Accepted Manuscript

Polycyclic aromatic hydrocarbons in consumer goods made from recycled rubber

material: A review

Astrid Diekmann, Ulrich Giese, I. Schaumann

PII: S0045-6535(18)32439-1
DOI: https://doi.org/10.1016/j.chemosphere.2018.12.111
Reference: CHEM 22810

To appear in: ECSN

Received Date: 13 September 2018

Revised Date: 13 December 2018
Accepted Date: 14 December 2018

Please cite this article as: Diekmann, A., Giese, U., Schaumann, I., Polycyclic aromatic hydrocarbons
in consumer goods made from recycled rubber material: A review, Chemosphere (2019), doi: https://
doi.org/10.1016/j.chemosphere.2018.12.111.

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1 Polycyclic Aromatic Hydrocarbons in Consumer Goods

2 Made from Recycled Rubber Material: A Review

4 Authors

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5 Astrid Diekmanna, Ulrich Giesea, I. Schaumann a

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7

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8 Deutsches Institut für Kautschuktechnologie e. V.

9 Eupener Straße 33

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10 30519 Hannover
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11 Germany

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13 E-mail addresses

14 astrid.diekmann@dikautschuk.de
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15 ulrich.giese@dikautschuk.de *
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16 phone: +49 511 8420110

17 ina.schaumann@dikautschuk.de
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18

19 Keywords
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20 End-of-life tires, PAH, artificial turf, sports flooring, carcinogenic potential, health risk
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21 assessment

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23 Abstract

24 Vast amounts of rubber waste are produced every year, where end-of-life tires (ELT) mount

25 up the largest share with several million tonnes in the EU each year. This points up the

26 necessity for reusing end-of-life rubber material. The recycled material shows nearly the

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27 same advantages like the origin materials. In consequence, the recycled material is

28 predestined for the use in sport facilities, which explains that around half of the recycled

29 ELTs are used to produce artificial turf, sports flooring and injury-prevention pavements on

30 playgrounds.

31 Since tires contain potentially toxic components, there is worry concerning the release of

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32 such chemical substances stemming from these products. As tires contain highly aromatic

33 oils and carbon black, the presence of polycyclic aromatic hydrocarbons (PAH) and their

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34 carcinogenic properties are discussed controversially. This review issues a comprehensive

35 overview of PAH release and a conclusive assessment on human health risk. Analytical

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36 studies dealing with the PAH content of consumer goods made from recycled rubber material

37 and associated risk assessments are reviewed.

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In conclusion PAHs can be detected in consumer goods made from recycled rubber and are
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39 released into the environment. They reach humans via leaching (soil, ground water, rivers),

40 oral intake, dermal exposure and inhalation. Thereby, dermal contact or inhalation is the
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41 primary route of exposure, whereas oral intake and environmental pollution are regarded as
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42 secondary risks. The amount of PAHs that could potentially harm humans is in the
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43 magnitude of urban pollution. Risk assessment studies reviewed in this article show no

44 serious risk potential.

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45 1. Introduction

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Every year people produce vast amounts of rubber waste, with end-of-life tires (ELT) from

47 passenger cars and trucks accounting for the lion’s share. In 2013 ELTs totalled 3.6 million
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48 tonnes in the European Union (EU) (plus Norway, Switzerland and Turkey), according to

49 statistics compiled by the European Tire & Rubber Manufacturers’ Association (ETRMA,

50 2015). This high amount points up the necessity for reusing end-of-life rubber material.

51 Unlike other materials - glass or plastic, for example - rubber cannot be "melted". Its

52 devulcanisation as well as the recovery of its educts are highly energy-consuming and result

53 in materials of inferior quality. Recycled carbon black from rubber recycling does not, for

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54 example, satisfy the specifications for carbon black as used in the manufacture of tires. That

55 is why the main areas for ELT reuse are markets other than the original one. While energy

56 recovery and the retreading of tires accounted for around 90% of ELT reuse in 1995,

57 recycling is gaining more and more in importance, making up already 35% in 2014 (ETRMA,

58 2015).

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59 Products made of recycled rubber materials are manifold. In line with their original use,

60 recycled rubber shows advantages in terms of elasticity, abrasion, fatigue and ageing

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61 resistance. The recycled material is, therefore, predestined for use in sport facilities, which

62 explains that around 50% of ELTs are used to produce artificial turf, sports flooring and

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63 injury-prevention pavements on playgrounds (Fornai, 2016). These products show high

64 bounce and shock absorption and flexibility against deformation and grip.

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Products other than those requiring shock-absorbent surfaces are acoustic and antivibration
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66 insulation objects. These are used, for example, in tram and railway transport systems,

67 where they are able to reduce noise by up to 5 dB and vibrations by up to 20 dB (ETRMA,

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68 2015).
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69 In addition, recycled rubber material is used in modified asphalt (rubberized asphalt) and
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70 sideways (Liu et al., 2000). These asphalt mixes with recycled rubbery infill exhibit better skid

71 resistance, reduced fatigue cracking and longer pavement life than conventional asphalt
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72 (Adams et al., 1985; Koshla, Trogdon, 1990).

73 Another growing market for rubber recycling is the cement industry, where crumb rubber is
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74 used. It is reported that the admixture of crumb rubber gives Portland cement reduced
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75 density, increased toughness and ductility, higher impact resistance and more efficient heat

76 and sound insulation (ETRMA, 2015; Nehdi, Khan, 2001).

77 Only about 1% of ELTs are used in their original shape for boat bumpers, dike protection,

78 waymarks, seawater breeding reefs and recreational equipment like playground swings, for

79 example (Wang et al., 2009).

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80 2. Concern about Polycyclic Aromatic Hydrocarbons (PAH)

81 Using consumer goods made from recycled rubber material raises certain concerns

82 regarding the release of toxic chemical substances. There is, in particular, worry regarding

83 the presence of polycyclic aromatic hydrocarbons (PAH). These are complex mixtures of

84 organic compounds whose molecular structure consists of at least two or more fused

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85 benzene rings. Polycyclic aromatic hydrocarbons can be carcinogenic, mutagenic and/or

86 toxic for reproduction (Crone, Tolstoy, 2010). The carcinogenic properties of polycyclic

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87 aromatics depend on their molecular structures, especially on the position of the aromatic

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88 rings in each molecule. Different authors explain the carcinogenic properties by referring to a

89 metabolism requiring the so-called bay structure of the aromatic rings. Figure 1 shows some

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90 examples of this based on NIOSH (National Institute for Occupational Safety and Health)
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91 Manual of Analytical Methods - Polynuclear Aromatic Hydrocarbons by HPLC (high

92 performance liquid chromatography) (NIOSH, 1998).

