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Survey of chemical substances in consumer products no. 70, 2006 Survey, migration and health evaluation of chemical substances in toys and childcare products produced from foam plasticContents
PrefaceThe project “Survey, migration and health evaluation of chemical substances in toys and childcare products produced from foam plastic“ was made on behalf of the Danish environmental protection agency. The project was a cooperation between The Danish Toxicology Centre, responsible for the survey and the health evaluation and Analytica AB, responsible for the chemical analysis. The purpose of this project was to make a survey of toys and childcare articles produced from foam plastic in Denmark. Based on the survey the purpose was to select a number of products for analyses for content of chemical substances know to cause health problems in humans. Based on the analytical results chemical substances were chosen to the health assessment. SummaryThe objective of Phase 1 was to make a survey of toys and childcare articles on the Danish market produced from foam plastic, including their chemical composition. Most wholesalers and distributors of toys and childcare articles have been very helpful providing lists of products of their assortment. It has however been difficult to obtain information on consumption and almost impossible to obtain information on the chemical composition of the products. Foreningen af Legetøjsfabrikanter i Danmark (FLD) (The Association of Toy Manufacturers in Denmark), whose members count seven of the largest manufacturers in Denmark estimates that less than 1% of all toys (by number) are produced from foam plastic (1). Based on data from the website “Danmarks statistik – www.statistikbanken.dk”, an estimate on toys and childcare articles on the Danish market was made (2). The website contains information on imported and imported products in kilos. Since DTC did not find any toys or childcare articles made from plastic foam produced in Denmark, only the number of imported toys was estimated. As it was not possible to select data on specific materials, a data selection from the statistic base on a superior level was made based on which foam plastic products were specified. The estimated total of imported toys and childcare articles made from foam plastic in 2004 was 171.2 ton. During the survey, it was not possible to obtain information on the complete chemical composition of the products. DTC obtained information on the use of two basic polymers, ethylene vinyl acetate (EVA) and polyurethane (PUR). Based on the survey, the Danish Environmental Protection Agency (Danish EPA) has selected the following products for testing:
The objective of Phase 2 is to determine the content of hazardous substances in the selected products. The selection of substances was based on knowledge of additives in plastic products as well as knowledge of substances that may be hazardous to humans. The process of analyses was iterative and initiated with qualitative and quantitative analyses of eight products for bromated flame-retardants, TCEP, phthalates and metals. Testing for content of organic tin compounds and colorants was also performed as well as a screening for volatile organic compounds in selected products. The test results are shown in the following survey.
The content of phthalates in two products (4 and 7) were higher than the limit value for phthalates in toys intended for children between 0-3 years of 0.05%, and the two products were ordered withdrawn from the Danish market (3). 5 chemical substances were selected for the safety assessment in phase 3; diisobutylphthalate (DIBP), di-n-butylphthalate (DBP), diisononylphthalate (DINP), monobutyltin (MBT) and dibutyltin (DBT). The purpose of phase 3 was to set up toxicological profiles for the above 5 substances and perform an exposure assessment of MBT and DBT in product 6. Based on the safety assessment in phase 3, the below assessments were performed. The highest DIBP measured in the remaining 6 products, was 6.5 mg/kg in product 5 (corresponding to 0.00065%). The amount is lower than the above limit value (3), and does not cause any health concern. The highest DBP measured in the remaining 6 products was 11.9 mg/kg in product 6 (corresponding to 0.00119%). The amount is lower than the above limit value (3), and does not cause any health concern. The highest amount of DINP measured in the remaining 6 products was 935 mg/kg in product 1 (corresponding to 0.0935%). The amount is higher than the above limit value (3), but as the product is intended for children > 3 years it was not withdrawn from the Danish market. The distributor of product 1 was informed of the content of DINP in the product and is working on eliminating the substance from the product. Foamed toys and childcare products are mainly produced from EVA and PUR foam. Based on this survey, it is recommended to focus on the content of phthalates of these products, as 2 of 8 products contained concentrations above the permitted limit value for phthalates (0.05%) in toys intended for children between 0-3 years, (3). DEHP is furthermore contained in all products. DEHP, DBP and BBP, which have been identified as reproduction toxic substances, will be prohibited in concentrations above 0.1% of all softened toys and childcare articles. DINP, DIDP and DNOP will be prohibited in toys and childcare articles intended for mouthing (4). The prohibition comes into force one year after the proportion is agreed upon in the council. 2 products (4 and 6) were analysed for organic tin compounds. Product 4 was withdrawn from the Danish market and consequently it was not assessed. 1.95 µg MBT/kg and 1.15 µg DBT/kg was measured in product 6 (a fabric book with PUR stuffing intended for children under 3 years). Sufficient data was not found on MBT and DBT’s toxic effects in animals and humans. The substances were assessed based on a Tolerable Daily Intake (TDI) for the two substances recommended by the Scientific Committee on Toxicity, Ecotoxicity and the Environment (CSTEE) (4). The assessment was based on a worst-case scenario under the assumption of a release of the total amount of MBT and DBT in one day and exposure of a newborn child and a child of 1.5 years of age. The average weight in Denmark of a newborn child is 3,450 g (5) and a child of 1.5 years weighs 9,850 g (6). An additive effect of the two substances is expected. A fraction sum < 1 means that the total content of MBT and DBT in the book does not cause any health concern.
