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Content

P RE F A C E 5SU M M A R Y A N D C O N C L U SI O N S 7

I N T R O D U C T I O N 92 L I T ER A T U R E SU R V E Y O F PA H I N P R O D U C T S

2.1 PA H S I N C L U D ED I N T H E SU R V E Y 112.2 O R I G I N O F SO U R C E S T O PA H S 122.3 SO U R C ES O F PA H S I N R U B B ER A N D P L A ST I C M A T ER I A L S 13

2.3.1 Natur al rubber and syntheti c rubber 132.3.2 Poly V inyl Chloride - PVC 142.3.3 Functional oils as addi ti ves 152.3.4 Carbon black 16

2.4 A L T ER N A T I V E PR O D U C T S O R A D D I T I V ES W IT H L O W O R N OC O N T EN T O F PA H S 18

2.4.1 Extender oil wi th low content of PAH s 182.4.2 Carbon black wi th low content of PAH s 182.4.3 Alternati ve materi als that do not contain extender oils 18

2.5 PA H I N SP EC I FI C C O N SU M ER P R O D U C T S 192.5.1 I nvesti gati ons of PAH s in products 19

2.6 R EG U L A T I O N O F PA H S I N C O N SU M ER PR O D U C T S 222.6.1 EU regulati on of chemical substances (REACH ) 22

2.6.2 T oy safety directi ve 222.6.3 Ecolabelling 232.6.4 Proposed regulat ion by Germany 24

2.7 SEL E C T I O N O F P R O D U C T S FO R T EST 24

3 T EST R E SU L T S 273.1 PR O C E D U R E FO R S EL E C T I O N A N D P U R C H A SE O F T H E SP EC I F ICP R O D U C T S 273.2 M ET H O D O F A N A L Y SI S, S C R EE N I N G 28

3.2.1 Sample preparat ion 283.2.2 Extracti on method 293.2.3 Quali ty assurance (QA/QC ) 29

3.3 A N A L Y T I C A L R ESU L T S 303.3.1 Comments on the analyt ical method 303.3.2 Analy ti cal resul ts from the investigati on 303.3.3 Compari son to other investi gations 323.3.4 Compari son of the resul ts to regulat ions 33

4 C O N C L U SI O N S 35R EFEREN C ES 37

A ppendix A 41

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Preface

Based on a G erman study of toys and childcare articles that found highconcentrations of Polycyclic A romatic H ydrocarbons ( PA H s) , the D anishEnvironmental Protection A gency initiated this survey of PA H s in toys andchildcare articles on the D anish market. T he project consists of a li teraturesurvey and a chemical screening of selected articles.

T he project has been performed by N ational Environmental R esearchI nstitute ( N ER I ) at A arhus U niversity by L eif H offmann, M arianneT homsen, C harlotte D ahl Schidt and P ia L assen as project leader.

T he project has been performed for the D anish Environmental P rotectionA gency ( D EPA ) .

T he contact person at the D anish EPA was Shima D obel.

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Summary and conclusions

Polycyclic Aromatic H ydrocarbons ( PA H s) have been detected in consumerproducts as well as toys and childcare articles in a number of G ermaninvestigations; the general tendency being that these products arecharacterised by being primarily made from natural rubber and syntheticrubber as well as plastics.

T he known sources to PA H s in consumer products are extender oi ls andcarbon black. T hese additives are mainly known to be used in production oftyres and the function is well described in the technical literature. I n otherconsumer products the necessity and function of these additives is not welldescribed, however, it must be expected that the function and purpose is moreor less the same. Furthermore, no information about the use, amount and type

of extender oils and black carbon in toys and childcare articles are available atpresent as such information is not required for by existing regulations.T herefore, i t has not been possible to estimate the PA H content in toys andchildcare articles from the use of different types and amounts of extender oilsin the production of these products.

T he knowledge on the content of PA H s in toys and childcare product arerelatively limi ted. H owever, B fR ( Bundesinstitut fr R isikobewertung) inG ermany has conducted several investigations of P A H s in consumer productsand toys which have shown that PA H s are common in products.

T here is no specifi c regulation on PA H s in toys and childcare articles at thepresent but the EU toy directive ( 88/378/EC ) regulates in general the contentof chemicals in toys. I n the EU R egulation R EA C H ( R egistration, Evaluation,A uthorisation and R estriction of C hemical substances) ( EC ) N o 1907/2006the content of P A H s in tyres is regulated on the extender oi ls used in therubber for tyres. T he oil content of benzo(a) pyrene must not exceed 1 mg/kgand the content of the sum of the 8 R EA C H PA H s must not exceed 10 mg/kgoil.

20 di fferent toys and childcare articles were analysed. A s this is a screeningproject the results are given in concentration ranges. H owever, the estimateswithin the concentration ranges are fairly precise due to the analytical method.

T he analytical method used a G erman standard method for analysing PA H sin consumer products. T he method was further developed in order to achievelower detection limits compared to the G erman method as well as lowuncertainty on the measurements. T he results showed that P A H s were foundin all analysed samples. I t can therefore be concluded that P A H s are commonin toy and childcare articles on the D anish market. H owever, i t is likely thatthe low detection limits in the present study have lead a higher number ofsamples with detectable PA H s compared to the G erman investigations, whichhave higher detection limits. T he results also showed that i t was mainly thesmall molecular size PA H ( compared to Benzo( a) pyrene) which were found.T his indicates that mainly lighter mineral oils were used in the materials. I ngeneral, the toxicity for P A H s increases with increasing molecular size.

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55% of the samples contained < 1 mg/kg sum of the 16 EPA PA H s; 40%contained 1-10 mg/kg and 5% ( one sample) contained 100-1000 mgt/kg.C onsidering the sum of the eight R EA C H PA H s 90% of the samples werebelow 1 mg/kg and 5% were at 1-10 mg/kg and 10-100 mg/kg, respectively.Benzo( a)pyrene were below detection limi t in 75% of the samples.

T wo products were produced within EU . O ne of the product have

concentration level between 10-100 mg/kg whereas the other were

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1IntroductionA report published by the G erman risk assessment institute BfR( Bundesinstitut fr R isikobewertung) in 2009 concluded that children are notsuff icient protected in the new toy safety D irective 2009/48/EC as theclassif ication limits for P olycyclic A romatic H ydrocarbons ( PA H s) will be toohigh. H owever, the new EU toy safety D irective 2009/48/EC , which for thechemistry part will be in force by July 2013, regulates the content of C M Rclassifi ed substances; substances which are carcinogenic, mutagenic or toxicfor reproduction and these compounds must not according to the newdirective be present in toys in concentrations above the classification limits.R EA C H has only limi ts for the PA H content in extender oils used in tyres.T he D anish EPA has previously investigated tyres used in playgrounds andconcluded that there were no risk of using tyres for that purpose.