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94 Fig.1: Bay structures of selected polycyclic aromatics based on NIOSH (NIOSH, 1998)
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96 The bay structure is a key to the biotransformation of PAHs into a toxic metabolite via a
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97 sequence of three enzymatic reactions. These result in a vicinal dihydrodiol-epoxide capable

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98 of reacting with DNA’s (deoxyribonucleic acid) nucleophilic regions (König, 2009; Kim et al.,

99 1997).

100 The International Agency for Research on Cancer (IARC) classifies different PAHs on the

101 basis of their carcinogenic potential (IARC, 1998) (see also Table 1). Exposure to PAHs

102 occurs mostly through a mixture of PAHs. There are synergistic, purely additive or

103 antagonistic effects that render it impossible to derive the total carcinogenic potential since it

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104 cannot be considered as the summation of the toxic potential of each individual PAH (Reichel

105 et al., 1985).

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106 Table 1: IARC classification of PAHs

Number of
PAH Carcinogenicity Mutagenicity
Rings

Naphthalene 2 3 -

Acenaphthene 2+ 3 ?

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Fluorene 2+ 3 -

Phenanthrene 3 3 ?

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Anthracene 3 3 -

Fluoranthene 3+ 3 +

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Pyrene 4 3 +

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Cyclopenta[c,d]pyrene 4+ AN 3 +

Benzo[a]anthracene 4 2A +

Chrysene 4 3 +
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Triphenylene 4 3 +

Benzo[b]fluoranthene 4+ 2B +
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Benzo[j]fluoranthene 4+ 2B +
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Benzo[k]fluoranthene 4+ 2B +

Benzo[e]pyrene 5 3 +
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Benzo[a]pyrene 5 2A +

Perylene 5 3 +
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Indeno[1,2,3-c,d]pyrene 5+ 2B +
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Dibenzo[a,h]anthracene 6 2A +

Benzo[g,h,i]perylene 6 3 +

Anthanthrene 6 3 +

Coronene 6+ 3 +

Dibenzo[a,i]pyrene 6 2B +

Dibenzo[a,e]pyrene 6 2B +

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Dibenzo[a,h]pyrene 6 2B +

Dibenzo[a,l]pyrene 6 2B +

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108 IARC classification:

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110 Group 3: Components which are not classifiable regarding their carcinogenicity to

111 humans

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112 Group 2B: Components which are possibly carcinogenic to humans

113 Group 2A: Components for which there is high evidence of carcinogenicity in

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114 experimental animals

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116 Mutagenicity:
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118 -: negative / +: positive / ?: questionable

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121 Since end-of-life tires account for most recycled rubber material, it is necessary to have a

122 precise view of the PAHs in them. Tires contain mineral oils which are used as plasticizers to

123 optimize running characteristics and process capability. Highly aromatic mineral oils, in

124 particular, contain carcinogenic polycyclic aromatic hydrocarbons. Furthermore, tires contain

125 carbon black (CB) which can also be contaminated with PAHs as CB is manufactured by

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126 pyrolysis at high temperature. In general, incomplete combustion of organic matter, such as

127 coal, wood or oil, results in the production of PAHs. PAHs are a natural part of fossil raw

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128 materials like coal and petroleum. They enter the atmosphere via different elemental or

129 manmade processes. While the occurrence of forest fires or volcano eruptions cannot be

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130 influenced, there are many manmade PAH-forming factors such as industrial processes

131 (where coal-fired power generation plays the predominant role), motor-vehicle traffic,

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133 2012).
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134 3. Studies Concerning PAH Content of Consumer Goods Made from

135 Recycled Rubber Material

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136 Since tires contain carbon black and plasticizer oils, PAHs can, of course, be detected in
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137 recycled rubber material. End-of-life tires are composed of different rubber types. These

138 cannot be separated. Therefore, tires are recycled in their entirety and shredded (if not used
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139 in their original shape). Most of the products made from recycled rubber material thus contain
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140 recycled rubber as a shredded component. Artificial turf, for example, is made of fibres
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141 stabilized by means of quartz sand and crumb rubber infill.

142 There are no regulations governing the declaration of the origin of rubber, i.e. a differentiation

143 between passenger car and truck tires or an indication of country of origin or age is not

144 possible. Consequently, the PAH content is hard to predict and consumer goods made of

145 recycled rubber may contain higher or lower concentrations of PAHs. In fact, the PAH

146 content varies from charge to charge. Various studies have dealt with this, resulting in

147 different estimates of PAH content.

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148 The Danish Ministry of the Environment commissioned a study on the "Migration and

149 assessment of health effects of PAHs and aromatic amines from tires" in 2005 (Nilsson et al.,

150 2005). The study deals with tires in their original shape used as playground equipment

151 (swings and sandpits) and as impact-absorbing playground surface material incorporating

152 granulated worn tires. The Danish Technological Institute, Materials Division performed the

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153 tests. To obtain the results, it extracted pulverized rubber samples using an ultrasonic bath

154 and investigated the concentrated extract by means of gas chromatography/mass

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155 spectrometry (GC/MS). The results showed a total PAH concentration of 18.8 – 92.7 mg/kg

156 (Table 2). An additional test was made sampling a tractor tire used as sandpit. The total PAH

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157 amount was 172 mg/kg. The dominant PAHs are ones like pyrene, chrysene and

158 benzo[a]pyrene with a relatively low molecular weight. In this study, there was a statistically

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significant correlation between benzo[a]pyrene and the total PAH concentration as well as
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160 between benzo[a]pyrene and individual PAHs. Benzo[a]pyrene can thus be considered a

161 PAH marker of relevance (R2 = 0.8523).

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162 The United States Environmental Protection Agency (EPA) also disclaims that concerns
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163 have been raised by the public about the safety of recycled rubber tire crumb used on
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164 recycled tire-derived material used on playgrounds and in artificial turf fields (e. g. Giuseppi-

165 Elie et al., 2017). In the end they summarized that there is no elevated health risk from
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166 playing on fields with tire crumb, although shown only by limited studies. To get further

167 information, the EPA started research activities according to the "Federal Research Action
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168 Plan on Recycled Tire Crumb Used on Playing Fields and Playgrounds" (FRAP).
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169 In order to examine the presence of hazardous substances in the crumb rubber stock used in

170 artificial turf, Act Global, a company in the sector, initiated three laboratory tests on the

171 material the company itself uses to fabricate artificial turf infill. One of these three laboratory

172 tests analysed the PAH content, applying the EPA methods 8270D and 3550C (semi-

173 volatiles) (Tilford, 2015). Herein, an ultrasonic bath extraction procedure was employed and

174 the extracted solution was analysed by means of gas chromatography. A total PAH

175 concentration of 46.1 mg/kg was observed. Table 2 presents the results in detail. Overall, the
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176 study concluded that the total PAH concentration is not higher than in other more prevalent

177 environmental sources like asphalt driveways or smoked meat.

