Study based on analysis by Arnika

ARNIKA – TOXICS AND

WASTE

TOXIC SUBSTANCES IN CHILDREN´S TOYS AND CHILDCARE PRODUCTS IN BELARUS

RNDr. Jindřich Petrlík, Mgr. Jitka Straková and Mgr. Vendula Krčmářová 0

This publication has been produced with the assistance of the European Union, Czech Development Agency and IPEN. The contents of this publication are the sole responsibility of the author and can in no way be taken to reflect the views of the donors.â&#x20AC;?

Contents Introduction ................................................................................................................................6 Toxic Substances in Toys, Products for Children and Care of Them in Belarus ......................6 Phthalates in Toys .......................................................................................................................8 Phthalates as PVC plasticizers .....................................................................................................8 Phthalate Analyses and Their Results .......................................................................................13 Analytical Methods and Sampling Procedure.......................................................................13 First Phase of the Phthalate Analyses ...................................................................................14 Discussion and conclusion about the first phase of testing .................................................15 Second Phase of Testing Phthalates in Toys and Other Products ........................................16 Third Phase of the Phthalate Analyses .................................................................................17 Overall Evaluation of the Analyses .......................................................................................19 Heavy Metals â&#x20AC;&#x201C; Cadmium and Lead .....................................................................................20 Determination of Cadmium and Lead Contents in the Materials ........................................21 Conclusions and recommendations..........................................................................................24 Annex No. 1: Overview of the Analysed Samples .....................................................................28 Annex No. 2: Phthalates in dust inside buildings......................................................................39 Annex No. 3: Marking of Toys and Limits of Phthalate Contents in Toys and Other Products in Belarus ...................................................................................................................40 Annex No. 4: Summary table with all results of the phthalate analyses ..................................42 References: ...............................................................................................................................46

Introduction Toxic Substances in Toys, Products for Children and Care of Them in Belarus

The Arnika Association - Toxics and Waste Programme cooperated with the Centre for Environmental Solutions on a several years lasting project, focusing on ensuring chemical safety in Belarus. Pregnant women and young children are among the groups that are the most vulnerable to environmental pollution problems and to problems related to chemical safety in particular. Developing organisms of children, both born and unborn, are extremely sensitive to exposure to toxic chemicals, be it through food chain, skin or air. Exposure to toxic chemicals can result in irreversible and chronic health problems affecting childâ&#x20AC;&#x2122;s life for the rest of its life. Prevention of this exposure on all levels (legislature, education, awareness raising, research, etc.) is therefore very important for their health. In the past, attention concerning human organism burden by toxic substances usually focused on pollution caused by industrial plants. Recently, it has been found that in the case of certain substances, especially children are at higher risk at home, in kindergarten, or at school. This is caused by the fact that toxic substances are present in products which children come into contact with, and in furnishings of rooms where children spend majority of their time. Because of that, we focused our attention on presence of several groups of substances in toys, in childcare articles, and, to a lesser extent, also in clothes and in wallpapers. Generally, we analysed products bought in Belarus, it means the ones parents have been buying for their children and which they have been using for furnishing their households in that country. We focused on analysing three groups of questionable substances: 1) phthalic acid and isophthalic acid esters (shortly, phthalates and isophthalates), 2) heavy metals, and 3) brominated flame retardants. For two reasons, we paid the highest attention to the first group, namely phthalates and isophthalates. On the one hand, analyses of presence of these substances in products for children have not been made so often in Belarus as, for example in the European Union countries, and, on the other hand, more and more new information has been being found about this group of substances, confirming their hazardousness, especially for health of children. As an example, there may be mentioned a growing number of studies finding connection of certain phthalates, in addition to their already proved reprotoxicity (Jurewicz and Hanke 2011), also with development of asthma in children (Jaakkola and Knight 2008); (Bornehag and Nanberg 2010); (Braun, Sathyanarayana et al. 2013) and disorders of child development and child intelligence (Braun, Sathyanarayana et al. 2013), including the ADHD syndrome (attention deficit/hyperactivity) (Kim, Cho et al. 2009); (Froehlich, Anixt et al. 2011); (Jurewicz and Hanke 2011). Moreover, phthalates are members of a group of substances found by Dodson, Nishioka et al. (2012) in a number of everyday products, in addition to 6

further endocrine disruptors. In 2013, bis(2-ethylhexyl)phthalate (DEHP) was included by the IARC Scientific Panel back into the 2B group of substances, i.e., the possibly carcinogenic ones (IARC 2014). The study has been further divided into parts concerning the individual groups of substances analysed in the products. Subsequently, basic recommendations and conclusions ensuing from the analysis results have been set for each group of substances. Chemical analyses were made by top scientific institutions in the Czech Republic, namely Institute for Testing and Certification in ZlĂn (ITC), and the University of Chemistry and Technology in Prague (VĹ CHT). Preliminary screening measurements were made by experts of the Arnika Association using X-ray spectrometer NITON XL2 980 GOLDD, borrowed from the company Hukos, s.r.o. Ostrava.

Phthalates in Toys Introduction Polyvinyl chloride, better known as PVC, belongs to the most used plastic materials for several decades. It is very widely used. Most of it is used for the production of pipelines, profiles, packing materials and other consumer products. It found its place in toys and children products, too. Despite its considerable proliferation, PVC is considered to be one of the most problematic plastic ecologically and in health point of view. One of the main disadvantages of PVC lies in its basic structural element, which is chlorine. Producing PVC or its burning causes a formation of dangerous organochlorine compounds of dioxins and furans as a by-product. Regarding consumers, especially using a great amount of additives, which are necessary in PVC, to reach requested technological qualities, seems to be problematic. Since PVC is a very tough material in raw form, plasticizers have to be added. Spectrum of substances, which can be used for plasticizing PVC, is rather extensive, but phthalic acid esters (phthalates) are used the most often. These substances then represent even tens of percents of PVC weight depending on required flexibility of the final product. Since these substances are not firmly chemically bound, they can successively leak from the product. When the manufacturer intention is, on the contrary, to achieve higher PVC hardness, certain heavy metals are added into it. However, in the case of toys, they may be much more often found in colours, and not in products made of PVC.