The fraction sum of the exposure of a newborn child and a child of 1.5 years old is 0.08 and 0.03, respectively. This means that there is no reason for health concerns based on the content of MBT and DBT in the book. The Margin of Safety (MoS) for the exposure of the two organic tin compounds from the book was calculated by dividing NOAEL with the exposure (under the assumption that the entire amount of MBT (1.95 µg/kg book) and DBT (1.15 µg/kg book) is released in one day. A NOAEL for DBT of 2.5 mg/kg bw/day was used for both MBT and DBT.
A MoS of 86000 and 250000 was calculated for a newborn child and a child of 1.5 years old, respectively, which is assumed to be sufficient for the protection of children. The used NOAEL for MBT and the assumption of a release of the total content of the organic tin compounds in one day underestimates the MoS. DTC estimates that exposure to organic tin compounds from the book does not cause any health concerns. Because of the large amount of organic tin compounds found in dust from European households, and the potential to ingest organic tin compounds through breast milk and food and from a number of other consumer products, DTC recommends that the contribution from other sources is calculated. An estimation of how large an amount of TDI that could be allocated to consumer products is then possible. IntroductionToys and childcare articles produced from plastic are predominating in nurseries. Many of these products may contain chemicals that may be potentially hazardous to human health and the environment. Since the central nervous system, the immune system and the reproductive ability of children are more vulnerable than those of adults (7), it is important to assess whether these products contain chemicals that may cause adverse effects on children playing with them. In this project, DTC has been requested to make a survey on toys and childcare articles specifically produced from foam plastic – phase 1. Based on the survey, a number of products to be tested by the analysis laboratory, Analytica AB were selected – phase 2. The test programme is based on knowledge of additives in plastic products as well as of substances that may be hazardous to humans. 1 Survey of toys
The objective of Phase 1 is to make a survey of toys and childcare articles produced from foam plastic on the Danish market, including their chemical composition. Phase 1 includes the following sub-activities:
1.1 Definition of productsIn the project description the Danish Environmental Protection Agency (DEPA) presented the following examples of toys and childcare articles produced from foam plastic: Floor puzzles and disguise items, such as masks, swords, and shields for role-playing. Most of the products intended for the formalized form of role-playing are made from latex and therefore excluded from this project. Apart from the product groups mentioned above, cuddly and soft-toys, handgrips on vehicles, support in rollers, protection equipment, soft balls, swim equipment, crowns and picture books were included in the survey, if they contained foam plastic. Mattresses and furniture containing foam plastics were excluded, as they are considered outside the target group of this project. 1.2 Survey of toys and childcare articles for children produced from foam plasticThe product survey of toys and childcare articles for children produced from foam plastic on the Danish marked was based on:
DTC estimates that the above activities adequately illustrate the Danish market for toys and childcare articles produced from foam plastic. A list of products on the Danish marked is presented in table 1.4. Table 1.1 Contacted wholesalers of toys (in bold), references from wholesalers to other distributors (not in bold)
* Distributor of toys and childcare articles produced from foam plastic. Table 1.2 Stores distributing toys and childcare articles
*Stores distributing toys and childcare articles produced from foam plastic. Table 1.3 References from Danish websites containing information on foam plastic products
Table 1.4 Products produced from foam plastic found on the Danish market.
* Estimated by DTC Figure 1 Distribution on different types of toys and childcare articles produced from foam plastic based on present survey
1.3 Chemical composition of toys and childcare articles produced from foam plasticExperience shows that it is often difficult to obtain information on complete chemical composition from manufacturers. Since most of the products relevant for this project are made in the Far East, the elaboration of the survey of the chemical composition was complicated and the available information very sparse. It was not possible to obtain full chemical composition of any of the products. Only two manufacturers returned partial information on the chemical composition of the products. As this information is given in confidence, we have abstained from presenting this information to prevent transparency in the product information. 1.4 Estimated consumptionDTC received information on sales numbers from very few distributors of toys and childcare articles produced from foam plastic. The Association of Toy Manufacturers in Denmark that counts seven of the largest manufacturers of toys in Denmark evaluates that less than 1% of the total amount of toys is produced from foam plastic (1). From the website “Danmarks statistik – www.statistikbanken.dk” information on imported products stated in either kilos or Danish crones was retrieved (2). DTC estimated that there are four main groups of toys primarily made from plastic foam. The four main groups are toy weapons, puzzles, balls, and swim equipment. The remaining products are more isolated examples. e.g. a blackboard with a sponge made from foam, doll's pram with handgrips made from foam or rollers with foam insertion. As the scope of this project does not admit a thorough investigation of the different products, we have decided to focus on the main groups described in table 1.5. It is not possible to select data on specific materials. Therefore data from the statistic base on a superior level have been selected followed by an estimate from DTC specified on foam plastic products. Data have been selected as follows: The names of the four main groups in the statistics database are “toy weapons”, “puzzles except from wooden puzzles”, “balls except from balls for golf, table tennis, tennis, cricket, polo and inflatable balls” and “swim equipment including swimming- and paddling pools and childcare articles for outdoor play”. DTC found neither toys nor childcare articles made from plastic foam, which have been produced in Denmark. Therefore, only imported numbers are included in the below estimate (Table 1.5). Table 1.5 Estimated amount of toys and childcare articles for children composed of foam plastic imported in 2004. The estimate is based on 4 main groups of toys.