178 There are, in addition, two reports from the pharmacological research institute Mario Negri

179 (Instituto di ricerche farmacologiche Mario Negri) dealing with the PAH content in ELTs and

180 the resulting risk to human health arising from them (see also Chapter 5) (Davoli, 2016;

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181 Davoli et al., 2016). The samples analysed originated from ELTs collected according to ISO

182 2859-1:1999 (International Organization for Standardization) and supplied for processing into

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183 artificial turf und protection plates. Table 2 also presents the results of this analysis. This

184 study focuses on PAHs cited as powerful carcinogens in a number of official

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185 pronouncements, like that of the International Agency for Research on Cancer in 2010 or that

186 of WHO’s (World Health Organization) International Programme on Chemical Safety (IPS) in

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1998 (see also NRCC 1983, NTP 2005). The total PAH content of 5 – 10 mg/kg was
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188 estimated by isotopic dilution and GC/MS, with the extraction employing an internal, custom-

189 developed method (double extraction with preliminary ultrasonic extraction).

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190 The Ecopneus study summarized the results of tests conducted in four laboratories on ELTs
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191 used as infill in artificial turf (Fornai, 2016). One of the laboratories cited was Mario Negri, the
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192 results of which are reported in detail above. These studies devoted special attention to the

193 origin of the ELTs (EU and non-EU) and the year of production. The PAH content was
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194 determined by the Grimmer and analogous methods (Grimmer et al., 1997). The Grimmer

195 method is based on isotopic dilution using GC/MS to quantify masses below 0.001 µg/g.
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196 Overall, a total PAH level of 5 – 10 mg/kg was not exceeded. In view of the fact that other
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197 studies resulted in a higher PAH content, the author doubts that all granules used to create

198 recycled rubber products originate in tires. He assumes that other elastomeric materials like

199 gaskets or brake tubes are often recycled as well. These contain higher PAH amounts. The

200 results of the Ecopneus study point to lower concentrations of PAHs in ELTs produced after

201 2010, when the REACH regulation aimed at eliminating aromatic oils in the tire industry took

202 effect (Annex XVII, Entry 50 of Reg. (EC) 1907/2006 REACH). This shows that the

203 replacement of aromatic oils has led to an evident reduction in PAHs in rubber granules
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204 recycled from end-of-life tires. A further progressive reduction is expected in the next few

205 years with the gradual reduction in the number of "old" tires. ELTs stemming from non-EU

206 countries contain more PAHs, however, suggesting that there is closer adherence to REACH

207 regulations in the EU.

208 Intron published a further study based on literature data and additional experimental results

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209 on rubber infill in artificial turf (Hofstra, 2007). A total PAH content of 20 – 40 mg/kg was

210 detected here.

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211 In an oral presentation (Applus Medio Ambiente, 2017), Applus provides results on PAH

212 content in samples containing 70% used truck tires and 30% used car tires. In this study, the

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213 total PAH amount is 192 mg/kg.

214 Dealing with the release of polycyclic aromatic hydrocarbons at synthetic turfs of different

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age (new ones and up to 8 years) Marsili et al. (2014) found contents of PAHs in all samples.
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216 They found that the highest amounts of PAHs are those of benzo[b]fluoranthene and/or

217 pyrene and that the football fields lost part of their PAH load over time.
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218 A further study arranged by the Danish Ministry (Nilsson, 2008) deals with a review of
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219 published data on the emissions and health assessment of chemical substances in artificial
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220 turf through to 2008. It reports on measurements taken by the Kemikalieninspektionen in

221 2006. The results indicate a very low benzo[a]pyrene content that is approximately 10,000
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222 times lower than the threshold set by the Swedish working environment authority. The review

223 also includes the results achieved at by Plesser and Lund on PAH content in rubber
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224 granulate intended for use in artificial turf (Plesser, Lund, 2004). Table 2 lists these results as
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225 well. The test methodology is based on NTR 329 Sintef 1997.

226 The report of the German Federal Institute of Sports Science on the environmental

227 compatibility of outdoor artificial turf (Kalbe et al., 2012) cites Wengert, who found a PAH

228 content of 1 - 77 mg/kg in styrene butadiene rubber (SBR) granulates used mostly as infill

229 material (Wengert, 2007).

230 In rubber granulates used for artificial turf, Zhang et al. (2008) detected a PAH concentration

231 partially exceeding the limit set by the New York State Department of Environmental
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232 Conservation. The authors also observe decreasing PAH concentration due to ageing effects

233 (thermal- and photo-degradation). In some cases, they identify an increase in PAHs in older

234 artificial turf fields, attributed to the refill of rubber granulate to compensate for its loss over

235 time.

236 The study of Mota et al. (2009) focused on coated recycled rubber granulates for sport

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237 facilities. These particles are coated to reduce the emission of leachates and other

238 substances into the air and to colour them (see also 4.4). Table 2 cites the PAH readings in

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239 this case.

240 Also dealing with coated rubber granules the study of Gomes et al. (2010) concentrated on

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241 PAH concentration and PAH leaching compared to uncoated rubber granules for the use in

242 sport facilities. Analysis was performed using extraction and GC/MS. Coating the granules

243
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244 compared to uncoated raw material whereas PVC coating (polyvinyl chloride) ends up in a

245 lower total PAH concentration. Nevertheless, coating leads to lower water leaching
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246 regardless of the chemical composition of the coating (see Chapter 4.1.).
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247 Llompart and coworkers (Llompart et al., 2013) focussed on the concentrations of organic
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248 chemicals in rubber recycled tire playgrounds and rubber pavers where they investigated

249 playgrounds in the Northwest of Spain as well as unused pavers. After extraction and GC/MS
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250 analysis they found a total PAH amount between 1.25 µg/g and 178 µg/g for the playgrounds

251 where the most relevant PAHs are pyrene, naphthalene, phenanthrene, fluoranthene and
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252 chrysene. Benzo[a]pyrene, which is considered as the most toxic PAH, was found in five
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253 samples. The pavers all showed much higher PAH concentrations of up to 2000 – 8000 µg/g.

254 Celeiro et al. (2014) investigated the PAH concentration of recycled rubber playground

255 surfaces in an indoor restaurant of a shopping centre by ultrasonic extraction and GC/MS.