Phthalates as PVC plasticizers Phthalates, or phthalic acid esters, represent a group of about 40 chemical substances. Some phthalates are provided to the market as chemical materials containing just one substance (for example bis(2-ethylhexyl) phthalate DEHP), while others are provided as complex mixture of isomers containing several different compounds with similar chemical structure (for example diisononyl phthalate DINP and diisodecyl phthalate DIDP). Phthalates today belong to the most widespread synthetic chemicals in the environment due to the fact that they are used in great extent outside of closed systems. In addition to already mentioned function of plasticizers in PVC, they are also used in cosmetic products and personal hygiene supplies. Further, they are used in wood surface finishing supplies, paints, cleaning and laundry detergents, glues, lubricants, medical tubes and bags for liquids, solvents and insecticides. More and more often, the most questionable phthalates have been replaced by other substances from this group 8

(in particular, DEHP). However, they prove to be no less hazardous (for example, dipentyl phthalate – DPP). Using of phthalates causes their extensive leaks into the environment. It happens during using of products and during their disposal, which makes thousands of tons annually. Consequently, phthalates have been considered to be one of the most frequent and most widespread synthetic contaminants of the environment for a long time. The individual phthalates show different properties, and whereas some of them, according to the up to now findings, do not damage health and the environment, phthalates include also a group of substances that are hazardous to human health (see summary of the basic effects of eight of them in Table No. 1). Some of the human health impacts were summarised in the study introduction already. We do not know much about many phthalates yet, similarly as about a high number of other chemical substances, because they have not been examined in detail up to now. Phthalates are mostly used as PVC plasticizers, however, they have found utilization also in cosmetics, as insecticides and adhesives. They are used also in paints. DEHP, which has been the most used phthalate to date, is known for being a dangerous substance for reproduction, which affects development of mammals’ testicles and is classified as a reprotoxic substance in the European Union. Its toxicity to developing male reproduction system has in fact been known for more than 50 years. Detected toxicity is caused mainly by mono-(2-ethylhexyl) phthalate MEHP compound, which is produced as a DEHP metabolite in the body; and it seems that it influences many aspects of liver development and functions, including hormones metabolism and immunity functions. During phthalate testing in articles from Belarus by the Central Laboratory of VŠCHT in Prague, it was found that one of the main additives is also bis(2-ethyhexyl) isophthalate (DOIP). It is probably used as a DEHP substitute. However, also this substances is ranked among

Table No. 1: Characterization of the individual phthalates. The basic table was taken over from the document „Viele Kitas stark mit weichmachen belastet – BUND fordert Verbot der Schadstoffe im Umfeld von Kindern“ (BUND 2011), and completed.

Plasticizer

Endocrine REACH disruptor (1) (2)

DEHP – bis(2ethylhexyl) phthalate

Cat. 1

DBP – di-n-butyl phthalate

Cat. 1

DIDP – di-isodecyl phthalate BBP – benzylbutyl phthalate

Cat. 2

DINP – di-isononyl phthalate DIBP – di-isobutyl phthalate

Cat. 1

Cat. 2

DNOP – di(n-octyl) phthalate DPP – dipentyl phthalate

DOIP – dioctyl isophthalate ; bis(2ethylhexyl) isophthalate

Health impact

toxic to reproduction (3), causes allergies and asthma toxic to reproduction (3), toxic to development liver damage

TDI (mg/kg body weight) (5) 0.05

0.01

0.15

Ban in products

toys, products for children, cosmetics toys, products for children, cosmetics toys intended to be put in the mouth toys, products for children, cosmetics toys intended to be put in the mouth -

toxic to reproduction (3), toxic to development liver damage, causes allergies and asthma

0.50

toxic to reproduction (3), toxic to development liver damage

not known

toxic to reproduction, toxic to development (4) toxic to reproduction (6)

toys, products for children -

0.15

Notes: (1) These materials are proposed to be banned according to the Regulation on Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH). (2) Preliminary list of substances ranked among endocrine disruptors (European Commission, 2010), i.e., substances disrupting the hormonal system. Substances ranked among endocrine disruptors (substances damaging the human hormonal system) (European Commission, 2010). In the case of substances listed in Category 1, harmful effect was found in at least one test animal. Category 2

(3) (4)

(5) (6)

comprises substances showing adverse hormonal effects in model experiments (in vitro tests). Reproductive toxicity includes damage to reproductive abilities, and damage to uterus. According to Hannase et al. (Hannas, Furr et al. 2011), DPP may be even more hazardous than the other phthalates, studied in longer term, from the point of view of impact on male genital system development. TDI: Tolerable Daily Intake according to the European Food Safety Authority (EFSA) On the basis of assessment of the substance reprotoxicity, it is ranked into category 1B (Sigma Aldrich 2013).

Because of provable toxic properties of phthalates, it is desirable that such compounds do not come into contact with the developing child organism. This concerns mainly the products that children could put into their mouths, that come into contact with their skin, or the case of presence of phthalates in the dust in the areas where children stay (Fromme, Lahrz et al. 2013); (Beko, Weschler et al. 2013); (Carlstedt, Jonsson et al. 2012). Phthalate releases from the surface of plasticized PVC are growing in particular when mechanical stress and temperature increase (chewing the toy, walking on the PVC flooring). One of the recent Danish studies showed that children are exposed to hazardous phthalates to higher extent than their mothers (Frederiksen, Nielsen et al. 2013). Since 1983 it has been known that DEHP, which is contained in children products in high concentrations, can be released by means of simulated dermal and oral contact. It turned out that there is no direct proportionality between phthalate concentration in the product or experiment duration and amount of leaked DEHP. Nevertheless, it was clearly proven that DEHP can leak from the product for a long time and when increased pressure is applied the amount of leaked substance is further increasing (Hanson 1983). Increasing fears connected with the danger of increased phthalates exposition led some countries of European Union to the steps leading to their restriction in children products. This trend ended up in temporary ban of six most common phthalates (DEHP, DBP, BBP, DINP, DIDP and DNOP) in toys for children under three years old and was accepted from 1999/815/ES decision of European Commission. In the Czech legislation, this requirement is stated in 521/2005 regulation. The ban was definitely confirmed by 2005/84 European Union directive concerning the ban of phthalates in children toys and goods, which states that: â&#x20AC;&#x153;The use of certain phthalates in toys and childcare articles made of plasticised material or including parts made of plasticised material should be prohibited as the presence of certain phthalates presents or could potentially present risks related to the health of children. Toys and childcare articles which, although not intended for that purpose, can be put in the mouth, may under certain circumstances present a risk to the health of small children if they are made of plasticised material, or include parts made of plasticised material, which contains certain phthalates.â&#x20AC;?