H owever, as BfR have found PA H s in consumer products the D anish EPAhas therefore decided to make a screening investigation of PA H s in toys. T heobjective of the study is thus to verify to which extent PA H s are present intoys and childcare articles on the D anish market.

T his report presents a screening survey of the P A H content in 20 selectedpieces toys and childcare articles. T he project is divided in two phases: A ninitial literature survey on information on the use of PA H -containing extenderoils and carbon black in the production of toys and childcare articles andselection of representative products of soft rubber or plastic materials. I n thesecond phase the selected toys and childcare arti cles were subjected toanalytical chemical screening for P A H s. A s the present project is a screeningstudy no risk assessment have been made on the basis of the results.

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2Literature survey of PAH inproducts

2.1 PAHs in cl uded in t he sur veyPolycyclic A romatic H ydrocarbons ( PA H s) are a large group of compoundswhich consist of two or more aromatic rings attached to each other. M orethan 100 PA H s are known. T hey are in general heavy compounds with lowvolati li ty and high boiling point. I n nature they are generally regarded aspersistent. Several of the PA H s are identif ied as carcinogenic and genotoxic,and PA H s are considered as the largest single group of carcinogeniccompounds. T he PA H s included in the present investigation is presented in

table 2.1. T he selection of the PA H s is based on 8 PA H s which are coveredby the R EA C H R egulation ( EC ) N o 1907/2006 as well as the 16 PA H s in theU S EPA list of PA H s1, often called the 16 EPA PA H s. T he table also presentthe classification of the individual substances according to the D angerousSubstances D irective 67/548/EE C and the new regulation on theclassification, labelling and packaging of substances and mixtures; i.e.R egulation EC N o. 1272/2008.

Tabl e 2.1. Cl assif icat io ns and TEF3val ues of PAHs in t he pr esent study

CAS no.Classification according to

67/548/EECClassification according to

1272/2008TEF3

1 Acenaphthene2 83-32-9 - - -

2 Acenaphthylene2

208-96-8 - - -3 Anthracene2 120-12-7 - - -

4 Benzo(a)anthracene1,2 56-55-3CARC2;R45 N;R50/53 Carc. 1B; Aquatic Acute 1;

Aquatic Chronic 10,1

5 Benzo(b)fluoranthene1,2 205-99-2CARC2;R45 N;R50/53 Carc. 1B; Aquatic Acute 1;

Aquatic Chronic 10,1

6 Benzo(k)fluoranthene1,2 207-08-9CARC2;R45 N;R50/53 Carc. 1B; Aquatic Acute 1;

Aquatic Chronic 10,1

7 Benzo(j)fluoranthene1,2 205-82-3CARC2;R45 N;R50/53 Carc. 1B; Aquatic Acute 1;

Aquatic Chronic 10,1

8 Benzo(g,h,i)perylene2 191-24-2 - - -1PA H s covered by R EA C H ( EC , 2006) .2EPA PA H s.

3

T oxicity Equivalence Factors ( B fR , 2009b) . - indicates that to that no values exi sts. T his means that there is not sufficient documentation of theeffects for these PA H s. E.g. i ndeno( 1,2,3-cd) pyrene is in U S EPA s I R I S database classified as B2,possible carcinogen, meaning that the compounds has been tested positive in animal tests but there areno data on humans which document the effect( http:/ /www.epa.gov/iris/) .

1

I n the late seventies the U nited States Environmental Protection A gency ( EPA )published at list of priority pollutants including 16 PA H s. T his list of the 16 EPApriority PA H s has become a standard for measurement of PA H s.

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Table 2.2. Continued. Classifications and TEF3values of PAHs in the present study

CAS no.Classification according to

67/548/EECClassification according to

1272/2008TEF3

9 Benzo(a)pyrene1,2 50-32-8

CARC2;R45 MUT2;R46 REP2;R60-61 R43 N;R50/53

2.5%C

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are being concentrated in the heavier fractions, e.g. aromatic oils and tar,whereas they have li ttle affinity for the lighter fractions, e.g. gasoline. M ainlyheavier mineral oils are used as additives in materials for the production ofe.g. toys and childcare articles and can therefore be expected to be a sourcefor PA H s in the products.

H owever, processes to extract the PA H s from the oil have been developed;

producing cleaner oil products for e.g. consumer products in general( BA uA 2010) . A lso carbon black with reduced content of PA H s can be foundon the market ( see section 2.4) .

T herefore, the amount of P A H s in the mineral oils and carbon black willdepend on the origin and the production process ( see section 2.3 and 2.4) .

2.3 Sour ces of PAHs in r ubber and pl ast ic mat er ial sFor consumer products the main source of P A H s is considered to be differentmineral oils which are used in the productions of the used materials, mainly asadditives.

C onsumer products consisting of the following materials or additives areconsidered to have potential PA H contami nation2:

R ubber and flexible plastics ( e.g. PV C ) : Softening oils and carbonblack as e.g. pigment

Plastics. B lack carbon used as e.g. black pigmentT he present study focus on toys and childcare articles where materials, thatmay contain PA H s, are applied; that are toys and childcare articles made of

rubber or plastics of different kinds.

2.3.1 Natural rubber and synthetic rubberN atural rubber is produced from latex of the rubber tree (Heveabrasiliensis) .By use of di fferent addi tives and production process the physical properties ofthe natural rubber can be altered and thereby manufactured to different enduses. N atural rubber is used within a range of different sectors ( U N C T A D ,2010) . Examples given below:

T ransport sector: pneumatic tyres and tyre products, inner tubes,automoti ve belts

I ndustrial sector: conveyor and transmission belting, tyres for li fttrucks, castors, seismic materials, hoses, belts, plates, packing andsealing devices, industrial gloves, automoti ve mats

C onsumer sector: threads, erasers, golf balls, inflatable articles, mats,toys and textiles

H ygiene and medical sector: examination and surgical gloves,contraceptives ( condoms, i ntrauterine devices) , other biomaterials( blood bags, syringes, implantable devices) .

2

T V R heinland G roup.http://www.twn.tuv.com/images/banner/T R % 20PA H % 20Fact% 20Sheet-English.pdf

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T he consumption of natural rubber for tyres constitute for about 50% of thetotal consumption of natural rubber worldwide ( U N C T A D , 2010) . D ue tothat most of the technical literature focuses on tyres.

T he chemi cal composition of natural rubber and latex iscis-Polyisoprene:

n

CHCHCHCCH 232

)(

N atural rubber is further processed before use. By adding sulphur and heat( vulcanization) cross-links are made between the polymer chains which resultsin a more stabilized polymer; a harder material.

