supervision < 8 year

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

warning nob nob nob nob nob nob nob nob no yes no yes no yes nob nob nob yes yes yes yes yes no no no yes no no no no

test reports yes yes yes yes yes yes yes yes yes yes yes yes yes yes no no no yes yes yes yes yes no no no no yes yes yes no

compliance German Standard yes yes yes yes yes yes yes yes yes yes no yes no yes unknown unknown unknown no no no no no unknown unknown unknown unknown yes yes yes unknown

N-nitrosamines (mg/kg)c 0.002 0.002 0.002 0.010d 0.010d 0.003 0.003 0.010d 0.008 0.005 0.013 0.009 0.008 0.010

nitrosatable substances (g/dm2)c 0.350 0.350 0.350 0.165d 0.165d 0.757 0.757 0.165d 0.091 mg/kge 0.071 0.164 mg/kge 0.106 0.131 mg/kge 0.081 mg/kge

0.012d 0.012d 0.012d 0.012d 0.012d

0.5d 0.5d 0.5d 0.5d 0.5d

0.001 0.001 0.001

0.519 0.519 0.519

sample nr.

compliance N-nitrosamines German Standard (mg/kg)c 46521455 balloons pastel supervision < 8 year yes yes yes 0.0009 46521463 10 balloons symbola + supervision < 8 year yes yes yes 0.0009 46521471 8 balloons symbola + supervision < 8 year yes yes yes 0.0009 46521498 balloons none no no unknown 46521501 balloons with text none no yes yes 0.001 47783267 10 balloons > 3 year no no unknown 47783275 6 balloons supervision < 8 year yes no unknown 47783305 balloons amazing supervision < 8 year no no unknown 47784131 balloons very bestf supervision < 8 year no no unknown 47784158 balloons 7years supervision < 8 year yes no unknown 47885183 24 balloons helium supervision < 8 year yes no unknown 47885191 8 giant balloons helium supervision < 8 year yes no unknown 47885205 metallic balloons helium supervision < 8 year yes no unknown 47885213 birthday balloons helium supervision < 8 year yes no unknown 47885361 round balloons 7 stars none no no unknown 47885388 standard balloons none no no unknown 47885396 round balloons soccer none no no unknown 47885418 round balloons smile none no no unknown 47885426 pink balloons hearts none no no unknown 47885434 round balloons ivory silk none no no unknown 47885442 round balloons yellow none no no unknown 48048625 red balloons > 5 year no no unknown 48048633 cobalt blue balloons > 5 year no no unknown 48048641 lemon yellow balloons > 5 year no no unknown 48048668 5 pink balloons supervision < 6 year no no unknown 48048684 apple green balloons supervision < 6 year no no unknown 48048692 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

Description

age indication

warning

test reports

nitrosatable substances (g/dm2)c 0.351 0.351 0.351 0.519

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

ANNEX II: MIGRATION OF NITROSAMINES AND NITROSATABLE SUBSTANCES Table 5: Migration of nitrosamines and nitrosatable substances from latex balloons N-nitrosamines (mg/kg) NDMA NDBA NDBzA NMPhA NDEA total Sample nr. 45109283 0.011 0.028 0.039 45109291 0.003 0.045 0.048 45109305 0.003 0.044 0.047 45109313 0.057 0.002 0.001 0.061 45109321 0.006 0.033 0.002 0.041 45109348 0.005 0.009 0.014 45109356 0.004 0.001 0.006 45109364 0.162 0.008 0.170 45109429 0.028 0.042 0.009 0.079 45109437 0.048 0.031 0.079 45109445 0.004 0.017 0.006 0.027 45109453 0.339 0.019 0.0004 0.358 45109461 0.014 0.036 n.d. 0.051 45109488 0.003 0.012 0.0007 0.016 45109526 0.003 0.028 0.031 45109534 n.d. 0.001 0.001 45109542 0.002 0.062 n.d. 0.063 46521234 0.087 0.004 0.091 duplicate 0.043 n.d. 0.043 46521242 0.067 0.002 0.069 46521269 0.003 n.d. 0.003 46521277 0.001 0.008 n.d. 0.009 46521285 0.028 0.025 0.053 46521293 0.056 0.013 0.070 46521307 0.174 0.005 n.d. 0.179 46521315 0.026 0.043 0.069 46521323 0.007 0.011 0.018 46521404 0.002 0.001 0.004 duplicate 0.003 0.021 0.024

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

total (g/dm2) 0.009 0.007 0.009 0.017 0.014 0.004 0.002 0.041 0.020 0.016 0.008 0.009 0.005 0.010 0.0003 0.020 0.020 0.012 0.017 0.001 0.002 0.015 0.014 0.040 0.016 0.004 0.001 0.007