In the Czech Republic, 284/2006 regulation (MŽP ČR 2006) lists banned phthalic acid esters (DEHP, DBP, BBP, DINP, DIDP and DNOP) and says that: “They cannot be used as substances or components of products in concentration higher than 0.1% of weight in plasticized plastic materials used for children toys and products for children care since 16 January 2007. Toys and products for children care which contain these phthalates in higher concentration than the above stated value cannot be introduced to the market. Product for children care is any product intended for facilitation of falling asleep, calming, hygiene, children feeding or for sucking by children.” TP TC 008/2011 Regulation (ECUC 2011), which is valid in Belarus, Russia, and Kazakhstan sets up limits for chosen phthalic acid esters (DBP, DMP, DOP and DEP): “Toxicological and hygienic characteristics of hygienic safety of toys must meet the requirements specified in Annex 2 to this technical regulation of the Customs Union.” In Annex 2, limits for migration of particular phthalates from toys are stated: “dibutyl phthalate cannot be released from toys at all, dimethyl phthalate is restricted to 0.3 mg/dm3 in the water and 0.007 mg/m3 in the air, dioctyl phthalate is restricted to 2 mg/dm3 in the water and 0.02 mg/m3 in the air, diethyl phthalate is restricted to 3 mg/m3 in the water and 0.01 mg/m3 in the air.” However, other phthalates are used as plasticizer much more often at present. In spite of the fact that the ban of use of phthalates as plasticizers in toys and childcare articles has been valid in the EU for a number of years already, scientific studies from Germany, Denmark and other countries show that children are highly burdened by these substances (Frederiksen, Nielsen et al. 2013); (Beko, Weschler et al. 2013); (Fromme, Lahrz et al. 2013); (Kim, Cho et al. 2009). The reason is that the ban, similarly as in the countries of the Eurasian Customs Union, does not apply to materials used to furnish children's rooms, kindergartens, and paediatric departments in hospitals, although they may be a contamination source of areas where children stay. In 2012, the Arnika Association carried out testing of phthalate contents in wallpapers and floor coverings in the Czech Republic (Petrlík and Kristian 2012), and found phthalates in the majority of the analysed products. Phthalate presence in PVC for furnishing of flats and buildings is mentioned also in some older studies from the EU countries, for example from Denmark (Danish Environmental Protection Agency 2009) and the United Kingdom (Allsopp, Santillo et al. 2000). Annex No. 2 to this study contains a summary of analyses of dust samples from various places in the Czech Republic.

Phthalate Analyses and Their Results Analytical Methods and Sampling Procedure In the beginning of the project in 2012, we have decided to take samples of toys, childcare articles and wallpapers made of plasticized PVC, to carry out analyses of the phthalate presence. In the last phase, clothes with printed films made of plasticized PVC were added. A simple criterion was used for the sampling: the products had to be commonly available in stores in Belarus, and they should have been made of plasticized PVC. The first selection was carried out during the actual purchase of the samples, started in August 2012 in brick and mortar stores. Later, we added goods from market places to a higher extent, too. They formed about a half of the purchased products during the last sampling, carried out in June 2014. In the next phase, we carried out verification whether the purchased goods were made of plasticized PVC, and, optionally, whether they contained also heavy metals and/or bromine (as an indicator of presence of brominated flame retardants). The verification was carried out in the Arnika's premises in Prague, using a borrowed X-ray spectrometer (XRF). Products made of plasticized PVC were handed over to expert laboratories for analyses of phthalate contents. In the first two phases, the analyses were carried out by the Institute for Testing and Certification (ITC) in Zlín. In the third phase, Central Laboratory of VŠCHT was chosen that offered the possibility of identification of a wider spectrum of phthalates and other plasticizers (isophthalates and adipates). The analytical methods used by these two laboratories are described below. Within the framework of analyses carried out in the ITC laboratory, content of extractable substances was determined (according to the standard ČSN EN ISO 6427), and, subsequently, presence of phthalic acid esters was determined (according to the standard ČSN EN 14372), expressed in % by weight, based on the whole product mass. Organic substance identification in the samples was carried out using gas chromatography with mass detector. In the case of DINP and DIDP phthalates, the analytical method sensitivity was between 0.005 - 0.010 % of the material weight, in the case of DNOP, BBP, DBP, DEHP and DPP phthalates it was at the level of 0.001 % by weight. Contents of other plasticizers were not quantified. Only the total content of extractable substances was determined. In the third sampling phase, phthalates were analysed in the Central Laboratory of VŠCHT in Prague using the following analytical procedure: phthalate contents in the supplied samples were determined according to the procedure CPSC-CH-C1001-09.3 Standard Operating Procedure for Determination of Phthalates, issued by the U.S. Consumer Products Safety Commission on April 1, 2010. The procedure is based on dissolving/extracting a portion (ca 50 mg) of the analysed sample of the child toy/ childcare article, that could contain the tested substances, in tetrahydrofuran (THF), precipitating the dissolved PVC by hexane, and subsequently analysing the produced solution using gas chromatography with mass spectrometry detection (GC-MS).

Detailed description of the sample preparation/extraction is given in the abovementioned standard procedure. For calibrating the mass spectrometer response, there was used a certified liquid standard designated EPA 506 Phtalate Mix (SUPELCO, supplier Sigma-Aldrich) containing 6 phthalates (BBP, DEHP, DnBP, DnOP, DEP and DMP) and one adipate (DEHA) in isooctane, with concentration of the individual components 1000 g/ml, from which a five-point calibration series in cyclohexane was prepared, with the addition of an internal standard – n-butyl benzoate (see the protocol), ensuring linear response of the mass spectrometer. Further, standard solutions of DPP and DIDP in cyclohexane, prepared in laboratory, were added to this calibration series, in order to meet the condition of linear response of the mass spectrometer. Due to their non-presence in the calibration mix, DnBP response factor was used for DiBP quantification, DEHP response factor for DOIP quantification, and DnOP response factor for DINP quantification. Analysis results are specified for each phase. Summary results concerning phthalates, in the case of which values exceeding the detection limits of the selected analytical methods were found, are presented in Annex No. 4.