256 The results are shown in Table 2.

257 As this review not only focusses on artificial turf grounds and playgrounds the studies of

258 Barrero-Moreno et al. (2018) and Geiss et al. (2018) on migration of polycyclic aromatic

259 hydrocarbons from plastics and rubber articles must be mentioned. Herein, the authors
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260 observe the migration of the eight priority PAHs restricted by the REACH regulation (REACH

261 regulation EC 1907/2006 Annex XVII, Entry 50) as the restriction is extended to consumer

262 products. These PAHs are in detail benzo[a]pyrene, benzo[b]fluoranthene,

263 benzo[k]fluoranthene, dibenzo[a,h]anthracene, chrysene, benzo[a]anthracene,

264 benzo[j]fluoranthene and benzo[e]pyrene. The study mainly analyses plastic and rubber

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265 consumer goods but is also dealing with recycled rubber granules from ELTs. A

266 differentiation between coated (polyurethane coating) and uncoated granules as well as

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267 granules stemming from before and after 2010 was carried out. In addition, tiles of recycled

268 rubber granules were analysed by using the same method as for the other granules which is

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269 extracting (Randell Extractor), cleaning up and subsequent GC/MS analysis. The maximum

270 concentration of PAHs amounts to 5 mg/kg (Table 2). Coated granules show less release

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than uncoated ones which is attributed to a barrier function of the coating to chemical
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272 migration. Due to the fact that the contact surface area is difficult to estimate when using

273 granules, the authors did not perform migration studies with sweat and saliva simulants as
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274 they did for plastics and rubber products. In the end, Barrero-Moreno and coworkers
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275 conclude that extender oils have the main impact on PAH migration, which is less after 2010
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276 since the REACH regulation took effect.

277 Another report on rubber crumb infill for the use on athletic fields and public parks (Lioy,
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278 Weisel, 2011) focusses on unused fiber, unused rubber crumb and field infill (up to 7 years).

279 Extraction and GC/MS analysis coupled with solid phase micro-extraction (SPME) lead to
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280 PAH concentrations labelled in Table 2. Here, the lowest PAH concentrations belong to fiber
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281 material whereas the highest amounts originate from unused rubber crumb. Further

282 investigations of the authors deal with the bioavailability of the polycyclic aromatic

283 hydrocarbons and are listed below (see in 4.2. – 4.4.).

284 Comparing the PAH concentration of different rubber granules for the use in artificial turf

285 fields with Italian standards for soils, Menichini et al. (2011) observed a benzo[a]pyrene

286 amount of up to 11 mg/kg (Table 2) which largely exceeds the pertinent standards of up to

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287 two orders of magnitude. They found high variability regardless of the origin of the rubber

288 and no association between the origin of the rubber and the PAH content could be made.

289 Summarizing all results, PAHs can be detected in consumer goods made from recycled

290 rubber. As most of the recycled rubber stems from shredded ELTs which contain highly

291 aromatic oils and carbon black, these results were expectable. The European Commission

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292 restricts the use of PAH containing components in the REACH regulation (Annex XVII, Entry

293 50 of Reg. (EC) 1907/2006 REACH). The amended paragraphs 5 and 6 limit the

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294 concentration of PAHs in consumer goods to 1 mg/kg and in materials with intensive contact

295 (such as toys) to 0.5 mg/kg (Regulation No. 1272/2013), where eight PAHs are of main

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296 priority: benzo[a]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene,

297 dibenzo[a,h]anthracene, chrysene, benzo[a]anthracene, benzo[j]fluoranthene and

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benzo[e]pyrene. At present, the recommended procedure to estimate the PAH concentration
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299 in consumer goods is according to the extraction method of Geiss et al. (2018). A current

300 work programme of the European Committee for Standardization and the European
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301 Committee for Electrotechnical Standardization (CEN, CENELEC, 2018) has started in order
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302 to reveal a standardized estimation method for PAH concentrations in rubber and plastic
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303 components. Besides, emission and migration of PAHs are of essential interest (see also

304 Chapter 4). In particular, concerning PAHs in materials with intensive contact, migration tests
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305 pursuant to the European Commission are intended. Taking into account current

306 developments, the study of Barrero-Moreno and coworkers (2018) focusses on the migration
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307 of polycyclic aromatic hydrocarbons from plastic and rubber articles.

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308 With regard to the REACH regulation according to the REACH regulation (Annex XVII, entry

309 28) recycled rubber granules are regarded as mixtures which is also agreed by the

310 commission with member states in the meeting of competent authorities for REACH and CLP

311 (Classification, Labelling and Packaging of Substances and Mixtures) (ECHA, 2018). Hence,

312 the limit values recycled rubber granules have to satisfy are more tolerant: 100 mg/kg for

313 benzo[a]pyrene and dibenzo[a,h]anthracene and 1000 mg/kg for the other six carcinogenic

314 PAHs (see above). Taking into account these limits, all reviewed studies detected PAH
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315 concentrations far below the critical values. As the mixture concentration limits are very high,

316 the European Chemicals Agency and the National Institute for Public Health and the

317 Environment (RIVM, 2017) recommend to lower the limit value for PAH concentrations in

318 granules through a restriction under REACH. In the course of this, the sum of PAH

319 concentration in granules or mulches for use as infill material in synthetic turf pitches or in

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320 loose form on playgrounds and in sport applications shall be limited to 17 mg/kg which would

321 impose concentration limits that are closer to the much lower limit values for individual PAHs

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322 in articles supplied to the general public of 1 mg/kg and in toys (0.5 mg/kg).

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323 Table 2: PAH concentrations in rubber material intended for recycling purposes

Nilsson et al. Nilsson et al. Davoli et al. Marsili et al. Plesser, Lund
Editor of Study Tilford (2015) Davoli (2016) Fornai (2016) Hofstra (2007) Applus (2017)
(2005) (2005) (2016) (2014) (2004)

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ELT as playing Tractor tyre ELT for artificial ELT for shock- ELT for shock- ELT Experiments 70 % truck Synthetic turfs, Artificial turf,
tools, impact used as turf infill absorbing absorbing granulates for on rubber infill tyres, 30 % rubber crumb, granulates
Object of Analysis absorbing sandpit surfaces and surfaces and artificial turf of artificial turf car tyres, different age

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study

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PAHs mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg ng/g mg/kg
Acenaphthene < 1.42 352 - 10150 < 0.08 - 0.32
Acenaphthylene < 1.42 < 0.08 - 1

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Anthracene < 1.42 7.6 - 283 < 0.08 - 0.76
Benzo[a ]anthracene n. d. - 1.2 2.8 2.24 0.42 0.7 5.4 - 1613 < 0.08 - 1.9

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Benzo[a ]fluoranthene
Benzo[b ]fluoranthene 2.48 0.9 1150 - 15715 < 0.08 - 3.9
0.3 - 3.0 (b+j+k) 8.0 (b+j+k)

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Benzo[j ]fluoranthene 0.9 0.3
Benzo[k ]fluoranthene 2.48 0.17 0.2 68 - 3616 < 0.08 - 1.5
Benzo[g,h,i ]perylene 2.1 - 10.7 21.5 < 1.42 240 - 903 < 0.08 - 5.8

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Benzo[a ]fluorene n. d.