NDMA 0.115 0.013 0.096 0.065 0.033 0.208 0.067 1.140 0.075 0.689 0.199 1.493 0.771 0.198 0.251 0.042 0.083 0.844 0.331 0.167 0.153 0.027 0.300 0.337 1.233 0.085 0.151 0.030 0.179

nitrosatable substances (mg/kg) NDBA NDEA total 0.016 0.454 0.030 0.180 0.007 0.411 0.027 n.d. 0.003 0.145 0.061 0.027 0.269 0.833 0.198 0.168 1.204 0.003 0.012 n.d. 0.772 0.143 1.327 0.061 0.016 0.327 0.469 0.035 n.d. 0.132 0.468 0.126 0.246 0.042 0.619 0.094 1.140 0.077 0.833 0.260 1.672 1.138 1.041 0.450 0.209 1.293 0.847 0.343 0.167 0.925 0.203 1.627 0.398 1.305 0.413 0.620 0.066 0.179

0.0009 0.002

0.153 0.098 0.010 0.006

0.036 0.056

total (g/dm2) 0.03 0.07 0.02 0.07 0.01 0.17 0.03 0.28 0.02 0.17 0.08 0.20 0.35 0.14 0.06 0.42 0.19 0.10 0.04 0.21 0.05 0.46 0.08 0.29 0.09 0.15 0.02 0.05

Sample nr. 46521412 duplicate 46521439 46521447 46521455 46521463 46521471 46521498 46521501 47783267 47783275 47783305 47784131 47784158 47885183 47885191 47885205 47885213 47885361 47885388 47885396 47885418 47885426 47885434 47885442 48048625 48048633 48048641 48048668 48048684 48048692 48048706

NDMA 0.004 0.006 0.005 0.017 0.073 0.207 0.010 0.001 0.001 0.747 0.011 0.014 0.019 0.123 0.011 0.007 0.008 0.001 0.023 0.010 0.001 0.016 0.002 n.d. 0.016 0.009 n.d. 0.005 0.021 0.006 0.021 0.019

NDBA 0.009 0.014 0.013 0.048 0.011 0.229 0.033 0.004 0.002 n.d. 0.012 0.054 0.031 0.029 0.187 0.007 0.044 0.030 0.122 0.014 0.015 0.057 0.007 0.004 0.025 0.002 n.d. 0.003 0.008 n.d. 0.022 0.006

NDBzA

N-nitrosamines (mg/kg) NMPhA NDEA

total 0.013 0.020 0.018 0.064 0.084 0.576 0.043 0.005 0.003 0.747 0.022 0.069 0.050 0.152 0.199 0.014 0.052 0.031 0.144 0.024 0.016 0.073 0.008 0.004 0.088 0.011 0.008 0.008 0.029 0.006 0.043 0.023

0.140 n.d.

n.d. 0.0003 0.047 0.008

total (g/dm2) 0.004 0.004 0.006 0.016 0.022 0.128 0.010 0.001 0.001 0.210 0.005 0.020 0.015 0.038 0.035 0.004 0.011 0.009 0.044 0.006 0.004 0.001 0.001 0.023 0.003 0.002 0.002 0.012 0.001 0.008 0.006

NDMA 0.083 0.441 0.152 0.483 0.342 0.317 0.085 0.018 0.058 1.331 0.763 0.346 0.061 0.051 0.277 0.092 0.094 0.040 0.421 n.d. 0.044 0.248 0.059 0.107 0.131 0.043 0.117 0.025 0.015 0.018 0.117 n.d.

nitrosatable substances (mg/kg) NDBA NDBA NDEA total 0.144 n.d. n.d. 0.074 0.028 0.223 0.145 0.006 n.d. n.d. 0.006 1.253 0.183 0.197 1.340 0.683 1.046 1.729 1.672 n.d. 1.101 2.927 0.964 1.701 0.382 n.d. n.d. 0.003 0.175 0.003 n.d. n.d. 0.227 0.441 0.152 0.556 0.370 0.565 0.230 0.024 0.063 1.331 0.767 1.599 0.244 0.247 1.617 0.775 1.140 1.769 2.146 n.d. 1.145 3.209 1.023 1.808 0.513 0.043 0.117 0.028 0.191 0.022 0.117 n.d.

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

0.026 0.004

0.053 0.034

n.d.

total (g/dm2) 0.07 0.10 0.05 0.14 0.10 0.13 0.05 0.01 0.02 0.37 0.16 0.46 0.07 0.06 0.29 0.22 0.25 0.49 0.65 n.d. 0.30 0.15 0.41 0.13 0.01 0.03 0.01 0.08 0.005 0.02 n.d.

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 2 NDMA NDBA NDMA NDBA N-nitrosamines X-gem (g/kg) 4.6 21.3 4.4 20.4 St. dev. (g/kg) 1.1 1.8 0.5 1.5 RSD (%) 23.4 8.7 10.4 7.4 Nitrosatable substances X-gem (g/kg) 695 816 400 1772 St. dev. (g/kg) 151 76 102 290 RSD (%) 21.7 9.3 25.3 16.4

VWA/KvW Noord, report: nd04o063/02, January 2005

Annex III