Synthetic rubber is used in combination with or as alternative to naturalrubber and can in many cases be used for the same purposes as naturalrubber.Synthetic rubber covers a group of different polymers:

Polybutadiene rubber Butyl rubber/Isobutylene-isoprene rubber H ydrogenated nitri le butadiene rubber Polychloroprene Polyolefin elastomer Fluoro elastomer A crylonitri le-butadiene rubber Styrenic block copolymers Styrene-butadiene rubber Ethylene-propylene-diene copolymer Polyisoprene

N atural rubber as well as synthetic rubbers is formulated together with a widerange of additives in order to achieve the optimal quality of the material.Examples of additives used for the production of natural rubber materials arelisted below ( U BA , 2003) :

vulcanisation agent ( sulphur) vulcanisation accelerators anti ageing agents fillers and pigments plasticisers processing aids

Plasticisers ( mainly softeners) are a group of additives that include extender

oils. T hese extender oi ls are also referred to as D isti llate A romatic Extract( D A E) or H ighly A romatic ( H A ) oil and are described in section 2.3.3

C arbon black is also used as an additive and even though PA H s are removedto some extend during the production of carbon black, PA H residues is stillexpected to be present as further described in section 2.3.4.

2.3.2 Poly Vinyl Chloride - PVCPV C is produced by polymerisation of vinyl chloride and the chemi calcomposition is presented below (A llsopp & V ianello, 2005) :

nCHClCH 2

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PV C can be manufactured by addition of different additives. T he potentialadditives are

heat stabilisers internal and external lubricants processing aids impact modifiers fillers pigments U V stabilisers primary and secondary plasticisers

T he actual composition of the PV C product will depend on the individualmanufacturer and the wanted material properties of the product. Extender oilscan be used in PV C as a secondary plasticiser and are also a cheaper addi tivethat can substitute part of the more expensive primary plasticisers ( e.g.phthalates) in flexible PV C or as process aid in rigid PV C ( N ynas, 2010) .T he H andbook of fi llers, extenders and diluents ( A sh & A sh 2007) mentionsseveral extender oils which can be used as plasticisers in PV C .

A dditives applied in P V C may therefore be a source to PA H s in consumerproducts.

2.3.3 Functional oils as additivesExtender oils in the rubber and plastic industry are mainly used by:

manufacturers of soften polymers. manufacturers of finished rubber products in order to aid processing; that

is mixing operation, reducing compounding time and improving processability and modify the physical properties of the finished product

T he main functions of extender oi ls are by swelling of the polymer and tofunction as lubricants between the stiff rubbery polymers and softeners. Byadding extender oils the molecular weight, viscosity and solvency of the basepolymers ( the rubber) can be varied. Further, because of oi l content moreadditional ingredients can be blended. A major use of extender oils istherefore as additives in rubber tyres where the additives add importantrubber characteristics and properties to, e.g. winter and summer, tyres.

T he content of P A H in extender oils may vary between mineral oil fractionsas mentioned in section 2.2. A n example of the composition of PA H s inextender oil is compiled and presented in table 2.2.

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Tabl e 2.2 An exampl e of t he PAH con t ent and pr of il e in an extender oi l(Kemikal iein spekt ion en, 2003).PAH CAS-nr. Content (mg/kg)Fluoranthene 206-44-0 11.0Pyrene 129-00-0 25.6Benzo(a)fluorine 238-84-6 0.9Benzo(a)anthracene1 56-55-3 34.2

Chrysene

1

218-01-9 395.3Benzo(b)fluoranthene1 205-99-2 72.9Benzo(e)pyrene1 192-97-2 113.2Benzo(a)pyrene1 50-32-8 13.4Dibenzo(a,j)anthracene 224-41-9 4.6Dibenzo(a,h)anthracene1 53-70-3 5.7Indono(1,2,3-c,d)pyrene 193-39-5 6.2Benzo(g,h,i)perylene 191-24-2 17.9Anthracene 191-26-4 6.6Total 707.5

1P A H s regulated by R EA C H ( EC , 2006) .

T able 2.2 presents an example of the content of P A H s in extender oil. I t

should be noted that the PA H content of this extender oil exceeds the limitvalues included in the R EA C H R egulation ( Benzo(a) pyrene< 1 mg/kg andsum of 8 PA H s < 10 mg/kg) .

H owever, the amount of extender oi ls used in the production of toys andchildcare articles is unknown and can vary significantly according to thedesigned properties of the rubber and plastic material and the use of otheradditives. A survey on producers and patents showed that the content ofextender oi ls ranged from 2 to 50 w/w% in the material. For comparison aSwedish investigation found that the content of extender oils in tyres rangefrom 10-40 w/w% ( K emikalieinspektionen, 2003) .

T here is only very little information in the li terature on the amount of PA H sin the different oils and further, no information on the PA H content andspecific type of oi l used in the products are available. I t was therefore notpossible to correlate different extender oils, their content of PA H s and thedifferent products.

Sti ll, it is known that the lower molecular weight PA H s have highest affinityfor being present in li ght mineral oils, whereas high molecular weight P A H shave highest affinity for being present in heavy mineral oils.

I n addition, toys and childcare articles may be produced by use high quali ty

extender oil wi th low PA H content ( see section 2.4) .

2.3.4 Carbon blackC arbon black ( C A S no.: 1333-86-4) is also an additive which is used in tyres,rubber and plastic products, printing inks and coatings ( I C BA , 2010) .

C arbon black is virtually pure elemental carbon in the form of colloidalparticles that are produced by incomplete combustion or thermaldecomposition of gaseous or liquid hydrocarbons under controlled conditions.

I ts physical appearance is that of a black, fi nely divided pellet or powder. I ts

use in tires, rubber and plastic products, printing inks and coatings is relatedto properties of specific surface area, reinforcement of the material, particle

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size, structure, conductivi ty and colour. D ue to the source and productionmethod carbon black may contain residues of P A H s.

C arbon black i s classified as a G roup 2B carcinogen by I A R C ( 2006) .H owever, carbon black i s not adopted on the list of harmonised classifi cationand labelling of hazardous substances ( A nnex V I to the C lassifi cationD irective 2008/1272/EC ) .

T sai et al. ( 2001) have investigated the amounts of P A H s and the massbalance during the production of carbon black. Examples on theconcentrations of P A H s in the crude oil used for production and in di fferentcarbon black products produced at different temperatures are presented intable 2.3.