* Estimated by DTC The total amount of toys and childcare products imported to Denmark in 2004 is estimated to be 171.2 tons. 1.5 Selection of products for analysisThe Danish EPA has selected the products stated in table 1.6 for testing. Table 1.6 Products for testing
2 Analyses
2.1 ObjectiveThe objective of phase 2 is to determine the content of hazardous substances in selected products, as it is not easily obtained from importers or producers. From the survey results of phase 1, The Danish Environmental Protection Agency and DTC selected a number of products to be analysed for certain chemical substances (Table 2.1). The products were selected to cover the most sold products on the marked and ages below and above 3 years. The three new toy standards EN71-9: 2005, Final draft PrEN71-10: 2004 and Final draft prEN71-11: 2005 contain recommended testing of 26 product types, which however of the 8 selected products only include the mask: “Toys worn over the mouth or nose”. The selection of the chemical substances was based on knowledge of additives in polymers and knowledge of substances hazardous to humans. Phase 2 was an iterative process that was initiated with qualitative and quantitative analyses of 8 products for bromated flame-retardants, TCEP, phthalates and metals. Based on the test for metals where two products were found to contain tin, these two products were furthermore tested for content of organic tin compounds. Two products representing a product with printed colours and a product with dyed colours were chosen for analysis for content of colorants. 4 Products were selected for a screening of volatile organic compounds, partly based on a RAPEX notification (Rapid Alert System for Non-Food Products) on an EVA product, witch contained organic solvents - and for one of the products also because of a chemical scent from the product. Table 2.2. shows a the performed tests. Analytica AB performed the analyses. Table 2.1 Selected products
2.2 Analysis ProgrammeEach section contains a description of the used analysis method, including detection limits and analysis uncertainties. All analyses are based on double determinations. Table 2.2 Performed tests
2.3 Analysis methodsA weighed sample (approx. 30 – 50 g) was taken from the foam matrices of all products and fractionized into particles with surfaces of maximally 6 mm. The colours of the products with different colours were equally distributed to make the sample representative for the complete product. From product no. 1 sample material was taken from the handle, as the handle is the most used contact surface of the product. The products containing several different materials (e.g. textile, elastic and foam), only partial samples of the foam material were taken (product no. 4, 5 and 6). 2.3.1 Flame retardantsThe method for testing the content of bromated flame-retardants and TCEP is Soxhlet extraction of 1 – 2 g material with toluene (4-5 hours). By Soxhlet extraction the test sample is heated and the chemical substances is trapped in a closed system. GC-MS-measurements were made. The uncertainty of the analysis for pentabromodiphenyle ether (PeBDE) and octabromodiphenyl ether (OBDE) is < 15% and for the remaining decabromodiphenyl ether (DeBDE) tetrabromobisphenol A (TBBPA), hexabromocyclododecan (HBCD) og tris(2-chloroethyl)phosphate (TCEP) < 25%. The internal standards used for PeBDE, OBDE, DeBDE, HBCD, and TCEP were: DBOFB (Dibromooctafluoro biphenyl) for "retrieve control" and PCB209 for “injectioncontrol”. For TBBPA the internal standard was: Tribromophenol. For external standards, the compounds tested for was used. 2.3.2 PhthalatesA Soxhlet-extraction (6 hours) with hexane is used for testing the content of phthalates. By Soxhlet extraction the test sample is heated and the chemical substances are trapped in a closed system. GC-MS measurements were performed. The analysis uncertainty of the determinations is 20-30%. The detection limits of the phthalate analyses stated below are for standard analyses in solid (not foamed) matrices with a fixed test quantity (10-20 g). The standardised amount of test material cannot be used for testing in foam matrices, because the large volume and surface would interfere with the analysis. 1-2 g test material is used for the analyses, and the detection limit is thus 10 times lower than the reported minimum values. Internal standards were hexaclorobenzene and deuteriummarked-DEHP. For external standards, the compounds tested for was used. 2.3.3 MetalsThe method for testing migration of metals is governed by The Toy Standard EN 71-3:1994. Besides the 8 metals in the Toy Standard, testing for tin and nickel is also performed. The sample is fractionized into particles with a surface of maximum 6 mm. The particles are placed in a 37oC hydrochloric acid solution (0.07 mol/l) – equal to 50 times the sample weight, shaked for 1 hour and filtrated and centrifuged before analysis. The analysis uncertainty of the metals given in table 2.6 is for the individual metal and not for the method in particular. The analyses methods for tin and nickel are not accredited and consequently their uncertainties are not stated. 2.3.4 Organic tin compoundsThe method used for testing the content of organic tin compounds is an extraction (2-3 hours) of 1-2 g material with a sodium diethyldithiocarbamate solution in ethanol, alkylated with sodium tetraethyborate and transferred to organic phase by extraction with hexane. The uncertainty of the analysis is 10-20%. 2.3.5 ColorantsThe method used for testing the content of aromatic amines was extraction of 2-5 g material at 70o C in a buffer solution with pH=6 followed by reduction for 30 min. and dredging by liquid/liquid extraction. GC-MS-measurements were performed. The method used for testing of content of the carcinogenic, allergenic and supplementary 4 colorants was extraction at 70 °C in methanol in 30 minutes and clean -p by filtration. LC-MS-measurements were performed. The reported results are the extractable parts of the colorants. The uncertainty of the analyses were < 20%. 2.3.6 Screening for volatile organic solventsThe method for screening for volatile organic compounds (VOC) was a fractionization into particles of approx. 0.5 – 4g material were To screen for organic volatile substances the samples were fractioned, whereupon 0,6 µg internal standard per sample was added (deuterated toluene, deuterated C2-aromates, deuterated decane, deuterated C3 aromates). The screening for VOC was in a mass area of 30 -.700 amu. The GC-MS headspace measurement method (at 80°C) was used. The screening approximately last for 30 minutes and the detection limit is estimated to be approximately 0.5 ug/sample. As the analysis was a screening for VOC without quantification or qualification of the substances, the uncertainty of the analysis is not indicated. If there had been more time in the project, analysis could have been made, that identified and quantified chemical substances present in the products. 2.4 Analyses results2.4.1 Flame retardantsThe content of flame-retardants above the detection limit has not been measured. EU has assigned a limit value of 0.1% for content of PeBDE and OBDE. Marketing of products containing one of these two substances above this limit value is not legal in the EU. The detection limit of all tested flame-retardants is below this limit value, and DTC evaluates that the results do not imply further testing. Table 2.3 Content of flame-retardants (mg/kg). The values are averages of duplicate determinations. The uncertainty of the analysis for pentabromodiphenyle ether (PeBDE) and octabromodiphenyl ether (OBDE) is < 15% and for the remaining decabromodiphenyl ether (DeBDE) tetrabromobisphenol A (TBBPA), hexabromocyclododecan (HBCD) og tris(2-chloroethyl)phosphate (TCEP) < 25%.