First Phase of the Phthalate Analyses Increased amount of phthalates was found only in thre tested toys of eleven analyzed toys (in sample no. 12 – yellow and white whistle pony, namely 23.88 % of weight of diisononyl phthalate DINP and 1.01 % of weight of bis(2-ethylhexyl) phthalate DEHP). In sample no. 17 – set of green, yellow and pink squeaky rubber animals for use in bath tub, the pink kitty consisted of 23.30 % of weight of bis(2-ethylhexyl) phthalate DEHP. In three of the analysed products for children (two swim rings and a nasal aspirator), the tested phthalates were not found. In three of four samples of wallpapers, increased values of diisononyl phthalate DINP were detected, namely in sample 001 Decori Exclusive (13.62 % of weight, 002 ART En Flor (4.64 % of weight DINP), 004 ART - Indigo (8.36 % of weight DINP). In sample 003 Sintra, increased value of bis(2-ethylhexyl) phthalate DEHP was detected (12.45 % of weight DEHP). From the point of view of DEHP contents, the sample 002 ART En Flor was not homogenous, and one of its parts slightly exceeded the DEHP content limit (found 0.167 % by weight DEHP). In other products, the amount of phthalic acid esters did not exceed detection limit of 0.1 % of weight for diisononyl phthalate DINP, diisodecyl phthalate DIDP, di-noctyl phthalate DNOP, butyl benzyl phthalate BBP, dibutyl phthalate DBP and bis(2ethylhexyl) phthalate DEHP.

Tabular results of the analysis of content of phthalates in toys are stated in table 2. Tabular results of the analysis of content of phthalates in samples of wallpapers are stated in table 3. Table No. 2: Results of the analysis for the presence of phthalic acid esters (phthalates). Sample

Value

Substance

sample no. 13 – yellow and white squeaky pony

23.88 % of weight

diisononyl phthalate DINP

1.01 % of weight

bis(2-ethylhexyl) phthalate DEHP

23.30 % of weight

bis(2-ethylhexyl) phthalate DEHP

0,226 % of weight

bis(2-ethylhexyl) ftalát DEHP

sample no. 13 – yellow and white squeaky pony sample no. 15 – set of green, yellow and pink squeaky rubber animals for use in bath tub, tested subject: pink kitty Sample no. 16 – squeeze balls, tested subject: orange ball

Table No. 3: Results of the analysis of samples of wallpapers for the presence of phthalic acid esters. Sample

Value

Substance

Sample 001 Decori – Exclusive, sand

13.62% of weight

diisononyl phthalate DINP

4.64% of weight

diisononyl phthalate DINP

0,002 – 0,167% hm.

bis(2-ethylhexyl) ftalát DEHP

Sample 003 Sintra, white with flowers

12.42 % of weight

bis(2-ethylhexyl) phthalate DEHP

Sample 004 ART – Indigo, architectonic patterns

8.36 % of weight DINP

diisononyl phthalate DINP

Sample 002 ART - En Flor, light blue Sample 002 ART - En Flor, light blue

Discussion and conclusion about the first phase of testing In two toys, significant amount of phthalic acid esters was found hence there is still a potential risk that children, who come into contact with them, will be exposed to higher exposition of those substances.

Yellow and white pony which consisted of increased amount of DINP and DEHP was not labeled considering suitability of the toy for toddlers and small children. Belarus was declared as the country of production. Set of toys for use in bath tub, where the tested pink kitty with increased content of DEHP was found, is according to producer labeling appropriate for children over 3 years old. Since both toys are made of rubber, they are rather suitable for smaller children and with the toy with the label for children over 3 years old it can happen that parents will ignore such warning. There is a good possibility that these toys can also be put into mouths by small children. Therefore, contained amount of phthalates in both toys is entirely inappropriate in such amount. Although the risk of putting in the mouth, or coming into direct contact with the body surface, usually does not exist in the case of vinyl wallpapers, plasticizers from the wallpapers may be released into the air and dust in the room, and, thus, they may cause health problems as a consequence of their inhalation (see Annex No. 2 to this report). To sum it up, the proportion of toys with unsatisfactory content of phthalates represents 1/6 of total amount of tested toys (that is circa 16%) according to the European standards. Belarus detection standards for phthalates do not yet exist hence it is possible to sell mentioned products on the market.

Second Phase of Testing Phthalates in Toys and Other Products Two samples of products for children care, one wallpaper, four soft PVC packaging for toys, and four toys were chosen for second round of analyses. These samples were chosen from a broader number of samples analysed by XRF first in order to get an idea about content of heavy metals, and whether the used material is PVC or not. Only one toy was analysed for lead. Increased amount of phthalates was found in 4 tested samples (in sample no. 3 transparent foil - diisononyl phthalate DINP 22.36 % and 0.410 % bis(2-ethylhexyl) phthalate DEHP, sample no. 5 transparent foil - bis(2-ethylhexyl) phthalate DEHP 12.5 %, sample no. 7 - plastic doll head - 25.06 % bis(2-ethylhexyl) phthalate DEHP and sample no. 8 plastic wallpaper - 27.17 % bis(2-ethylhexyl) phthalate DEHP. In other products tested for phthalates, the amount of phthalic acid esters did not exceed detection limit of 0.1% of weight for diisononyl phthalate DINP, diisodecyl phthalate DIDP, di-n-octyl phthalate DNOP, butyl benzyl phthalate BBP, dibutyl phthalate DBP and bis(2-ethylhexyl) phthalate DEHP.