Tabl e 2.3 PAH con cent r at io n i n car bon bl ack pr oduct s and cr ude oi l (Tsai etal ., 2001)

Carbon blackSubstance Crude oil

mg/l (n=3)Manufacturing

at 1780 oC1

mg/kg (n=9)

Manufacturingat 1950 oC2

mg/kg (n=9)Naphthalene 925 2.3 8.68Acenaphthylene 159 2.11 15.2Acenaphthene 52.9 0.526 0.870Fluorene 115 0.457 0.194Anthrecene 555 4.86 4.92Phenanthrene 4.61 0.455 0.215Fluoranthene 96.4 10.6 8.74Pyrene 459 73.2 11.4Cyclopenta(cd)pyren 79.9 6.19 5.91Benzo(a)anthracene 56.0 4.67 7.74Chrysene 22.3 0.083 0.032Benzo(b)fluoranthene 34.0 0.026 0.057

Benzo(k)fluoranthene 24.3 0.026 0.001Benzo(e)pyrene 69.5 0.718 0.774Benzo(a)pyrene 62.1 0.238 0.366Perylene 11.4 0.086 0.042Indeno(1,2,3-cd)pyrene 4.79 0.155 0.112Dibenzo(ah)anthracene 96.0 0.002 0.008Benzo(b)chrysene 55.4 0.223 0.185Benzo(ghi)perylene 77.9 1.06 1.04Coronene 20.1 0.531 0.392Total PAHs 2980 109 66.91A verage for three types of carbon black: N -550, N -660, and N -774.2 A verage for three types of carbon black: N -220, N -330, and N -339

I n the process a signifi cant amount of the PA H s is removed. For most of thePA H s only 0-5% of the incoming PA H s are present in the carbon blackproducts compared to the crude oil, but still in high amounts for certainPA H s. Further, it can be noticed that the production temperature has aninfluence on the content of the PA H s in carbon black, but the effect vary forthe different PA H s.

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2.4 Al t er nat ive pr oducts or addit ives with l ow or no cont ent of PAHs

2.4.1 Extender oil with low content of PAHsT here are alternative oils with low content of PA H s which can be and are

used in consumer products. K emikalieinspektionen ( 2003) and BA uA ( 2010)have listed a number of alternatives to the traditional extender oils whichcontain signifi cant lower content of PA H s:

T reated D istillate A romatic Extract ( T D A E) , e.g. C A S: 90641-09-1 isproduced from distilled aromatic extracts ( D A E) which are furthertreated by a solvent extraction to remove the aromatic componentswith three rings and higher.

T reated R esidual A romatic Extract ( T R A E) is produced fromresidual aromatic extract ( R A E) , a heavy oil fraction produced fromthe de-asphalting of heavy petroleum residues, by solvent extraction ofaromatic components.

M ild E xtract Solvate ( M ES) consists mainly of paraffinic oils, i.e.linear alkanes, which result from the lube base oil production andwhere aromatic components with two and more rings have beenremoved by extraction.

H ydrotreated Paraffinic D istillate ( H PD ) consists mainly of paraffinicoils, i.e. linear alkanes, which have been treated with hydrogen in thepresence of a catalyst of heavy petroleum distillates.

H ydrotreated N aphthenic D istillate ( H N D ) consists mainly of cyclicalkanes. I t i s produced by hydro-treatment of heavy vacuumpetroleum distillates.

A s several of these oils have gone through an additional treatment forremoving the PA H s, they are expected to be more expensive than traditionallyextender oils, and it is possible that these alternative oils may only be used inthe more expensive toys and childcare articles.

Substitution of the traditional extender oils with these alternative oils hasmainly been investigated for tyres, where there are specific demands for theproperties of the rubber material. B owman et al. ( 2004) have investigated theeffect of substituting H A oil in Styrene butadiene rubber with two alternativeextender oils containing less PA H s; T D A E or M ES. T hey concluded thatsubstitution was possible with respect to the physical properties; however, thebest results were obtained by using T D A E. T he long term service life

performances were not clarified.

2.4.2 Carbon black with low content of PAHsT he amount of P A H s in carbon black can further be reduced by certainextraction procedures: e.g. soxhlet extraction with organic solvents under hightemperatures ( I C BA , 2010) or by thermal treatment under vacuum or inertgas atmosphere at temperatures > 300C and solvent extraction ( BA uA 2010) .

2.4.3 Alternative materials that do not contain extender oilsA nother option is a substitution of natural rubber or synthetic rubber with

thermoplastic elastomers ( T PE) ( BA uA , 2010) . P T S ( 2007) presented anumber of thermoplastic elastomers based on D I N I SO 18064 definitions:

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T PE-S: B lock copolymers based on styrene, butylene, ethylene,propylene and modifications hereof

T PE-U : B lock copolymers based on polyurethane T PE-E: B lock copolymers based on polyesters and polyethers T PE-A : B lock copolymers based on polyamides T PE Si licone: B lock copolymers based on silicone T PE-O : O lefin based thermoplastic elastomers T PE-V : D ynamic vulcanisates T PE radiation crosslink-able

T hermoplastic elastomers contain a hard, thermoplastic compound and a soft,elastomeric compound which are physically bound to each other to form thefinal elastic polymer.

T hese alternative polymers do not need to contain extender oil in order toobtain the right material properties which has been verifi ed by the G ermansurvey ( BA uA , 2010) , as the study concludes that thermoplastic elastomers

do not contain P A H s. T hermoplastic elastomers can be produced withdifferent material properties and they are therefore capable of replacing arange of rubber products. T he thermoplastic elastomers have therefore notbeen investigated any further in the present study.

2.5 PAH in specif ic con sumer pr oduct sI t has not been possible to correlate different kind of extender oi ls and theirPA H content with the different rubber and plastic materials used and neitherto correlate this information to the different toys and childcare articles. T he

reason is that there are no precise data on the content of P A H s in the differentextender oils. Further, it has not been possible to correlate the differentextender oi ls to different rubber and plastic materials. T his situation appearedalso for the carbon black products as there are no specifications of theseadditive materials or in which products they are used as well as in whatamounts.

D ue to the lack of specific information on additives in toys and childcarearticles the focus has been laid on products of soft plastic and rubbermaterials. H ard plastic materials can also contain extender oi ls, however, itwas estimated that the content of extender oi ls and thereby the possible PA Hcontent would more common in soft plastic materials, and products of hard

plastic materials was therefore not included in this study.

2.5.1 Investigations of PAHs in productsA t the moment the knowledge of PA H s in child articles on the D anish marketis very limi ted. I n G ermany the BfR ( Bundesinstitut fr R isikobewertung)have made larger investigations on PA H s in both consumer products and intoys. T he investigations found that a number of products contained PA H s.H owever, i t has not been possible to obtain these reports only summaryfrom them. A part from the G erman investigations the number of report onPA H s in toys and childcare articles is very scarce.