DL*: Detection limit 2.4.2 PhthalatesPhatalates have been found in all products. The products 4 and 7 both exceed the permitted limit (0.05%) for phthalates in toys intended for children between 0-3 years (3). On the packaging of product no. 7 is indicated that the product is intended for children of more than 3 year. However, as The Danish Safety Technology Authority has decided that the product because of appearance and shape also appeals to children of less than three years. The Danish EPA has decided that the limit value for phthalates in toys for children between 0-3 years should be observed. Product 4 contains totally 1867.8 mg/kg (corresponding to 0.19%), diisobutylphthalate (DIBP) (1800 mg/kg) being the absolutely largest quantity. Product 7 contains totally 1451.8 mg/kg (corresponding to 0.15%) with di-n-butylphthalate (DBP) (780 mg/kg) as the greatest quantity. The two products (4 and 7) were therefore withdrawn from the Danish market. All 8 products also contain di-2-(ethylhexyl)phthalate (DEHP). Table 2.4 Content of phthalates (mg/kg) in all 8 products. The results are averages of duplicate determinations. The analysis uncertainty of the determinations is 20-30%.
* DL: Detection Limit In the process of evaluating the above results, DTC realized that tests were not performed for diisodecylphthalate (DIDP) and diisononyl phthalate (DINP), and testing for these phthalates was performed. Product 4 and 7 were not tested, because they had been withdrawn from the Danish market. Table 2.5 Content of phthalates (mg/kg) in the selected products. The results are averages of duplicate determinations. The analysis uncertainty of the determinations is 20-30%.
* DL: Detection limit Based on the above analyses, DIBP, DBP and DINP were selected for toxicological assessment in Phase 3. 2.4.3 MetalsThere is no migration of metals in concentrations above the migration limits as stipulated in DS/IN 71-3. There is a migration of tin compounds from product 4 and 6 45 mg/ and 21 mg/kg), which is calculated as the average of two determinations. As the products are produced from polyurethane (PUR), the tin present may be from organic tin compounds, which are used catalyst in the production of PUR. Table 2.6 Migration of metals in mg/kg. The values are averages of duplicate determinations.
DL: Detection limit AU: Analysis Uncertainty 2.4.4 Summary of initial qualitative and quantitative analysesThe conclusion of the above results:
It was decided to analyse product 4 and 6 to clarify, if they contained organic tin compounds, and in the affirmative which. 2.4.5 Organic tin compoundsMonobutyltin (MBT) and dibutyltin (DBT) were measured above the detection limit in product no. 4 and 6. Table 2.7 Content of organic tin compounds (µg/kg) in the selected samples. The values are averages of duplicate determinations. The analysis uncertainty of the determinations is 10-20%.
DL: Detection limit Based on the data shown in table 2.7, MBT and DBT have been selected for assessment in phase 3. 2.4.6 IsocyanatesProducts produced from polyurethan (PUR) foam may contain isocyanates, if they are packed prematurely in tight plastic. Testing for isocyanates was not performed, because the two products produced from PUR foam were not packed in air free packaging and their hardening process thus considered completed. 2.4.7 ColorantsTwo products to be tested for colorants were selected. The products were selected from the remaining 6 products (1, 2, 3, 5, 6 and 8) were sword and floor puzzle (1 and 2), as they represent a product with printed colours and a product with many dyed colours. Testing was performed for azo colorants, colorants that are known as allergens or carcinogens, and 4 supplementary colorants from EN71-9. The specific colorants are listed in table 2.8. Table 2.8 Tested colorants and detection limits. The analysis uncertainty of the determinations is < 20 %.
No colorants above the detection limit have been measured in the two products. According to the Toy Standard “Organic chemical compounds – requirements”, EN71-9, the limit value of aromatic amines is the detection limit (5 mg/kg. As described in Section 2.1, this standard does not cover products such as the sword and the puzzle. However, judged from the limit value assigned for other product types, the content of azo colorants should not cause any concern. The detection limit of the carcinogenic, allergenic and supplementary 4 colorants are however markedly higher than the limit proposed in Final draft prEN71-11 of 10 mg/kg. As is the case for the phthalate analysis described in paragraph 2.3.2, this is caused by the smaller amount of sample material compared with the standard analyses in solid (not foam) matrices, because a larger amount of sample would interfere with the analyses in the test. Therefore, it is not possible to evaluate if the amount of colorants exceeds the limit values proposed in EN71-11. This assessment would require a test method to analyse the colorants with a lower detection limit in complex polymer matrices. 2.4.8 Screening for organic solventsThe last test was a screening for volatile organic solvents. The method detects the presence of volatile solvents (< C14 – C16), but a qualification and quantification of the compounds were not carried out. 4 products were selected for the screening: Sword, floor puzzle 1, mask and ball (product no. 1, 2, 5 and 8). The products were selected on the basis of a RAPEX information (Rapid Alert System for Non-Feed Products) concerning an EVA product containing organic solvents – and for the ball also based on a chemical smell from the product. The puzzle and the ball were wrapped when purchased, and to perform a test with an optimal simulation of the exposure to a child, when opening a new product, it was decided to repurchase these two products. However, the ball was out of stock and only the puzzle was repurchased. Testing of the ball, the mask and the sword was performed in previously purchased products. Table 2.9 Screening for volatile organic solvents in the selected samples (C14 – C16).