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Benzo[a ]pyrene 0.4 - 2.6 8.1 < 1.42 1.3 1.0 - 1.63 1-3 52 - 663 0.12 - 3.1
Benzo[e ]pyrene 0.9 - 9.6 10.3 2.86 3.2
Chrysene 1.4 - 12.3 4.1 6.62 0.74 1.0 244 - 3422 < 0.08 - 4.2
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Dibenzo[a,j ]anthracene n. d.
Dibenzo[a,h ]anthracene n. d. - 1.3 < 1.42 0.17 0.1 73 - 573 < 0.08 - 0.44
Indeno[1,2,3-c,d ]pyrene 0.2 - 2.0 4.4 < 1.42 < 0.08 - 1.4
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Fluoranthene 2.1 - 16.0 37.4 10.8 710 - 3740 0.12 - 11

Fluorene
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< 1.42 427 - 11026 < 0.08 - 0.68

Phenanthrene 4.0 38 - 1560 0.43 - 5.9
Pyrene 11.4 - 34.0 75.6 17.5 1909 - 10281 0.16 - 37
Naphthalene < 1.42 223 - 2040 0.19 - 0.72
Sum 172.7 5 - 10 5 - 13 20 - 40 192 8021 - 58211 1 - 76
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Barrero-
Kalbe et al. Zhang et al. Mota et al. Gomes et al. Llompart et al. Celeiro et al. Lioy, Weisel Menichini
Editor of Study Moreno et al.
(2012) (2008) (2009) (2010) (2013) (2014) (2011) (2011)
(2018)
SBR granulates Artificial turf, Sport facilities Coated rubber Recycled tire Playground Recycled Unused infill, Different

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bioaccessibilit granules and playgrounds, surfaces, rubber fiber, field infill rubber
Object of Analysis y by digestive uncoated raw pavers indoor granules, granules,
fluids material coated, artificial turf

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uncoated, tiles fields
PAHs mg/kg mg/kg mg/kg mg/kg µg/g µg/g mg/kg mg/kg mg/kg
Acenaphthene n. d. - 0.16 0.04 0.04 - <0.08 0.045 - 12.8 2.0 - 2.5 <0.01 - <0.03

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Acenaphthylene 0.27 0.27 - 0.38 0.037 - 13.4 0.79 - 1.6 <0.01 - 2.48
Anthracene n. d. - 0.17 0.13 0.13 - 0.19 0.14 - 4.72 8. 5 - 11 <0.01 - <0.02
Benzo[a ]anthracene

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n. d. - 1.26 1.31 0.82 - 1.31 0.12 - 2.02 12 - 30 0.05 - 0.32 <0.02 - <0.08 0.001 - 0.51
Benzo[a ]fluoranthene

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Benzo[b ]fluoranthene n. d. - 3.39 <0.08 <0.08 1.67 - 4.32 10 - 18 0.19 - 0.43 <0.09 - <0.30 0.001 - 2.30
Benzo[j ]fluoranthene ([b ] + [k ])
0.06 - 0.15
Benzo[k ]fluoranthene n. d. - 7.29 <0.08 <0.08 0.27 - 1.69 n. d. - 2.2 0.05 - 0.24 <0.10 - <0.34

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Benzo[g,h,i ]perylene n. d. - 7.75 <0.08 <0.08 0.22 - 11.9 0.01 - 29.2
Benzo[a ]fluorene

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Benzo[a ]pyrene 0.06 - 8.58 1.19 <0.08 - 1.19 0.42 - 4.66 6.4 - 17 0.95 - 1.49 <0.11 - <0.37 <0.001 - 10.7

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Benzo[e ]pyrene 1.08 - 1.60
Chrysene n. d. - 7.55 2.83 2.12 - 2.83 0.13 - 9.16 18 - 62 0.10 - 0.49 <0.08 - <0.27 0.01 - 5.01
Dibenzo[a,j ]anthracene
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Dibenzo[a,h ]anthracene n. d. - 3.52 <0.08 <0.08 0.97 - 0.97 0.08 - 0.17 <0.14 - <0.49 <0.001 - 0.36
Indeno[1,2,3-c,d ]pyrene n. d. - 0.4 <0.08 <0.08 0.31 - 2.77 n .d - 5.8 0.001 - 1.08
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Fluoranthene n. d. - 25.4 4.5 3.74 - 5.98 0.17 - 8.24 25 - 33 <0.01 - <0.03

Fluorene n. d. - 0.77 0.12 0.12 - 0.18 0.056 - 47.7 8.5 - 11 <0.01 - <0.02
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Phenanthrene n. d. - 4.35 1.41 1.23 - 1.58 0.082 - 25.5 42 - 52 <0.01 - <0.02

Pyrene n. d. - 13.5 14.42 13.95 - 21.10 0.77 - 29.5 34 - 51 <0.01 - <0.02 0.02 - 14.2
Naphthalene n. d. - 0.86 0.16 0.13 - 0.35 0.06 - 24.2 0.43 - 0.52 <0.00 - 0.27
Sum 1 - 77 0.4 - 38.15 26.77 23.15 - 34.17 1.25 - 178 170 - 295 2.58 - 4.66 0.04 - 45.1

325 n. d. - not detected

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326 4. PAH Emissions

327 As all studies detected PAHs to a certain extent, it is advisable to consider the ways in which

328 humans could possibly be harmed by consumer goods made of recycled rubber and the

329 PAHs contained in them. Both, environmental inflow and human contact with consumer

330 goods must be considered. Of particular interest are the PAH emissions into the atmosphere

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331 and the environmental impact of PAHs on the soil and groundwater. In addition, humans

332 could be at risk if they inhale, dermally absorb or orally take in PAHs stemming from recycled

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333 rubber material.

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334 The risk of PAHs leaching out of tires is considered to be very low (International Carbon

335 Black Association, 2014). But most products made of recycled rubber material contain rubber

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336 in a shredded form which increases the surface of the rubber material. As a result, this
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337 material might emit PAHs at a higher rate than tires themselves. Several studies have thus

338 dealt with the emission and migration of PAHs out of recycled rubber material. A summary of
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339 these follows below.

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340 4.1. Leaching of PAHs out of Recycled Rubber Material

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341 There is a risk of PAHs coming into contact with the groundwater and soil in the case of

342 consumer goods made of recycled rubber material and intended for out-of-door use like
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343 playground equipment and surfacing, asphalt, outdoor sports flooring or artificial turf.

344 The Intron study concerning the environmental and health aspects of rubber infill (Hofstra,
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345 2007) revealed no environmental risk from PAHs leaching into the soil and groundwater.
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346 The study conducted by H. J. Kolitzus (Kolitzus, 2006) used lysimeter devices in

347 investigating the water leaching of PAHs from synthetic sports surfaces. A one-year

348 collection period was scheduled. Results present a PAH concentration of around 0.02 µg/L

349 each, with a total sum of 16 PAHs of 0.1 – 0.3 µg/L. Since PAHs are ubiquitous substances

350 in the environment and in water, the author classifies the PAH concentration as not

351 noteworthy.

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352 Mota et al. (2009) also conducted a study dealing with the leaching of PAHs into water,

353 focussing on coated recycled rubber granules for sport facilities. They performed the

354 leaching experiments for 48 hours and investigated the leachates by means of GC/MS.