BA uA ( 2010) has summarised a number of investigations of PA H in toys andother consumer products as background information for a proposal of a

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restriction of PA H s under the R EA C H R egulation. T he investigations weremade by T V R heinland, Stiftung W arentest and K O -T EST .

T he results of the investigation done by different research teams andconsumer groups have been aggregated within a number of categories ( seealso table 2.4) :

Electrical devices G rips and handles ( grips/handles made of rubber or plastic e.g. of tools

( hammer, screwdriver, knives, pliers, bicycles, gardening tools, buggies,stationary bicycles, walki ng frames, torches, handle coating)

C ontact areas of sports equipment and other articles T oys ( balls, figures, toy cars, run bi kes, coloured pencils, shuttlecocks, toy

guns, electrical parts of toy train sets) M aterials with close contact to the body (shoes, gloves, underwear,

working clothes, fli p-flops) O ther products with skin contact ( ski goggles, headphones, pulse

monitors, eye-cups, desk pads, bracelets, steering wheel covers, computer

mice, mouse pads, furniture handles, watch straps) T yres and rolls ( car tyres, tyre cover, transport wheel, rolls of transport

aid) O ther productsI n table 2.4 are given two concentrations of sum ( sum P A H ) , where theconcentrations on selected PA H s are summed up; the sum of 16 EP A PA H s( EPA PA H sum) and 6 selected PA H s which also are included in the 16 EPAPA H s. T he maximum levels of Benzo(a) pyrene, E PA PA H s and PA H -6 arefound in tyres. T his is also the group wi th the highest fraction of samplescontaining PA H s. T he maximum levels for toys were 65.9 mg

benzo(a) pyrene/kg, 1992 mg EP A PA H s/kg, and 447 mg PA H -6/kg. T hefraction of toy samples below detection lim it was 94.7% , 18.5% , and 87.8%for respectively Benzo(a)pyrene, E PA PA H sum and PA H -6.

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T oys and childcare articles containing PA H s: C hildren footwear: P lastic clogs/sandals, rubber boots, sneakers T oy and products used in water: I nflatable water toys, Swimming aids,

C hildren swimmi ng pools Baby strollers and buggies D oll buggies

Erasers C hildren's bicycles: horns, grips and seats Plastic toy figures C arnival masks C hildren's trainer bikes C hildren's mud pants T eething rings C hildren's tooth brushesT hese results from the G erman investigations were used in the final selectionof products ( see chapter 2.7) .

2.6 Regul at io n of PAHs in consumer pr oduct sT his section presents European regulation of P A H in products andecolabelling criteria.

2.6.1 EU regulation of chemical substances REACH)T he European regulation of chemicals, R EA C H regulation (EC ) N o.1907/2006 (EC , 2006) include certain P A H s in a specified use i.e. the content

in extender oils used for production of tyres. T he limi t values for P A H s are:

< 1 mg benzo(a)pyrene/kg extender oi l < 10 mg PA H /kg extender oil, where PA H /kg = Benzo(a) pyrene,

benzo( e) pyrene, benzo( a)anthracene, chrysene, benzo( b) fluoranthene,benzo( j) fluoranthene, benzo( k) fluoranthene, dibenzo(ah)anthracene.

2.6.2 Toy safety directiveR egulation by EU on safety of toys is at the moment covered by directive88/378/EEC .

A new directive 2009/48/EC will be in force in 2011, except the requirementsset out in Part I I I of A nnex I I concerning chemical properties, which will be inforce by the 20 July 2013.

D irective 88/378/EEC ( EC , 1988) do not address PA H explicit; however, itstates that T oys must not contain dangerous substances or mixtures withinthe meaning of D irectives 67/548/EE C and 88/379/EEC in amounts whichmay harm the health of children using them. A t all events it is strictlyforbidden to include, in a toy, dangerous substances or mixturesif they areintended to be used as such while the toy is being used .

T he new toy safety directive 2009/48/EC ( EC , 2009) do not address PA Hexplicit, however, C M R substances must only be used in not available part oftoys or in concentrations below the classifi cation limits. T his means that

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classified PA H s ( see table 2.1) in the new toy directive must have aconcentration limit on 0.1% w/w or less depending on the specificclassification limit.

2.6.3 EcolabellingBesides the restriction in R EA C H and the new toy safety directive

2009/48/EC , cri teria have also been laid down under the N ordicEnvironmental labelling scheme. So-called Ecolabelling criteria have beendeveloped for two product groups relevant for exposure to PA H s. T heproduct groups are:

T oys ( N ordic Ecolabelling, 2009) V ehicle tyres ( N ordic Ecolabelling, 2010)2.6.3.1 ToysT he N ordic Ecolabelling criteria for toys contains requirements to a numberof materials e.g. plasti c and rubber, textiles, skins and leather, wood and wood

based materials etc. For plastics and rubber one of the criteria focuses onadditives. C riteria R 5 is presented in the box below (N ordic Ecolabelling,2009) .

R5 Additives to plastic and rubber

The following addit ives must not be actively added to plastics/plastic parts and rubber:

substances classified in any of the following hazardous classification lists (actual riskphrases in brackets):May cause cancer with symbol T (R45, R49)May cause cancer with symbol Xn (R40)May impair infertility with symbol T (R60, R61).

May impair infertility with symbol Xn (R62, R63)May cause heritable genetic damage with symbol T (R46)May cause heritable genetic damage with symbol Xn (R68).In accordance with regulations in force in any Nordic country and/or with the EUclassification system Directive 67/548/EEC (with adaptations and amendments).

substances based on lead, cadmium, mercury and their compounds and organotincompoundsphthalateshalogenated organic compoundsBisphenol A

Tin organic compounds are defined as compounds in which tin is bound directly to the

carbon atom.Eco labelling is therefore a good tool for supporting the new toy directive asthe producers of toys, that are approved to such a labelling, have taken anextended responsibility that the quality of the materials used in the productionof toys follows the legislation. T hereby the eco labelling will contribute as anadditionally insurance of the quality of the product by controlling the wholeproduction chain in relation to the producer as well as the consumer.

T he cri teria concerning hazardous classifi cation of additives may be relevantfor P A H s in toys added as mi xtures ( e.g. extender oils) . E xtender oilscontaining e.g. more than 0.01 % w/w of benzo( a) pyrene has to be classified as

hazardous and labelled by C A R C 2, R 45. Eco labelled products must notcontain oils that are classified due to their content of P A H s.

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2.6.3.2 Vehicle tyresT he envi ronmental labelli ng cri teria for vehicle tyres contain requirements tocontent of P A H s in oils used in the tyres as well as limi t values for P A H s intyres. C riteria R 6 considers a lim it of the total content of measured PA H saccording to I P 3463method ( max 3% ) and a limit for 8 PA H s included in theR EA C H R egulation and for Benzo( a)pyrene at 8 mg/kg and 1 mg/kg,

respectively ( N ordic Ecolabelling, 2010) .