Only in product no. 2 and 8, signals for VOC were detected (C14 - C 16). Only in product 8, the signals were significant, and the analysis laboratory has identified the substances to be hydrocarbons with a carbonic chain length of C10 to C14. Due to shortage in time, these signals were not further qualified or quantified. If there had been more time in the project, analysis could have been made, that identified the chemical substances and the concentration. 2.5 Summary of analysis results
3 Health assessmentBased on the results of the analysis of diisobutylphthalate (DIBP), di-n-butylphthalate (DBP), diisononylphthalate (DINP), monobutyltin (MBT) and dibutyltin (DBT) were selected for assessment. The toxicological profiles for the 5 chemical substances are described in the following. 3.1 Toxicological profiles3.1.1 Diisobutylphthalate3.1.1.1 UseIs used as softener in plastic, paint, lacquer, glue and die (8). 3.1.1.2 Identification
Physical-chemical properties (14).
The highest amount of DIBP measured in the 6 products (product 4 and 7 are not included as they were withdrawn from the Danish market) was 6.5 mg/kg in product 5 (corresponding to 0.00065%). The amount is markedly lower than the permitted limit for phthalates in toys intended for children between 0-3 years of 0.05% (3) and the substance is not further assessed. 3.1.2 Di-n-butylphthalate3.1.2.1 UseIs used as softener in plastic, paint, lacquer, glue and die (8). 3.1.2.2 Identification
Physical chemical properties (14).
The highest amount of DIBP measured in the remaining 6 products was 11.9 mg/kg in product 6 (corresponding to 0.00119%) The amount is considerably lower than the permitted limit for phthalates in toys intended for children between 0-3 years of 0.05% (3) and the substance is not further assessed. 3.1.3 Diisononyl PhthalateUseUsed as softener in plastic (8). Identification
Physical-chemical properties (14), (22)
The highest amount of DIBP measured in the 6 remaining products was 935 mg/kg in product 1 (corresponding 0.0935%.) The amount is higher than the permitted limit for phthalates in toys intended for children between 0-3 years of 0.05% (3) However, as the product is intended for children > 3 years, it has not been withdrawn from the Danish market. The distributor of product 1 has been informed of the content of DINP in the substance and is working on eliminating the substance from the product. 3.1.4 MonobutyltinUseIs used as catalyst in the production of PUR foam. Organic tin compounds are also used in other kinds of polymers (e.g. PVC), packaging for foodstuff, pesticides and paints (23). Identification
Physical-chemical properties
No data were found on the toxic effects of monobutyltin in animals and humans, by searching toxicological databases (Micromedex[13] and TOXNET[14]) and standard literature at DTC. The compound is assessed in section 3.1.7. 3.1.5 DibutyltinUseIs used as catalyst in the production of PUR foam. Organic tin compounds are also used in other kinds of polymers (e.g. PVC), packaging for foodstuff, pesticides and paints (23). Identification
Physical-chemical properties
Sufficient data has not been found on the toxic effects of DBT in animals and humans. Literature has been searched for in toxicological databases (Micromedex and TOXNET) and standard literature at DTC. The substance is assessed in section 3.1.7. 3.1.6 Tin compounds generallyTin can combine with other chemicals to form compounds. Combinations with chemicals like chlorine, sulfur, or oxygen are called inorganic tin compounds. These are used in toothpaste, perfumes, soaps, food additives and dyes. Tin also can combine with carbon to form organic tin compounds like the compounds above, monobutyltin and dibutyltin (23). Tin metal is used to line cans for food and beverages. Exposure to inorganic tin compounds can occur by eating food or drinking liquids from tin-lined cans (today greater than 90% of tin-lined cans used for food are protected with lacquer). Metallic tin is not very toxic due to its poor gastrointestinal absorption. Human and animal studies show that ingestion of large amounts of inorganic tin compounds can cause stomachache, anemia, and liver and kidney problems (23). Exposure to some organic tin compounds can occur by eating seafood from coastal waters (23) or from contact with consumer products i.e. toys produced from PVC or PUR, supports in shoes, biker’s pants, foot spray and silicon coated cooking paper (26). Inhalation of dust can also cause exposure to organic tin compounds from floor- and wall covers that releases organic tin compounds due to wear and tear. Levels of MBT and DBT have been found in dust from European households of respectively 2.8 and 1.3 mg/kg dust (27). Breathing or swallowing, or skin contact with some organotins, such as trimethyltin and triethyltin compounds, can interfere with the way the brain and nervous system work. In severe cases, it can cause death. Some organic tin compounds, have been shown to affect the immune system in animals and to affect the reproductive system. This has not been examined in people (23). Inorganic or organic tin compounds placed on the skin or in the eyes can produce skin and eye irritation. There is no evidence that tin or tin compounds cause cancer in humans. Studies in animals have not shown evidence of carcinogenicity for inorganic tin. A study in rats and another in mice showed that a specific organic tin compound, triphenyltin hydroxide, could produce cancer in animals after