Table No. 4: Results of the analysis for the presence of phthalic acid esters â&#x20AC;&#x201C; phase 2 of sampling. Sample

Value

Substance

sample no. 3 transparent foil

22.36 % of weight

diisononyl phthalate DINP

sample no. 3 transparent foil

0.410 % of weight

bis(2-ethylhexyl) phthalate DEHP

sample no. 5 transparent foil

12.15 % of weight

bis(2-ethylhexyl) phthalate DEHP

sample no. 7 plastic doll head

25.06 % of weight

bis(2-ethylhexyl) phthalate DEHP

sample no. 8 plastic wallpaper

27.17 % of weight

bis(2-ethylhexyl) phthalate DEHP

Third Phase of the Phthalate Analyses In the third phase, we commissioned, in total, 30 analyses of various parts of 21 products. This time, the laboratory of VĹ CHT Prague was chosen for carrying out the analyses, because it offered a wider spectrum of the analysed phthalates, using the analytical procedure used by the US EPA. The detection limit of the chosen method is 0.05 % by weight for the individual phthalates, isophthalates and adipates. Table No. 5 shows the analysis results exceeding the detection limit of the analytical method. It is obvious from the results that the prevalent plasticizer in a part of the materials was bis(2-ethylhexyl) isophthalate, designated also dioctyl isophthalate (DOIP). Although these samples would be in compliance even with the EU standards, it ensues from the safety sheet of the substance (Sigma Aldrich 2013) that this plasticizer is ranked among reprotoxic substances, too, similarly as DEHP. Some of the DEHP, DINP, and DBP phthalates was found in an amount exceeding 0.1 % by weight in 18 of the 30 analysed samples. In the remaining twelve analysed samples, the only detected plasticizer was DOIP isophthalate. Thus, three fifths of the analysed materials would not be in compliance with standards used in the EU, due to the health risk ensuing form the use of the banned phthalates. In three cases, the toys were even made of PVC more than half of which (50 % by weight) was formed by the DEHP phthalate. They represent an enormous risk for children.

Table No. 5: Summary table showing results of analyses for presence of phthalates and other plasticizers in samples from the third phase of sampling of toys, products for children and childcare articles and clothes in Belarus. Sample Sample description 2 animal toys KungFu Panda; any part of one 1 of the animals pink raincoat; pink plasticized PVC of the 2 raincoat rainbow inflatable ball; part of the ball made 3 of PVC, without printing red-black inflatable toy; some plastic mix 4 pink inflatable ball; 5 inflatable dolphin - body of the toy; plastic 6a from which the dolphin itself is made inflatable dolphin - inflation valve; inflation 6b valve Barbie doll; head, body 7a Barbie doll; shoes 7b Barbie doll; handbag 7c orange swim vest; plastic from which the vest 8a itself is made orange swim vest; inflation valve 8b yellow floating duck - ring; plastic from which 9a the ring itself is made (without printing) yellow floating duck - ring; inflation valve 9b baby doll; plastic part 10 squeaky toy pink pig; unprinted part of the 11 plastic yellow inflatable ring with fruits (yellow); plastic from which the ring itself is made 12a (without printing) yellow inflatable ring with fruits (yellow); 12b inflation valve puppet toys, three small pigs; plastic pig heads 13 blue-pink inflatable toy - hand; blue part 14a (without printing) blue-pink inflatable toy - hand; pink part 14b (without printing) blue-pink inflatable toy - hand; inflation valve 14c squeaky toy yellow fish; without printing 15 inflatable green swim sleeves; plastic from which the sleeves themselves are made 16a (without printing) inflatable green swim sleeves; inflation valve 16b 2 dolls Pinocchio; one of the dolls (plastic 17 18

DEHP DINP* DOIP

DBP

DEHA

34.9

16.1

11.7 -

4.7 -

16.7 23.2

29.3

39.9 23.2 33.1 30.2

24.2 32.0

2.5 -

20.8

20.4 30.9 -

56.2

22.6

52.3

28.5 -

22.8

18.8 24.7 52.6

21.4 21.0 -

29.9

18 19 20 21

without printing) child transparent bag with blue flowers; plastic of the bag big red inflatable toy - cow; plastic of the toy yellow T-shirt with printing - Skate Academy; plastic film of the printing T-shirt with printing - Lion; plastic film of the printing

17.0 -

19.9

28.7

2.1

3.6

11.1

[-] â&#x20AC;Ś < 0.05 % by weight. * â&#x20AC;Ś in relation to the DnOP response factor.

Overall Evaluation of the Analyses In three phases in the course of the project (in the interval of two years), we commissioned, in total, 59 analyses for presence of phthalates in toys, childcare articles, children's clothes and wallpapers that may be used for internal decoration of flats, i.e., areas where children stay. At first, the taken samples of products were subjected to screening analysis using an X-ray spectrometer XRF, in order to verify whether the product in question was made of plasticized PVC. Simultaneously, this method was used for rough finding of contents of heavy metals and brominated flame retardants. Only products made of plasticized PVC were subjected to further analyses for phthalate presence in laboratories. The products suspected for high contents of heavy metals and/or brominated flame retardants were further subjected to more detailed analyses of these substances. In total 36 analyses, i.e., about two thirds of the overall number of analyses, examined materials used for producing toys and their packaging with which children often play, too. The second group of most often analysed products was formed by childcare articles, including mostly swimming aids. In the first two phases of sampling, we focused, in particular, on products purchased in the so-called brick and mortar stores. In the case of the last sampling, about a half of them originated from markets. Of the 36 toy analyses, none of the studied phthalates was found in concentration exceeding 0.1 % by weight in 12 cases, of the 16 analyses of childcare articles, this happened in 6 cases. However, it has to be emphasized that all these cases concerned analyses when the ITC laboratory did not analyse the DOIP isophthalate that is not regulated yet. Numbers of cases when phthalates were found in the analysed materials in amounts exceeding 0.1 % by weight are specified in Table No. 6. Bis(2-ethylhexyl) phthalate (DEHP) was the most often found phthalate, namely 22-times of 59 analyses, and of this number 13-times in toys. Of the 59 analyses, phthalate amounts exceeding 0.1 % by weight were found in 41 cases, however, only 29 materials, i.e., about a half of the 59 analysed materials, would not be in compliance with the European legislation. 19

This was caused by the fact that in twelve cases from the last set of samples only isophthalate DOIP was found in amounts exceeding 0.1 % by weight, and the amount of this substance has not been limited by any legislation measure yet.

Table No. 6: Numbers of cases when phthalates were found in the analysed materials in amounts exceeding 0.1 % by weight.