R6 PAHs in oilThe total content of polycyclic aromatic compounds (PAH) in oil used in the tyre mustnot exceed 3% measured according to IP 346 method.

Analysis of PAHs in the tyre must be performed according to procedures in Appendix 2.The limit values for the contents of a total of 8 PAHs (according to EU Directive2005/69/EC) and benzo(a)pyrene (BaP) must not exceeded 8 ppm for the 8 PAHs and 1ppm for BaP.

A pplication of the IP 346 method and the calibration conditi ons is described

in foreword to annex 1 to 6 in the R EA C H regulation EC no. 1907/2006referring to PA H s.

2.6.4 Proposed regulation by GermanyU BA ( 2010) has proposed R EA C H , A nnex X V I I to be changed/extended tocover P A H s in consumer products by adding a Fifth paragraph to the sectionon PA H : 5. A rticles which could be used by consumers ( including articles incontact with the oral mucosa, toys, and childcare articles) shall not be placedon the market, if they contain any of the PA H s listed in column 1 at levelsabove the limit of quantification ( L O Q ) . C urrently the L O Q is located at 0.2mg/kg for any of the listed PA H s . T he eight PA H s included in this proposal

are: Benzo( a)pyrene Benzo(e) pyrene Benzo( b) fluoranthene Benzo( j) fluoranthene Benzo( k) fluoranthene Benzo(a)anthracene C hrysene D ibenzo( a,h) anthracene

2.7 Sel ectio n of pr oduct s f or t estT here is no legal demand for product declaration for toys. Based on thepresented knowledge on potential PA H content of additives, the followingcriteria have therefore been considered in the selection ( not prioritised) :

3M ethod I P 346 is a chemi cal screening assay for dermal carcinogenicity. T he princip

is that the principal carcinogens in oi ls are PA H s, and that the biologically activemembers of the class are extractable into dimethyl sulfoxide, D M SO . T he end-point

measured in I P 346 is the weight percent of extracted compounds which equal to thePA H s. T he European C omm ission mandates that M ethod I P 346 be used as the basisfor labelling certain petroleum refinery products for carcinogenicity.

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Products in which PA H s have been found in other investigations rubber like material4 imported cheap products made from rubber-like material black products made from rubber-like material imported products ( e.g. from A sia) made from rubber like material products with close contact to skin or designed to be mouthed common products products made of recycled materials

For more details on the considerations of the selection of the specificproducts, see section 3.1. T able 2.5 present the candidates of products for thescreening survey of the PA H content in toys and childcare articles.

Tabl e 2.5 Toys and chi l dcar e ar t icl es suggest ed f or t h is scr eeni ng t est f orPAH cont entNo. Product category Comments Reference1 Toothbrush for children PAH content verified in

selected productsBAuA, 2010

2 Plastic clogs for children PAH content verified inselected products. BAuA, 2010SwedishNatureConservation,2010

3 Beach sandals High levels of PAHs found infootwear

BAuA, 2010

4 Rubber bracelet Skin contact5 Wheels/tyres from childrens

carts/doll buggiesPAH content verified inselected products

BAuA, 2010

6 Wheels/tyres from scooters PAH content verified inselected products

BAuA, 2010

7 Tyres from bicycles PAH content verified in

selected products

BAuA, 2010

8 Grips from scooters High levels of PAHs found ingrips

BAuA, 2010

9 Grips from bicycles High levels of PAHs found ingrips

BAuA, 2010

10 Erasers PAH content verified inselected products

BAuA, 2010

11 Plastic toy figures PAH content verified inselected products

BAuA, 2010

12 Plastic dolls Skin contact, common use BAuA, 201013 Teething rings Skin contact, PAH content

verified in selected productsBAuA, 2010

14 Carnival masks Skin contact, PAH content

verified in selected products

BAuA, 2010

15 Swimming aids (e.g. goggles) Skin contact, PAH contentverified in selected products

BAuA, 2010

16 Baby bib of plastic Skin contact17 Plastic balls, soft PAH content verified in

selected productsBAuA, 2010

18 Plastic balls, solid PAH content verified inselected products

BAuA, 2010

19 Product made of recycledmaterial

The specific product willdepend on what is available

20 Products of synthetic leather Material: PVC. Extender oils areused to improve the texture,

4R ubber-lik e material: natural rubber, synthetic rubber and mixtures of natural andsynthetic rubber.

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common use21 Wheels from toy cars Expected to contain extender

oils, common use22 Balloons Material: Latex. Extender oils

are used to improve thetexture, common use

T he products in table 2.6 were considered; however, according to the materialcomposition they were found not to be relevant to include in the investigation.

Tabl e 2.6. Pr oduct s excl uded f r om t he st udyNo. Product Comments1 Slime Slime is made from guar gum and borax

(sodium borate)2 Magic sand Magic sand is made from sand and

trimethylsilanol3 soft floor puzzles Is made of foam plastic polymer (MST report

nr 70 2006)

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Tabl e 3.1 Toys and chi l dcar e ar t icl es pur chased f or t h is scr eeni ng t est f orPAH con t ent .No. Articles Land of origin1 Toothbrush for children China2 plastic clogs for children China3 Bathing shoe Italy4 bracelet for children, synthetic

leatherChina

5 Bicycle 3-5 years, Tyre Indonesia6 Scooters, grip China7 Bicycle 3-5 years, grip Indonesia8 Eraser ??9 Rubber duck China10 squeeze ball with liquid inside China11 Plastic doll China12 Cooling teething ring China13 Goggles for children China14 Baby bib, plastic Italy15 rubber ball, solid ??16 Toy bag in synthetic leather China

17 Toy car with rubber wheels China, Hong Kong18 Balloons ??19 Squeeze-bulb horn ??20 Pen with rubber handle ??

Tabl e 3.2. Pr oduct s given up uponNo. Product Comments1 Products made of recycled

materialSearched for on the internet. However, veryfew products have been found and it wasdifficult to judge the "softness" of thematerial on the screen

2 Carnival masks of latex Toy shops: only masks of foam plastic or

vinyl have been found. Role-playing shops:latex products were of a too good quality(Danish produced) and primarily for adults.

3 Wheels/tyres from childrenscarts/doll buggies

Apart from Brio, there was only foundproducts with handles of plastic foam andhard wheels

4 Wheels/ tyres from scooters It was not possible to find products with softwheels, only hard wheels or wheels was madeof foam plastic

3.2 Met hod o f anal ysis, screen in gT he products were analysed according to a G erman standard for analysis ofPA H s in consumer products ( Z EK 01-2-08) . T he method is published by C entral Experience Exchange C ommittee ( Z EK ) together with the G ermanaccreditation body G erman A ccreditation Body for G S M ark issuing Bodies( Z L S) . T he method was used in this investigation with some modifications,as there in this project only have been done a screening for P A H s. Further thedetection li mits has been improved compared to the G erman standard.