long-term oral administration. There is conflicting evidence as to whether tin compounds can be transferred to offspring through breast milk (23). Data from a study of women in Zaire and Guatemala has shown tin levels in the breast milk of respectively 0.24 and 2.81 µg/l breast milk. There is no mention of whether the tin originates from inorganic or organic tin compounds (28). Children under 6 months are mainly expected to ingest breast milk or milk substitute (29). If the measured concentrations of tin in breast milk originate from organic tin compounds, food can be a source of exposure for infants (28). Furthermore exposure from inhalation of dust containing organic tin compounds can also be a source of exposure (27). Children of more 6 months are mainly exposed to tin through the feed, by eating contaminated soil, and by inhalation of dust containing organic tin compounds. A 7-day study of 1.75 – 2.2 year-old children illustrated that the daily intake of tin through feedstuff was 1.78 mg/kg bw and the daily exposure through intake of contaminated soil was 1-200 µg Sn (23). There is no specification of whether the measured tin levels originate from inorganic or organic tin compounds (23). 3.1.7 Assessment of organic tin compounds in product no. 6Testing was performed for organic tin compounds in 2 products (4 and 6). As product 4 had been withdrawn from the Danish market, it was not included in the assessment. In product 6 (a fabric book with PUR-stuffing intended for children under 3 years) was measured 1.95 µg MBT/kg and 1.15 µg DBT/kg. The exposure route of the fabric book with PUR-stuffing is mainly oral, as children are expected to mouth things. By contact with saliva, the external fabric layer may be soaked and possible chemical substances in the PUR-stuffing may be available for ingestion. Testing for release of organic tin compounds to sweat and saliva has not been performed and the below assessment is therefore based on a worst-case scenario. Table 3.1 Concentration of MBT and DBT in product no. 6. The values are averages of duplicate determinations. CSTEE’s recommended TDI for MBT and DBT.
The average weight of a newborn child in Denmark is 3,450 g (5), and of a child of 1.5 years 9,850 g (6). It is assumed that the measured total amount of MBT and DBT is released in one day and that the substances have an additive effect. The following form is used to calculate the total effect of MBT and DBT. A fraction sum < 1 means that the total content of MBT and DBT in the book do not cause any health concern. Daily exposure, tin, child:
Daily exposure, tin, newborn:
Daily exposure, tin, 1.5 years:
The above calculation shows that the content of MBT and DBT in the book does not cause reason for health concern. The Margin of Safety (MoS)[15] for the exposure of the two organic tin compounds from the book is calculated by dividing NOAEL with the exposure (under the assumption that the entire amount of MBT (1.95 µg/kg book) and DBT (1.15 µg/kg book) is released in one day. A NOAEL for DBT of 2.5 mg/kg bw/day was used for both MBT and DBT. MoS, MBT + DBT, child:
MoS, MBT + DBT, newborn:
MoS, MBT + DBT, 1,5 year:
A MoS of 86000 and 250000 was calculated for a newborn child and a child of 1.5 years old, respectively. A high MoS means a good protection of the consumer. In this case it is recommended that the MoS is at least 1000, corresponding to 10 in order to account for sensitive individuals, 10 to account for difference between animals and humans, and 10 in order to account for quality and relevance of the data that NOAEL is based on. Furthermore the used NOAEL for MBT and the assumption of a release of the total content of the organic tin compounds in one day underestimates the MoS. DTC estimates that exposure to organic tin compounds from the book does not cause any health concerns. Because of the large amount of organic tin compounds found in dust from European households, and the potential to ingest organic tin compounds through breast milk and food and from a number of other consumer products, DTC recommends that the contribution from other sources is calculated. An estimation of how large an amount of TDI that could be allocated to consumer products is then possible. 4 Summary and ConclusionsBased on the survey phase the Danish Environmental Protection Agency selected the following products for testing:
The analysis part, which was an iterative process, was initiated with qualitative and quantitative analyses of 8 products for bromated flame-retardants, TCEP, phthalates and metals. Performed were also tests for content of organic tin compounds, content of colorants and screening for volatile organic compounds in selected products. Only concentrations of phthalates and organic tin compounds above the detection limit were measured. Based on the phthalate analyses, two products were withdrawn (4 and 7) from the Danish market because the contained amount was higher than the permitted limit value for phthalates in toys intended for children between 0-3 years (0.05%) (3). 