355 Leaching is very low overall in all samples and is slightly reduced by coating to 0.016 mg/kg

356 (total PAH sum) compared to < 0.05 mg/kg in the uncoated material.

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357 Another study dealing with coated and uncoated rubber granules was performed by Gomes

358 and coworkers (2010). Table 3 shows that water leaching is negligible regardless of the

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359 coating as the PAH concentrations are very low or even below the detection limit.

360 Plesser and Lund (2004) investigated the contact water of rubber granulates used in artificial

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361 turf by performing leaching tests with deionized water (Table 3). As drinking water

362 requirements define specific limits only for benzo[b]fluoranthene, benzo[k]fluoranthene,

363
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indeno[1,2,3,c,d]pyrene, benzo[g,h,i]perylene and benzo[a]pyrene content, the leachate is in
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364 compliance with this requirement. Plesser and Lund thus compared his results for

365 anthracene, fluoranthene and pyrene content with the limits defined in the Canadian
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366 Environmental Quality Guidelines. The anthracene, fluoranthene and pyrene content is in
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367 excess of the Canadian limits. Accordingly, the author recommends more detailed risk
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368 analysis as to whether there is a real danger to human health and the environment in this

369 case.
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370 Källqvist and Kopangen performed this risk analysis on the basis of the data provided by

371 Plesser and Lund (Källqvist, Kopangen, 2005). They concluded that PAHs leached out of
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372 artificial turf contribute marginally to environmental pollution (see Chapter 5).
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373 The analyses conducted by the German Federal Institute of Sports Science on the leaching

374 of artificial sport fields showed an overestimation of PAHs in extraction experiments (Kalbe et

375 al., 2012). To obtain realistic results, the institute recommends column experiments that take

376 into account the complete artificial turf system. This is advisable because different

377 components in the system may interact and ultimately affect leaching. In such column

378 extraction experiments, the authors employ a PAH-detecting HPLC device that yields results

379 for total PAH concentration of about 0.5 – 6 µg/L, which is assessed as a low value for
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380 leachates. PAH leaching decreases over time, although experiencing several interim rises

381 due to ageing and polymer degradation effects after weathering. The observed increase

382 during weathering does not exceed the initial values.

383 Moretto performs another study dealing with the environmental impact of rain water

384 (lysimeter) and assessing the associated health risk where PAHs are involved (Moretto,

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385 2007). He found no negative impact on the environment.

386 In a review of recycled rubber in light-fill applications, Liu et al. (2000) observed that leaching

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387 of PAHs from asphalt takes place at more basic conditions, with a pH of around 8. Liu

388 reported on a study conducted by the Twin City Corporation (1990) in which the

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389 recommended allowable limits (RAL) are exceeded for all PAHs under basic conditions. In

390 there, the authors thus recommend a roadway design based on rubberized asphalt with

391
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water infiltration. However, Liu et al. view the results sceptically, as the report of the Twin
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392 City Corporation references evidence of contamination from other sources as well. In

393 addition, all the other studies reviewed by Liu do not conclude any hazard risk. Liu and
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394 coworkers calculated higher PAH emissions into the atmosphere when higher temperatures
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395 prevail during laying of the asphalt. In view of the thousands of pounds of abraded rubber
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396 automobile traffic releases into the environment on a daily basis, the authors regard the

397 influence of a negative effect by rubbered asphalt as negligible.

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398 Although probed in an indoor restaurant Celeiro et al. (2014) investigated the PAH water

399 leaching of recycled rubber playground surfaces and observed partial leaching. Nine of
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400 sixteen investigated PAHs could be found in the water where the total concentration was in
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401 the level of two mg/L.

402 Nordgren and Preinfalk (2009) report the results of leaching tests on rubberized asphalt

403 performed by the Swedish Geotechnical Institute in Linkoping. No leachate exhibited any

404 detectable carcinogenic PAH.

405 Overall, the results of all studies fall below the limits published by the German Federal

406 Environment Agency (2012), which postulates a benzo[a]pyrene content of 2 mg/kg in the

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407 soil in children’s play areas and up to 12 mg/kg for industrial and commercial plots of land.

408 The restriction for drinking water is cited as 10 ng/L.

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409 Table 3: PAH concentrations in leaching experiments

Mota et al. Mota et al. Gomes et al. Plesser, Lund Kalbe et al. Celeiro et al.
Editor of Study Kolitzus (2006) Moretto (2007)
(2009) (2009) (2010) (2004) (2012) (2014)

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Sports surfaces, Uncoated Coated rubber Coated rubber Artificial turf, Complete Artificial turf, Playground
lysimeter tests rubber granules granules and granulates, artificial turf lysimeter surfaces,

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Object of Analysis granules uncoated raw leaching in system, indoor
material deionised leaching
water

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PAHs µg/L mg/kg mg/kg mg/kg µg/L µg/L µg/L ng/mL
Acenaphthene <0.003 <0.001 <0.001 - <0.003 0.03 15
Acenaphthylene <0.003 <0.001 <0.001 - <0.003 0.27 26

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Anthracene <0.003 <0.001 <0.001 - <0.003 0.03 211

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Benzo[a ]anthracene <0.003 <0.001 <0.001 - <0.003 <0.01 681
Benzo[a ]fluoranthene
Benzo[b ]fluoranthene <0.003 <0.001 <0.001 - <0.003

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Benzo[j ]fluoranthene
Benzo[k ]fluoranthene <0.003 <0.001 <0.001 - <0.003

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Benzo[g,h,i ]perylene <0.003 <0.001 <0.001 - <0.003
Benzo[a ]fluorene

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Benzo[a ]pyrene <0.003 <0.001 <0.001 - <0.003
Benzo[e ]pyrene
Chrysene
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<0.003 <0.001 <0.001 - <0.003
Dibenzo[a,j ]anthracene
Dibenzo[a,h ]anthracene <0.003 <0.001 <0.001 - <0.003
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Indeno[1,2,3-c,d ]pyrene <0.003 <0.001 <0.001 - <0.003

Fluoranthene <0.003 <0.001 <0.001 - <0.003 0.06 243
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Fluorene <0.003 <0.001 <0.001 - <0.003 0.04 111

Phenanthrene <0.003 <0.001 <0.001 - <0.003 0.16 709
Pyrene <0.003 <0.001 <0.001 - <0.003 0.13 222
Naphthalene <0.005 <0.001 <0.001 - <0.005 0.15 5.2
Sum 0.1 - 0.3 <0.05 <0.016 <0.016 - <0.050 0.87 0.5 - 6 < 0.1 2223
410

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411 4.2. PAH Exposure due to Oral Intake

412 In the case of recycled rubber and the products manufactured from it, oral ingestion might be

413 possible through hand to mouth exposure to dust and/or small particles. This has to be taken

414 into consideration particularly in the case of artificial turf, where shredded rubber infill is used

415 to stabilize the fibres.