3.2.1 Sample preparationA representative partial sample was taken from the material. T he sample was

cut in small pieces approx. 2-3 mm. For products which were larger or more

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inhomogeneous, samples were taken from surfaces where the skin contact wasexpected to be high (e.g. collar of a baby bib) .

3.2.2 Extraction methodT he samples each of approximately 0.5 g was placed in a 25 ml extractionbottle and spiked with 5 13C - or deuterium labelled PA H s ( 2-methyl-

N aphatalene, phenanthrene, anthracene, fluoranthene and pyrene) 2-methyl-N aphatalene, phenanthrene and fluoranthene was used for Q A /Q C , and for afew samples where there were interferences anthracene or pyrene were used.T he samples were extracted with 10 ml of toluene by ultra sonification in a60C water bath for one hour. 2 ml of the extract was fi ltered through a paperfi lter and washed wi th pentane. T he combined solvents were evaporated to 1ml and analysed directly on G C -M S. For a few products it was nessesary todi lute the extract as the consistency of the extract was too thick. I n those casesthe detection limit was elevated ( is indicated under the results) .

3.2.2.1 Analysis on GC-M S5 deuterium labelled PA H s were added to the extract as injection standards.T he samples were analysed on G C -M S in SI M mode. A n external standardfor verifi cation of the PA H s was analysed together with the samples.

T he samples were screened for 17 PA H s, including the 8 PA H s regulatedunder the R EA C H R egulation and the 16 EPA PA H s, i n order to make surethat the screening cover the PA H parameter group relatively broadly. Some ofthe PA H s are reported as sum, as these are diff icult to separatechromatographically.

T he following PA H s were included in the analysis:N aphthalene, A cenaphthylene, A cenaphthene, Fluorene, Phenanthrene,

A nthracene, Fluoranthene, Pyrene, Benzo(a)anthracene, C hrysene/T riphenylene ( sum) , B enzo(b+ j+ k) fluoranthenes ( sum) , B enzo(e) pyrene,Benzo( a)pyrene, I ndeno(1.2.3-cd) pyrene, Benzo( ghi) perylene, D ibenzo( ah) -anthracene.

3.2.3 Quality assurance QA/QC)A s this is a screening project the quality assurance and documentation as wellas the analytical quality was more limited as the exact concentrations were notdocumented. T he D anish EPA standard demand for documentation ofanalysis was therefore not followed strictly. I n order to make sure that therewere no false positive or negative results and that the analysis was performed

with a known and documented detection limi ts the following parts of Q A /Q Cwas included in the analysis.

R ecovery standards for control of the analytical quality I njections standards to control the performance of the G C -M S C ontrol against an external standard on high and low concentrations

levels of P A H s in order to verify the found P A H s and estimate the rangeon the concentration level ( semi quantitative)

B lind samples

T he detection li mits was based on 5 times the signal-to-noise ratio on the G C -M S. T he detection limi ts are given in table 3.3.

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Tabl e 3.3. Det ect io n l imit s of t h e specif ic PAHsPAH Detectionlimits mg/kgNaphthalene 0.003Acenaphthylene 0.01Acenaphthene 0.01Fluorene 0.005Phenanthrene 0.005Anthracene 0.005Fluoranthene 0.002Pyrene 0.002Benzo(a)anthracene 0.005Chrysene/Triphenylene 0.01Benzo(b+j+k)fluoranthenes 0.01Benzo(e)pyrene 0.005Benzo(a)pyrene 0.01Indeno(1.2.3-cd)pyrene 0.025Benzo(ghi)perylene 0.01Dibenzo(ah)anthracene 0.01

3.3 Anal yt ical r esul t s

3.3.1 Comments on the analytical methodI n the proposal it was suggested to concentrate the extracts quite a lot in orderto obtain a low detection limit as possible. H owever, for the soft rubberproducts it appeared that the consistency of the extracts became too thick, andit was therefore decided to increase the final solvent volume for all the

samples. T his increased the detection limits ( see table 3.3) .

3.3.2 Analytical results from the investigation20 samples were analysed. T he results are shown in table 3.4 and 3.5. A s thisis a screening investigation a concentration range is given for the single PA H sas well as the sum of P A H concentrations ( see below table 3.4) . T he sum ofPA H s was calculated from all PA H s ( total PA H sum) as well as from the 8R EA C H PA H s ( R EA C H PA H sum) . Further, the sum of PA H s wascalculated from the 16 EPA PA H s ( EPA PA H sum) as well as the 6 EUPA H s ( 6-PA H sum) ( see below table 2.4) that were included in the G ermaninvestigations in order to be able to compare the results from this investigationwith the G erman investigations. I n the following evaluation the results forEPA PA H sum is compared with the G erman investigations. H owever, for allproducts the sum of all PA H s ( total PA H sum) are within in the sameconcentration range as EPA PA H sum.

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Tabl e 3.4 PAHs in t oys and ch il dcar e ar t icl es (mg/ kg). The l evel s ar e semi quant it at ive det er min ed

PAH Toothbrushplasticclogs

Bathingshoe bracelet

Bicycle,Tyre

Scooters,grip

Bicycle,grip Eraser

Rubberduck

squeezeball

Naphthalene 0.5-1.0

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A s this is a screening project the results are given in concentration ranges ( seebelow 3.4) . H owever, the estimates within the concentration ranges are fairlyprecise due to the analytical method.

I n general, PA H s were detected in all samples analysed. For the 20 samples11 samples had concentrations in the range 0-1 mg/kg based on the EP A PA Hsum. I n these samples there was found 4 to 12 P A H s above the detection

limits. 8 samples had a concentration range 1-10 mg/kg ( 7-13 PA H s werefound above D L ) and 1 sample 100-1000 mg/kg (19 PA H above D L ) . T helatter was analysed twice on G C -M S in order to verify the results. I f the datais evaluated as sum of the 8 R EA C H PA H s 18 samples were in theconcentration range 0-1 mg/kg, one sample in the range 1-10 mg/kg and onein the range of 10-100 mg/kg. F or B enzo( a) pyrene 5 samples had valuesabove detection limit.

I n general mainly the small molecular size PA H s were found in this study; i.e.the PA H s are arranged according to increasing molecular size verticaldownwards in table 3.4 and 3.5. T his could indicate that the extender oils

used for many of products are relatively light mineral oils which mainlycontain the small to medium molecular size PA H s. T he tyre from the bicycle,however, shows a different pattern as it was dominated of the mediummolecular size PA H s indication that a heavier mineral oil was used as extenderoil. A s a general rule the toxi city of P A H s increase with increasing molecularsize.