5 chemical substances were selected for the health assessment to be performed in phase 3; diisobutylphthalate (DIBP), di-n-butylphthalate (DBP), diisononylphthalate (DINP), monobutyltin (MBT) og dibutyltin (DBT). The highest amount of DIBP and DBP (0,05%) in the remaining 6 products was measured in product 5 and 5 respectively. The amount was considerably lower than the permitted limit value for phthalates in toys intended for children between 0-3 years (3) and does not give reason for health concern. The highest amount of DINP (0.05%) in the remaining 6 products was measured in product 1. The amount was higher than the permitted limit value for phthalates in toys intended for children between 0-3 years. However, as the product is intended for children of more than 3 years, it was not withdrawn from the Danish market. The distributor of product 1 has been informed about the content of DINP in the product and is working on eliminating the substance completely from the product. Foamed toys and childcare products are mainly produced from EVA and PUR foam. Based on this survey, it is recommended to focus on the content of phthalates of these products, as 2 of 8 products contained concentrations above the permitted limit value for phthalates (0.05%) in toys intended for children between 0-3 years, (3). DEHP is furthermore contained in all products. DEHP, DBP and BBP, which have been identified as reproduction toxic substances, will be prohibited in concentrations above 0.1% of all softened toys and childcare articles. DINP, DIDP and DNOP will be prohibited in toys and childcare articles intended for mouthing (4). The prohibition comes into force one year after the proportion is agreed upon in the council. Testing for organic tin compounds was performed in 2 products (4 and 6). Product 4 has been withdrawn from the Danish market and is not included in the assessment. In product 6 (a fabric book with PUR-stuffing intended for children under 3 years) was measured 1.95 µg MBT/kg and 1.15 µg DBT/kg. An exposure assessment based on a worst-case scenario was made: A newborn child and a child of 1.5 years were exposed and the total concentration of MBT and DBT was released and ingested in one day. As sufficient data was not found on the toxic effects of MBT and DBT in animals and humans, the assessment was based on the content of tin and a Tolerable Daily Intake (TDI) for the two substances which is recommended by Scientific Committee on Toxicity, Ecotoxicity and the Environment (CSTEE) (30). The additive effect of MBT and DBT was calculated. A fraction sum < 1 means that the total MBT and DBT in the book do not cause reason for health concern. The additive effect of the substances was calculated to be 0.08 and 0.03 for a newborn child and a child of 1.5 years, respectively. Based on this calculation the content of MBT and DBT in the book should not cause any health concern. The Margin of Safety (MoS) for the exposure of the two organic tin compounds from the book was calculated by dividing NOAEL with the exposure (under the assumption that the entire amount of MBT (1.95 µg/kg book) and DBT (1.15 µg/kg book) is released in one day. A NOAEL for DBT of 2.5 mg/kg bw/day was used for both MBT and DBT. A MoS of 86000 and 250000 was calculated for a newborn child and a child of 1.5 years old, respectively. DTC estimates that exposure to organic tin compounds from the book does not cause any health concerns. DTC recommends however that the contribution from other sources is calculated. An estimation of how large an amount of TDI that could be allocated to consumer products would then be possible. 5 References1. Mattel, Zapf Creation, Brio et al. Kommunikation med medlemmer i FLD ved deres generalforsamling d. 23.5.05. 2005. 2. Danmarks statistik. Statistikbanken. Danmarks Statistik 2005. Available from: www.statistikbanken.dk. 3. Bekendtgørelse om forbud mod phthalater i legetøj til børn i alderen 0-3 år samt i visse småbørnsartikler m.v. Bekendtgørelse nr 151 af 15.marts 1999. Miljøstyrelsen 1999. Available from: http://www.retsinfo.dk/. 4. European Commission. Permanent ban of phthalates: Commission hails long-term safety for children's toys. European Commission 2005. Available from: http://europa.eu.int/rapid/pressReleasesAction.do?reference=IP/05/838&format=HTML&aged=0&language=EN&guiLanguage=en. 5. "Statistik på vægt og længde for baby 0-12 mdr.". Internet 2005. Available from: http://morsverden.dk/statistik/baby_statistik.php. 6. Bremmer HJ,van Veen MP. Children's toys fact sheet : to assess the risks for the consumer. Bilthoven: Rijksinstituut voor Volksgezonheid en Milieu;National Institute of Public Health and the Environment; 2002. (RIVM report; 612810012 Available from: www.rivm.nl/bibliotheek/rapporten/612810010.html. 7. Miljøstyrelsen. Children and the unborn child: exposure and susceptibility to chemical substances - an evaluation http://www.mst.dk/udgiv/Publications/2001/87-7909-574-7/html/default_eng.htm. Environmental project 2005;589: 8. Sheftel VO. Indirect Food Additives and Polymers : Migration and Toxicology. Boca Raton, Fla : Lewis: 2000. 9. Listen over farlige stoffer. Bekendtgørelse nr. 923 af 28. september 2005 . Miljøstyrelsen 2005. Available from: http://www.retsinfo.dk/. 10. Arbejdstilsynet. Grænseværdier for stoffer og materialer. At-vejledning C.0.1 April 2005. Arbejdstilsynet 2005. Available from: http://www.at.dk/graphics/at/pdf/at-vejledninger/gv-liste-april-2005.pdf. 11. Orientering fra miljøstyrelsen nr. 8: Listen over uønskede stoffer 2004. Opdatering af listen over uønskede stoffer, 17.06.05. København: Miljøministeriet, Miljøstyrelsen; 2004. (Orientering fra Miljøstyrelsen; vol. 2004:8) 12. European Commission. ECB. European Chemicals Bureau . European Commission 2005. Available from: http://ecb.jrc.it/. 