Group Toys Clothes Childcare articles Wallpapers Total (all analyses)

Number of analyses 36 2 16 5 59

DEHP 13 2 5 2 22

DINP 4 1 0 3 8

DOIP 7 (18) 0 (2) 6 (10) NA 13 (30)

DBP 3 0 0 0 3

Table No. 7: States the minimum and maximum values exceeding 0.1 % by weight of the material, found in any of the 59 analysed samples. The complete overview of results of chemical analyses is presented in Annex No. 4. From these tables, it is obvious that the DEHP phthalate formed more than a half (50 %) of weight of the plasticized PVC used for the toy production in three cases, whereas in the other product categories the maximum DEHP amounts were between a fifth and a quarter of the plasticized PVC weight. Another noteworthy fact is that the minimum amounts of the DOIP isophthalate were not below a fifth of the total weight of the plasticized PVC.

Group Toys Clothes

Number of analyses 36 2

Childcare articles

Wallpapers Total (all analyses)

5 59

DEHP 0.167 - 56.2 2.1 - 28.7

DINP DOIP DBP 4.7 - 23.88 23.2 - 39.9 16.7 - 23.2 3.6 20.4 2.5 - 21.5 32.00 4.64 12.45 - 27.17 13.62 0.226 - 56.2 3.6 - 23.88 20.4 - 39.9 16.7 - 23.2

Heavy Metals – Cadmium and Lead Although analysis showed the presence of cadmium and lead in products, migration limits for heavy metals in toys have not been exceeded – according to The Technical Regulation of the Customs Union TP TC 007/2011 “on Safety of Toys” (ECUC 2011) and even according to the Toy Safety Directive 2009/48/EC (European Parliament and Council 2009). Nevertheless, we consider unnecessary to use lead for production of teething toys for infants in the amounts in which it was found in the analysed teething 20

toy samples in the both colours, green and red ones. The analysis results are summarised in the following Tables Nos. 8 – 11.

Table No. 8: Determination of lead migration according to EN 71-3 Unit 412104892/10 - car body blue plastic 412104892/11A - teething toy - red plastic 412104892/11B - teething toy - green plastic

mg/kg

Measurement result1) 1.09

Measurement uncertainty2) 0.11

mg/kg

< 0.50

mg/kg

0.92

0.10

Notes to Table No. 12: 1) The symbol "<" designates the method detection limit. 2) Sample standard error of the sample average σn-1/√n; n=2

Determination of Cadmium and Lead Contents in the Materials Results of determination of cadmium contents in the materials are given in Tables Nos. 13 to 15 Table No. 9: Sample 412104892/10 - car body - blue plastic Parameter

Unit

Cd contents Pb contents

mg/kg mg/kg

Measurement result1) 5.40 239

Measurement uncertainty2) 0.10 5

Table No. 10: Sample 412104892/11A - teething toy - red plastic Parameter

Unit

Cd contents Pb contents

mg/kg mg/kg

Measurement result1) < 2.0 1100

Measurement uncertainty2) 12

Table No. 11: Sample 412104892/11B - teething toy - green plastic Parameter

Unit

Cd contents Pb contents

mg/kg mg/kg

Measurement result1) < 2.0 1690

Notes to Tables Nos. 13 to 15: 1) The symbol "<" designates the method detection limit. 2) Sample standard error of the sample average Ď&#x192;n-1/â&#x2C6;&#x161;n; n=2

Measurement uncertainty2) 46

Conclusions and recommendations In three phases in the course of the project (in the interval of two years), we commissioned, in total, 59 analyses for presence of phthalates, and 3 analyses for migration and contents of heavy metals in toys, childcare articles, children's clothes and wallpapers that may be used for internal decoration of flats, i.e., areas where children stay. At first, the taken samples of products were subjected to screening analysis using an X-ray spectrometer XRF, in order to verify whether the product in question was made of plasticized PVC. Simultaneously, this method was used for rough finding of contents of heavy metals and brominated flame retardants, which are dealt with in a completely separate part of the study. Subsequently, the analysis results were compared with phthalate regulation valid in the EU, because majority of the found phthalates was not regulated by the Belorussian legislation. Only in three cases, the toys contained dibutyl phthalate (DBP), which, according to ТР ТС 008/2011 (ECUC 2011), must not be released from toys at all. Concerning phthalates use of which is banned in toys and childcare articles in the EU, DEHP was found in amounts exceeding limits in 22 cases of 59 analyses, and of these number 13-times in toys. Of the 59 analyses, phthalate amounts exceeding 0.1 % by weight were found in 41 cases, however, only 29 materials, i.e., about a half of the 59 analysed materials, would not be in compliance with the European legislation. This was caused by the fact that in twelve cases from the last set of samples only isophthalate DOIP was found in amounts exceeding 0.1 % by weight, and the amount of this substance has not been limited by any legislation measure yet. The DEHP phthalate formed more than a half (50 %) of weight of the plasticized PVC used for the toy production in three cases, whereas in the other product categories the maximum DEHP amounts were between a fifth and a quarter of the plasticized PVC weight. It follows from the study obviously that legislative regulation of phthalates is insufficient, both in the Belarus and in the EU, because the manufacturers have been replacing toxic phthalates by other ones, that were examined by a lower number of studies, but, in spite of that, they were already included onto the list of substances with hazardous properties (DOIP). The study also showed that although toys bought in marketplaces were more problematic, also in the case of products bought in brick and mortar stores and manufactured in European countries, including Belarus, it cannot be said with certainty that they were free of hazardous phthalates. This also proves the need of more often inspections, for which, however, the state authorities in Belarus lack a legislative basis, namely a ban of toxic phthalates, such as DEHP and DOIP. The consumers have a simple possibility for avoiding phthalates – not to buy toys made of plasticized PVC. However, marking of the material from which the toy in question was produced is a problem. Even we had to make an X-ray spectrometer analysis in order to be sure what the material was.

As proved by studies focusing on presence of phthalates in dust in the indoor environment of buildings (Kolarik, Naydenov et al. 2008, Kim, Yang et al. 2011, PetrlĂk and Kristian 2012, Beko, Weschler et al. 2013), toys and childcare articles are not the only way through which young children are exposed to toxic phthalates. Because of that, it is important to eliminate these substances, without exceptions, also from products used for internal decoration of flats and other areas where children stay. Again, the simplest way for the consumers is to avoid products made of plasticized PVC.