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416 Most studies regard this scenario as of minor importance and do not analyse a potential risk

417 due to oral intake. The "Environmental and health aspects of rubber infill" study (Hofstra,

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418 2007), for example, describes the risk of swallowing rubber infill as irrelevant in view of a

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419 background PAH exposure in food of 4 ng/kg body weight.

420 There are, however, publications dealing with the risk of oral ingestion and the

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421 bioaccessibility/bioavailability of PAHs. In the case of tires reused in their original shape for
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422 sandpits (Nilsson et al., 2005), PAHs could migrate into the sand and small children might

423 then be at risk of oral intake of contaminated sand. Table 2 presents the results on the PAH
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424 content of the tractor tire used as sandpit in this study. The sand was analysed for PAHs

425 prior to the exposure experiment and over a period of about 6 weeks. The sand’s PAHs
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426 concentration increases over time. But, taking into account the reference samples and the
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427 tractor tire’s initial PAH content, the authors come to the conclusion that the main reason for

428 the PAH increase in the sand is the deposition of PAHs from the atmosphere (due to rain
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429 water). PAH migration from the tire into the sand occurs only to a minor degree. After this, a

430 health assessment was carried out according to the EU’s Technical Guidance Document
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431 (TGD, 2003), calculating oral intake of sand on the part of the young children, the major
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432 group exposed. It came to the conclusion that the potential long-term risk from all PAHs

433 analysed is insignificant (see also Chapter 5).

434 Zhang et al. (2008) address the oral intake issue by investigating the dissolution of PAHs

435 from rubber infill in artificial turf in digestive fluids like saliva, gastric fluid and intestinal fluid.

436 After extraction in a Soxhlet apparatus, the PAH concentration was analysed using an HPLC

437 system. The subsequent bioaccessibility simulation study suggests that the absorption of

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438 PAHs through ingestion is unlikely for the very reason that PAHs do not readily dissolve in

439 synthetic digestive fluids.

440 Again, dealing with the bioavailability of PAHs from rubber crumb Lioy and Weisel (2011)

441 analysed possible ingestion risks via digestive fluids extraction (saliva, gastric and intestinal

442 fluid). None of the tested samples exceed the NJ DEP (New Jersey Department of

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443 Environmental Protection) soil cleanup criteria (NJ DEP 1999) so that this route of exposure

444 is not considered to be of major health concern.

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445 4.3. Dermal Exposure

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446 Consideration of the recycled rubber material used in consumer goods must also take into

447 account dermal contact. Involved here are direct skin contact as well as the migration of

448 PAHs through sweat.

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449 In the aforementioned Danish Ministry study dealing with playground equipment and shock-

450 absorbing playground surface material (Nilsson et al., 2005), a defined surface of the tires
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451 analysed was exposed to artificial sweat (to ISO 12870:1997 (E)) at 30 °C for one hour. PAH

452 migration could be observed for fluoranthene (0.029 – 0.277 ng/cm2) and pyrene (0.032 –
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453 0.487 ng/cm2). Migration testing did not succeed in detecting any other polycyclic aromatic
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454 hydrocarbons (Table 4). In the case of both, fluoranthene and pyrene, the authors rate the

455 potential risk to human health as insignificant.

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456 The laboratory Mario Negri also did migration testing with artificial sweat to analyse dermal

457
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exposure, with the artificial sweat prepared according to EN 1811 (Davoli et al., 2016). This

458 involved storing ELT material in artificial sweat under sample agitation at 37°C for 24h. The
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459 study distinguished tires of EU origin from those of non-EU origin and also took date of

460 production into account. This was done to differentiate between rubber material produced

461 before and after the introduction of the REACH ban. The measured number of PAHs

462 released is below the detection limit or at a level of 0.0002 – 0.06 %, depending on grain

463 size. As expected, smaller particles release more PAH due to their greater surface. The

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464 origin of the ELT does not allow for the postulation of any obvious trend with regard to sweat

465 migration.

466 The Ecopneus study (Fornai, 2016) summarized the results of tests conducted in four

467 laboratories on ELT granulates used in artificial turf, with one being the study carried out at

468 Mario Negri. Amongst other things, dermal exposure was investigated by means of sweat

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469 migration tests. These tests were performed at 37 °C for 24 hours using artificial sweat

470 (Nichel migration, modified EN 1810 – European Norm). The PAH concentration in the sweat

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471 migration tests is lower than or near the detection limit for each polycyclic aromatic

472 hydrocarbon species (Table 4). In addition, the dermal exposure of workers installing artificial

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473 turf and athletes playing on it was checked by dermal polypropylene patches on chest,

474 shoulder, wrist and calf. Here the dermal exposure risk was found to be lower than the risk in

475 conjunction with inhalation (see 4.4).

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476 A second Ecopneus study conducted in collaboration with Waste and Chemicals (Persici,

477 Lupi, 2016) was performed to analyse PAH exposure during installation of artificial turf with
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478 rubber infill against infill with other granulates made of vegetable oil. In addition, the players’
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479 exposition during use was investigated. This was done by analysing inhalation exposure on
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480 the basis of samples of PAH dust particle deposition on the skin surface, where readings

481 were corrected for values in the surrounding air. As there are, to date, no standardized
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482 studies dealing with dermal exposure, the sampling was done analogous to Jongeneelen et

483 al. (1988), Van Rooij et al. (1993) and McClean et al. (2004), with pads placed at different
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484 spots on the body (chest, shoulder, wrist, calf) covering a monitoring area of 20 mm
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485 diameter. The environmental sampling for the correction values complied with ISO 12884

486 and US EPA TO9 (United States Environmental Protection Agency), US EPA TO13A.

487 Analytical methods were based on extraction with Soxhlet apparatus and assessment via

488 high resolution gas chromatography with mass selective detection HRGC/HRMS. In sum, 22

489 PAHs were quantified, of which 11 PAHs were considered a more relevant health risk. The

490 final results are presented as a benzo[a]pyrene (BaP) concentration, with no sample

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491 exceeding a value of 0.2 ng/cm2 (Table 4). The authors note that there are no regulatory

492 limits against which these results can be compared.

493 The aforementioned Intron study (Hofstra, 2007) calculated a dermal uptake of

494 benzo[a]pyrene of 0.12 ng/kg body weight, using benzo[a]pyrene as a marker for the total

495 PAH uptake (Table 4). This does not exceed the limit-value of 1 ng/kg body weight of

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496 benzo[a]pyrene per day. The study concludes that during a match, an athlete experiences

497 only limited additional PAH intake due to dermal contact. This is corroborated by urine-

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498 analysis, with 1-hydroxypyrene (metabolite of pyrene) being analysed before and after a

499 match.

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500 The dermal uptake of PAHs from rubber crumb was investigated by Lioy and Weisel (2011)

501 using sweat biofluid extraction. Analyses were performed using GC/MS coupled with SPME.