For products with expected high skin contact; plastic clogs, scooters grips,squeeze ball and bathing shoes had PA H levels 1-10 mg/kg. T oothbrush,plastic doll and toy car wheels also had PA H levels 1-10 mg/kg, but these areconsidered to have less skin contact or for shorter period.

T he two specifi c baby articles ( baby bib and teething ring) both had levelsbelow 1 mg/kg.

C oncerning country of origin most of products were from C hina. T woproducts came from I taly, ( bathing shoe and baby bib) . For the bathing shoethe total sum of P A H s ranged 1-10 mg/kg whereas the baby bib was below 1mg/kg. T his shows that also European products can contain P A H s. O neproduct came from I ndonesia ( bicycle, grip and tyre) . T he tyres had thehighest amounts of P A H s among the products. T he grip from the samebicycle had levels below 1 mg/kg for the sum of P A H s.

3.3.3 Comparison to other investigationsA s mentioned earlier, several G erman investigations on PA H s in toysperformed by the Bundesinstitut fr R isikobewertung ( BfR ) has assessed anumber of toys and childcare articles with respect to P A H concentrations indifferent product types. I n about 70% of the 104 examined toy samples,PA H s were below detectable levels or contained less than 1 mg/kg PA H s.Between 1-10 mg/kg PA H s were detected in 19% and between 10-100 mg/kgPA H s in 7% of the samples. Furthermore, highest values between 100-1000mg/kg PA H s were detected in 3% of the samples. A recent investigation of 40toys found PA H content of < 0.2 mg/kg in 39 samples ( BfR 2009a) .

I n comparison to the G erman investigations this screening study found 55%of the toy and childcare articles to contain less than 1 mg/kg PA H s. 1-10

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mg/kg was detected in 40% of the samples and 100-1000 mg/kg was detectedin 5 % of the samples ( 1 sample) . D ata is summarised in table 3.6.

Tabl e 3.6 Number of sampl es found wit h PAH con t ent in t h e pr esent st udy andin Bf R st udy

Present study BfR study

No. of samples 20 140

Concentration of PAHs number % of total number % of total

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4ConclusionsT he aim of the present study was to investigate, at screening level, thepresence of PA H s in toys and childcare articles in D enmark.

Extender oils and carbon black are considered to be the two main sources toPA H s in rubber and plastic materials.

I t has not been possible to correlate different kind of extender oi ls and theirPA H content with the different rubber- and plastic materials and further tocorrelate this information to the different toys and childcare articles. T heliterature survey showed that data are not available on the contents of thePA H s in the different extender oils, the use of extender oils and black carbonin rubber and plastic materials as well as the use in toys and childcare

products.

T he current regulations do not oblige producers to supply information aboutthe quality, types and amounts of materials and additives used in the productsthey put on the market.

I n quali tative terms, however, there seems to be a tendency for bias towardsthe low molecular weight PA H s being present i n the selected survey products.T his indicates the use of extender oils of the light mineral oi l type as furtherdescribed below. I n general, the toxicity for PA H s increases with increasingmolecular size.

For selection of relevant products for the investigation, the limited knowledgeon the use of extender oi ls was used together with the results of G ermaninvestigations on PA H in toys and other consumer products. I n the selectionand purchasing, products which potentially might have a high content ofPA H s were chosen.

20 toys and childcare arti cles were analysed. T he results showed that PA H swere found in all analysed samples. I t can therefore be concluded that it iscommon for toy and childcare articles in the D anish market to contain PA H s.

I n comparison to the G erman investigations the present study found a higher

number of samples with detectable PA H s. T his is probably due to lowerdetection limi ts compared to the G erman investigations.

55% of the samples contained

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T wo baby articles were included in the study; both at concentration levels < 1mg/kg. For products with expected high skin contact four products have levelsof 1-10 mg/kg, the rest were below 1 mg/kg.

I f the found concentrations were compared to the limi ts for P A H s withinR EA C H only one product ( tyre from a bicycle) exceeded this lim it evenunder the assumption that the tyre contains relatively high amount of extender

oil ( 40% ) . T he bicycle tyre is not regulated under the limi ts for car tyres inR E A C H .

A t the present there are no specific regulation limits on PA H s in toys andchildcare articles at the present but the EU toy directive ( 88/378/EC )regulates in general the content of chemi cals in toys. T he G erman authoritieshave suggested a lim it of 0.2 mg/kg article of the 8 R EA C H PA H s. I f thesuggested limits are compared to the results in the present study exceed thebicycle tyre the limits for all 8 P A H s, whereas the scooter grip exceed for onePA H , benzo(e) pyrene.

Based on the investigation i t must be concluded that even though this projecthave focussed on products where it would be more likely to find PA H s, PA H sare common in toys and childcare articles in D enmark, but for most productsin relatively low concentration levels compared to the G erman studies.

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Appendix A

Pr oduct det ail s

No. product Description of productCountry oforigin comment

1 Toothbrush brush forchildren

Toothbrush for children withrubber handle

China

2 plastic clogs for children black plastic clogs China

3 Bathing shoe Material: clear soft rubber Italy cheap beach sandals are notavailable at time of the year

4 bracelet for children,synthetic leather

Material: Vinyl China The round rubber braceletwas not possible to find. Aremaybe not trendy anymore.

5 Bicycle 3-5 years, Tyre Ordinary tyres for bicycle Indonesia

handle and tyre from thebicycle was used

6 Scooters, grip Black grips, black hard plasticwheels

China

7 Bicycle 3-5 years, grip Black rubber handle Indonesia

handle and tyre from thebicycle was used

8 Eraser multicoloured, phthalate free ??

9 Rubber duck flexible rubber China

10 Rubber ball with liquidinside

very flexible rubber, has to besqueezed to be funny, high skin

contact

China

11 Plastic doll Baby doll with body of fabricand head, arms and legs of softplastic

China

12 Cooling teething ring Soft plastic with cooling liquidinside

China

13 Goggles for children Goggles with rubber edge China

14 Baby bib, plastic Flexible cast plastic Italy The product is not commonoutside baby shops. Onlyfew products found andnone from Asia

15 rubber ball, solid Material: Transparent rubber ??

16 Toy bag in synthetic leather Material: vinyl, another typethan the bracelet China

17 Toy car with rubber wheels Metal toy car with soft wheels China Many toy cars have hardplastic wheels

18 Balloons Balloons with flags, materiallatex

??

19 Squeeze-bulb horn Squeeze-bulb horn of metalwith handle of black rubber

??

20 Pen with rubber handle Handle of rubber ??