13. European Commission. Synoptic document: Provisional list of monomers and additives notified to European commission as substances which may be used in the manufacture of plastics intended to come into contact with foodstuffs. European Commission 2003. Available from: http://cpf.jrc.it/webpack/downloads/synoptic%20document(2003.04.15).PDF. 14. National Library of Medicine (NLM). Hazardous Substances Data Bank (HSDB). USA [updated 2005]. Available from: http://www.toxnet.nlm.nih.gov/cgi-bin/sis/htmlgen?HSDB. 15. Registry of Toxic Effects of Chemical Substances (RTECS). Diisobutylphthalat. Micromedex 2005. Available from: http://csi.micromedex.com. 16. Altstoffe : Daten Zur Beurteilung Der Wirkung Auf Mensch Und Umwelt : Datensätze. Band 16. Frankfurt am Main: Verband der Chemischen Industrie e.V.; 1994. 17. GDCh-Advisory Committeeon Existing Chemicals ofEnvironmental Relevance (BUA). Diisobutylphthalate (DIBP). BUA report German Chemical Society;Gesellschaft Deutscher Chemiker; 1997;201. Available from: http://www.hirzel.de/bua-report/PDF/Summary_Report201.pdf. 18. Seed JL. Abstract from: Mutagenic activity of phthalate esters in bacterial liquid suspension assays. Environmental Health Perspectives. 1982;45:111-4. 19. Sullivan FM, Watkins WJ, van Venne MT, editors. The Toxicology of Chemicals. - Series 2: Reproductive Toxicity. - 1: Summary Reviews of the Scientific Evidence. Luxembourg : Office for Official Publications of the European Communities: Commission of the European Communities, Directorate-General for Employment, Industrial Relations and Social Affairs, Health and Safety Directorate;UMDS, Division of Pharmacology;University of London, St. Thomas' Hospital; 1993. EUR; 14991 EN). 20. Oishi S., Hiraga K. Abstract from: Effect of phthalic acid esters on mouse testes. Toxicological Letter. 1980;5(6):413-6. 21. European Commission. European Union Risk Assessment Report. DIBUTYL PHTHALATE. European Commission 2004. Available from: http://ecb.jrc.it/DOCUMENTS/Existing-Chemicals/RISK_ASSESSMENT/REPORT/dibutylphthalatereport003. 22. European Commission. European Union Risk Assessment Report. 1,2-BENZENEDICARBOXYLIC ACID, DI-C8-10-BRANCHED ALKYL ESTERS, C9-RICH AND DI-"ISONONYL" PHTHALATE (DINP). European Commission 2003. Available from: http://ecb.jrc.it/DOCUMENTS/Existing-Chemicals/RISK_ASSESSMENT/REPORT/dibutylphthalatereport003. 23. Harper C, et al. Toxicological Profile for Tin and Tin Compounds : Draft. Atlanta, Ga: United States Department of Health and Human Services, Public Health Service, Agency for Toxic Substances and Disease Registry; 2003. 4, 257p . 24. RTECS. Registry of Toxic Effects of Chemical Substances. Dibutyl-Stannane. http://csi.micromedex.com 1998 Aug. Available from: http://csi.micromedex.com/DATA/RT/RTWH6883600.HTM?Top=Yes. 25. Risk & Policy Analysts Limited. Assessment of the risks to health and the environment posed by the use of organostannic compounds (excluding use as a biocide in antifouling paints) and a description of the economic profile of the industry. Draft Final Report. European Commission - Directorate General Enterprise; 2002. 26. Helle Buchardt Boyd, Lena Hùglund. Consumer exposure to organotins prepared for the EU Commission. EU Commission DG Sanco; 2003. 27. Santillo D, Labunska I, Davidson H, Johnston P, Strutt M, Knowles O. Consuming chemical. Hazardous chemicals in house dust as an indicator of chemical exposure in the home. Greenpeace Research Laboratories. 2003. 28. Minor and Trace Elements in Breast Milk : Report of a Joint WHO/IAEA Collaborative Study. Geneva: World Health Organization;International Atomic Energy Agency; 1998. 29. van Engelen JGM,Prud'homme de Lodder LCH. Non-food products : how to assess children's exposure? Bilthoven: Rijksinstituut voor Volksgezonheid en Milieu;National Institute of Public Health and the Environment; 2004. (RIVM report; vol. 320005001) 30. Scientific Committee on Toxicity and the Environment (CSTEE). Opinion on the non-food aspects of "Assessment of the risks to health and the environment posed by the use of organostannic compounds (excluding use as a biocide in antifouling paints) and a description of the economic profile of the industry." . European Commision, Health & Consumer Protection Directorate-General 2003. Available from: http://europa.eu.int/comm/food/fs/sc/sct/out188_en.pdf. Fodnoter [1]. Danmarks statistik – www.statistikbanken.dk provided information on imported products stated in tons (2). [2] Group: Quantitative restrictions for migration in feedstuffs [3] bw: Body weight [4] LD50: The lethal dose for 50% of a given population [5] OECD: Organization for Economic Co-operation and Development [6] NOEL: No Observed Effect Level [7] TDI: Tolerable Daily Intake [8] NOAEL: No Observed Adverse Effect Level [9] NOAEC: No Observed Adverse Effect Concentration [10] LOAEC: Lowest Observed Adverse Effect Concentration [11] LOAEL: Lowest Observed Adverse Effect Level [12] Margin of Safety [13] Micromedex includes the following databases: MEDITEXT®, HAZARDTEXT®, CHRIS, Dolphin MSDS, HSDB®, IRIS, LOLI®, New Jersey Hazardous Substance Fact Sheets, NIOSH Pocket Guide (TM), OHM/TADS, RTECS®, REPROTEXT®, REPROTOX®, Shepard's Catalog of Teratogenic Agents, TERIS, - Teratogen Information System og Martindale. [14] TOXNET includes the following databases: CCRIS, ChemIDplus Lite, ChemIDplus Advanced, DART/ETIC, DIRLINE, GENE-TOX, Haz-Map, Household Products, HSDB, IRIS, ITER, TOXLINE, TOXMAP, TRI. [15] Margin of Safety (MoS) expresses the factor, that NOAEL is higher than the estimated exposure level. A high MoS means a smal risk.
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