Annex No. 1: Overview of the Analysed Samples Samples â&#x20AC;&#x201C; First Set of Analyses (January 2013) Total amount of 20 products of PVC was tested for the presence of phthalic acid esters (16 toys, 4 samples of wallpapers). More parts of some toys were tested (for example the valve of inflatable toys). List of pictures, including description, information about producer, country of origin and place of purchase are stated below. Testing was done by Institute for testing and certification, Inc. in ZlĂn.

Number of sample

Description

Country of origin, producer

Parts tested for content of phthalates

China

Material of the pool and of valve

China (Disney)

Material of the ball and of the valve

Poland (Canpol)

Material of the book

Set of rubber, plastic and inflatable animals for use in water (pool) 001

Beach ball for use in water (pool)

002

Squeaky bath book with the sun for toddlers

003

Beach ball for use in water (pool) Johny Eagle

006

China

Material of the ball

Taiwan, (Canpol company)

Squeezable blue bulb

China

Material of the ring and of the valve

China

Material of the toy

011

Russia

Material of the book

012

origin unknown

Material of the toy

Nasal aspirator with two ends â&#x20AC;&#x201C; hard and soft

007

Inflatable swim ring Cindy Star

008

Four yellow rubber duck for use in bath tub

009

Small book with the sun and tulips

Yellow and white squeaky rubber pony

Inflatable swim ring

014

China (INTEX)

Material of the ring and of the valve

China

Material of the toy – pink kitty

origin unknown

Material of the toy – orange ball

Set of green, yellow and pink squeaky rubber animals for use in bath tub

017

Yellow and orange squeaky rubber ball

018

ple

Description 001 002 003 004

Decori – Exclusive, sand ART - En Flor, light blue Sintra, white with flowers ART – Indigo, architectonic patterns

Country of origin Italy Russia Ukraine Russia

Overview of analyzed samples – 2. set of analyses – March 2014 Total amount of 11 plastic products (toys and 1 wallpaper) was tested for the presence of phthalic acid esters, cadmium, lead or polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs). More parts of some toys were tested. List of pictures, including description is stated below. Testing was done by Institute for testing and certification, Inc. in Zlín.

Number of sample

412104892/01

412104892/02

412104892/03

412104892/04

Description

Photo

Inflatable swim ring

Tested parts Transparent foil + blue foil (mixed sample) Tested chemicals: Phthalates

Yellow softened plastic Tested chemicals: Phthalates

Plastic duck

Toys cover

Transparent foil Tested chemicals: Phthalates

Toy cover

Transparent foil Tested chemicals: Phthalates

Toy cover Transparent foil Tested chemicals: Phthalates

412104892/05

412104892/06A

Transparent foil Tested chemicals: Phthalates

Toy cover

412104892/06B

Toy made of blue softened plastic

412104892/07

Doll

412104892/08

Plastic wallpaper

412104892/09

Rubik's cube

Material of the toy Tested chemicals: Phthalates

Material of the doll (head) Tested chemicals: Phthalates

Material of wallpaper Tested chemicals: Phthalates

Black plastic Tested chemicals: PBDE, PBB

Car Material of the toy â&#x20AC;&#x201C; blue plastic Tested chemicals: Cd, Pb

412104892/010

Teething toy 412104892/011A

Material of the toy - red plastic Tested chemicals: Cd, Pb

412104892/011B

Material of the toy â&#x20AC;&#x201C; green plastic Tested chemicals: Cd, Pb

Teething toy

Overview of Analyzed Samples – Third Set of Analyses (Focused on Phthalates, Isophthalates and Adipates) – October 2014 Sample number

Description

Country of origin, manufacturer

Parts tested for phthalate contents

China

Any part of one of the animals

China

Pink plasticized PVC

origin unknown

PVC – part of the ball without printing

origin unknown

Mixed plastic sample

origin unknown

2 animal toys KungFu Panda

Pink raincoat

Rainbow inflatable ball

Red-black inflatable toy

Pink inflatable ball

Inflatable dolphin – body of the toy

origin unknown

Inflatable dolphin – inflation valve (photo – see 6a)

Plastic from which the dolphin itself is made

Inflation valve

Barbie doll

China

Head, body

China

Shoes

Barbie doll

Barbie doll (photo see 7b) Orange swim vest

Handbag

Orange swim vest (photo see 8a)

origin unknon

Plastic from which the vest itself is made

China

Inflation valve

Swim ring – yellow duck

China

Swim ring – yellow duck (photo see 9a) Baby doll

Plastic from which the ring itself is made (without printing)

Inflation valve

origin unknown

Plastic part

Russia

Unprinted part of the plastic

China

Plastic from which the ring itself is made (without printing)

Squeaky toy – pink pig

Yellow inflatable ring with fruits (yellow)

12a

12b

Yellow inflatable ring with fruits (yellow) (see photo at 12a)

Inflation valve

Puppet toys „Three little pigs“

Russia

Plastic pig heads

origin unknown

Blue part (without printing)

Blue-pink inflatable toy - hand

14a

14b

14c

Blue-pink inflatable toy - hand (see photo at 14a)

Pink part (without printing)

Blue-pink inflatable toy – hand (see photo at 14a)

Inflation valve

Squeaky toy – yellow fish

origin unknown

Plastic without printing

China

Plastic from which the sleeves themselves are made (without printing)

Inflatable swim sleeves, green

16a

16b

Inflatable swim sleeves, green (see photo at 16a)

Inflation valve

2 dolls Pinocchio

China

One of the dolls (plastic without printing)

Belarus

Plastic of the bag

China

Plastic of the toy

Turkey

Plastic film of the printing

Belarus

Plastic film of the printing

Child transparent bag with blue flowers

Inflatable toy – big red cow

20 21

T-shirt with printing, yellow – Skate Academy T-shirt with printing, with lion

Overview of Analyzed Samples and Used Methods – Fourth Set of Analyses (Focused on BFRs) – October 2014 Test samples: VŠCHT codes LN 248/14 LN 249/14 LN 250/14

Customer's sample designation 22 23 24

LN 251/14

Customer's sample description 2 pieces Rubik's cube Toys Rubik's cube Magic Cube children set of knives, forks and spoons and kitchen equipment - black plastic red cup for hot drinks– Banquets – black holder

Annex No. 2: Phthalates in dust inside buildings Global production of phthalates has grown many times since the end of the second world war, from a very low volume up to 3.5 million tons annually in the beginning of the 21st century. Chronic allergies of children, and asthma development, very often connected with it, have shown a growing tendency, too. Scientists were concerned by these grows, not related to each other at first sight, and, in the 1990's, they started studying possible links between presence of certain phthalates in the indoor environment of buildings, in particular of flats, and incidence of asthma and allergies (Oie, Hersoug et al. 1997) , (Allsopp, Santillo et al. 2000). Conclusions of some of the studies were clear – phthalates, such as butylbenzyl phthalate (BBP), di(2-ethylhexyl) phthalate (DEHP), and di-iso-nonyl phthalate (DINP), may cause allergies (Bornehag and Nanberg 2010), (Hsu, Lee et al. 2011), (Bornehag, Sundell et al. 2004). DEHP is also most often said to be related to development of asthma disease in children. A Swedish study published in 2010 found relation directly between PVC used in children's room, parents' bedroom, or more rooms of the flat, with asthma of children (Larsson, HägerhedEngman et al. 2010). A Norwegian study got to a similar conclusion twenty years sooner already (Jaakkola, Oie et al. 1999). The amount of phthalates in the indoor environment is monitored in dust samples most often. Because of that, Arnika took dust samples in various flats and public buildings in the Pardubice Region, Region Vysočina, and in Prague in 2008. Dust samples, to be analysed for phthalates, were taken in ten rooms in total. These rooms were located in flats, offices, as well as, for example, in elementary schools. In total, ten dust samples were analysed in the laboratory of the Health Institute in Ústí nad Labem for the presence of fifteen phthalates. In the case of ten of them, there were not found concentrations exceeding the limit of quantification of these substances by the used laboratory method, whereas in the case of five of them, concentrations exceeding this limit were found. The found concentrations are presented in Table No. 3. It is obvious from the results that phthalate amounts in dust reached concentrations exceeding 1000 mg.kg-1 in four cases. The main contaminant was DEHP, and the second one was di-nbutyl phthalate (DnBP), however, in much lower concentrations. The highest phthalate concentration was found in dust from a school dining room in Pardubice (PAR1), with floor covering made of PVC, whereas the found phthalate concentration was significantly lower in the teacher's room of the same school (PAR2) with floor covering made of linoleum. Surely, some of the found out conclusions may also apply to potential phthalate concentrations in indoor areas where plasticized PVC is used as floor covering in Belarus.

Annex No. 3: Marking of Toys and Limits of Phthalate Contents in Toys and Other Products in Belarus 1. Mark that the product is not suitable for children under the age of 3 years

However, a product may be unsuitable for children under the age of 3 years for several reasons: there may be a risk of separation of small parts and their subsequent inhalation, or, for example, the product may have sharp portions or projections by which a child may get hurt. Thus, it does not follow from the marking unambiguously what risk the product has.

Annex No. 4: Summary table with all results of the phthalate analyses Sample 1 3 4 5 6a 6b 7a 7b 7c 10 11 13 14a 14b 14c 15 17 19

Sample description 2 animal toys KungFu Panda; any part of one of the animals rainbow inflatable ball; part of the ball made of PVC, without printing red-black inflatable toy; some plastic mix pink inflatable ball; inflatable dolphin - body of the toy; plastic from which the dolphin itself is made inflatable dolphin - inflation valve; inflation valve Barbie doll; head, body Barbie doll; shoes Barbie doll; handbag baby doll; plastic part squeaky toy pink pig; unprinted part of the plastic puppet toys, three small pigs; plastic pig heads blue-pink inflatable toy - hand; blue part (without printing) blue-pink inflatable toy - hand; pink part (without printing) blue-pink inflatable toy - hand; inflation valve squeaky toy yellow fish; without printing 2 dolls Pinocchio; one of the dolls (plastic without printing) big red inflatable toy - cow; plastic of the toy

sample No. 13 yellow-white squeaky horse sample No. 15 â&#x20AC;&#x201C; set of green, yellow and pink squeaky rubber 1.15 animal toys into the bath; tested article: pink cat

1.13

DEHP

DINP*

DOIP

DBP

DEHA Kind of the sample

34.9

toy

11.7 -

4.7 -

16.7 23.2

toy toy toy toy

56.2 52.3

20.8 -

29.3 39.9 23.2 33.1 30.2 -

22.8

18.8 24.7 52.6

1.01

23.88

29.9 NA

19.9 -

23.30

toy toy toy toy toy toy toy toy toy

toy toy toy toy toy toy

2.3 2.5 2.7

toy bag - transparent foil toy cover - transparent foil Plastic doll head

yellow T-shirt with printing - Skate Academy; plastic film of the printing T-shirt with printing - Lion; plastic film of the printing pink raincoat; pink plasticized PVC of the raincoat orange swim vest; plastic from which the vest itself is made orange swim vest; inflation valve yellow floating duck - ring; plastic from which the ring itself is made (without printing) yellow floating duck - ring; inflation valve yellow inflatable ring with fruits (yellow); plastic from which the ring itself is made (without printing) yellow inflatable ring with fruits (yellow); inflation valve inflatable green swim sleeves; plastic from which the sleeves themselves are made (without printing) inflatable green swim sleeves; inflation valve child transparent bag with blue flowers; plastic of the bag wallpaper: Decori â&#x20AC;&#x201C; Exclusive, sand colour

20 21 2 8a 8b 9a 9b 12a 12b 16a 16b 18 1.1 1.2

ART - En Flor, light blue colour

1.3 1.4 2.8

sample No. 003 Sintra, white colour with flowers ART â&#x20AC;&#x201C; Indigo, architectural design PVC wallpaper

toy toy toy

0.410 12.15 25.06

22.36 -

NA NA NA

28.7 2.1 16.1

3.6 -

24.2 32.0

2.5 -

20.4 30.9

22.6 28.5

21.4 21.0

17.0 12.45 27.17

13.62 4.64 8.36 -

NA NA NA NA NA

children's clothes 11.1 children's clothes article for children article for children article for children article for children article for children article for children article for children article for children article for children article for children NA wallpaper NA wallpaper NA wallpaper NA wallpaper NA wallpaper

Notes: 43

NA : the phthalate in question was not analysed in the sample - : the substance was not detected in the sample in an amount exceeding the limit of quantification shown by the used analytical method (limits of quantification of the used methods are stated in Annex No. 1).

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