502
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The results are denoted in Table 4. The authors conclude, that dermal uptake do not appear
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503 to present a major health concern.

504 Overall, it should be noted that analysing dermal exposure by means of sweat migration
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505 testing with aqueous artificial sweat underestimates the real exposure. Even though not
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506 dealing with recycled rubber goods but with handles of hammers and a wheel of a childrens
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507 handcart in first use, Bartsch et al. (2016) investigated PAH skin permeation by the analysis

508 of benzo[a]pyrene. The authors performed skin permeation tests on real human skin and
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509 compared the results with benzo[a]pyrene-migration tests in artificial sweat (aqueous) and

510 ethanolic simulant by means of GC-MS/MS and LC-MS/MS (liquid chromatography - mass
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511 spectrometry/mass spectrometry). They found good agreement of permeation results with
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512 migration in ethanolic simulant but an underestimation of migration in artificial sweat by two

513 orders of magnitude.

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514 Table 4: Dermal uptake of PAHs

Nilsson et al. Davoli et al. Persici, Lupi Lioy, Weisel

Editor of Study Fornai (2016) Hofstra (2007)
(2005) (2016) (2016) (2011)

ELT as playing ELT for artificial ELT granulates, ELT for artificial Rubber infill of Unused infill,
tools, artificial turf, release in sweat migration turf, pads for artificial turf, fiber, field infill,
Object of Analysis sweat artificial sweat test dermal uptake estimated sweat biofluid
uptake from extraction
migration data
PAHs ng/cm² % % ng/cm² ng/kg bw mg/kg

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Acenaphthene <0.00 - <0.11
Acenaphthylene <0.01 - <0.17
Anthracene <0.00 - <0.08
Benzo[a ]anthracene 0.006 - 0.095 <0.01 - <0.32

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Benzo[a ]fluoranthene
Benzo[b ]fluoranthene <0.04 - <1.23
0.009 - 0.016
Benzo[j ]fluoranthene
Benzo[k ]fluoranthene

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0.005 - 0.008 <0.04 - <1.38
Benzo[g,h,i ]perylene
Benzo[a ]fluorene
Benzo[a ]pyrene 0.001 - 0.002 0 - 0.19 <0.05 - <1.46
Benzo[e ]pyrene

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0.001 - 0.002
Chrysene 0.005 - 0.0155 <0.03 - <1.07
Dibenzo[a,j ]anthracene
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Dibenzo[a,h ]anthracene <0.06 - <1.97
Indeno[1,2,3-c,d ]pyrene
Fluoranthene 0.029 - 0.277 <0.00 - <0.12
Fluorene <0.00 - <0.07
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Phenanthrene <0.00 - <0.10

Pyrene 0.032 - 0.487 <0.00 - <0.10
Naphthalene <0.00 - <0.03
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Sum 0.002 - 0.006 0.12

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516 4.4. Inhalation of PAHs

517 PAH inhalation, especially during the installation or use of artificial turf with rubber infill,

518 seems the most likely scenario. Therefore, many studies deal with this topic.

519 In an open letter, the Fédération Internationale de Football Association (FIFA) cites no or, at

520 the most, very negligible release of PAHs from granulate infills in artificial turf and concludes,

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521 therefore, that there is no cancer risk (FIFA, UEFA, 2006).

522 The Federal Office of Public Health (BAG, 2006) summarizes results on the inhalation of fine

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523 dust particles (< 10 µm) in indoor sport halls covered with artificial turf. It qualifies the PAH

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524 concentration in the air of Norwegian sport halls as of the same level as the concentration in

525 the air in Oslo in summer. The level of benzo[a]pyrene (BaP) in the air complies with the

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526 recommended value of 1.3 ng/m3 BaP in Germany. BaP was used here as a marker for PAH
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527 as it normally makes up a constant share of approximately 10 % in all PAHs. Further results

528 in this review of the literature calculated a worst-case scenario with a possible PAH
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529 inhalation of 3.8 ng/kg body weight. This poses no risk to health.

530 Based on their own studies and on literature data, Intron (Hofstra, 2007) concluded that there
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531 is no risk due to inhalation when using indoor and outdoor installations made of recycled
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532 rubber material. They recommend, however, that indoor sports fields be sufficiently

533 ventilated.
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534 Taking into account indoor artificial turf halls the Norwegian Pollution Control Authority and

535 the Norwegian Institute for Air Research (Dye et al., 2006) investigated the air pollution of
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536 three different artificial turf pitches. Airborne dust as well as gas phase compounds were
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537 collected in this study using glass fibre filter and polyurethane plugs with subsequent Soxhlet

538 extraction and GC/MS. The total PAH concentration in the gas phase amounted from 121 up

539 to 364 ng/m3.

540 Comparing indoor and outdoor artificial turf fields, Ginsberg and Toal (Ginsberg, Toal, 2010)

541 investigated PAH concentrations in air by stationary and personal sampling. A variety of

542 PAHs showed amounts above the background level but at low concentrations (Table 5). In

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543 general, the PAH content of the indoor field was higher and PAHs were more numerous.

544 Naphthalene and its derivates could be observed only at the indoor field whereas multi-ring

545 PAHs occurred just outside. Table 5 denotes the PAH concentrations of this study at what

546 the derivates of naphthalene are not listed here (indoor 0.206 µg/m3, outdoor 0.0093 µg/m3).

547 In an oral presentation, Applus (Applus Medio Ambiente, 2017) discusses the use of PUF

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548 (polyurethane foam) filters with high-volume containers to track PAH emissions into the

549 atmosphere. Table 5 presents the results. Benzo[a]pyrene, chosen as a PAH marker, was

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550 found to not exceed the limit value of 5 µg/m3 proposed by the European Parliament.

551 Dealing with the release of polycyclic aromatic hydrocarbons at synthetic turfs of different

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552 age (new ones and up to 8 years) Marsili et al. (2014) reveals that the PAH release into the

553 air by rubber crumb is not decreasing with time (Table 5) although the fields lose PAH load

554 over time.

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555 The inhalation risk was investigated by Lioy and Weisel (2011) using lung biofluid extraction

556 (Table 5). Only one single extract exceeded the detection limit in acenaphthylene to a higher
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557 level of 2.48 mg/kg. The application of rubber crumb infill is therefore not considered as of
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558 major health concern for outdoor fields.

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559 TRC published a comprehensive survey study prepared for the New York City Department of

560 Health and Mental Hygiene on the air quality of synthetic turf fields containing crumb rubber
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561 infill (Vetrano, 2009). The study compares air quality results with those of a grass field. In

562 order to examine ageing effects, the study included a newer (< 1 year) and an older
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563 (> 3 years) synthetic turf field. The samples were collected at a height simulating the
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564 breathing zone of young children (US EPA 2008). As a means of capturing the potentially

565 highest concentration due to temperature effects, the samples were additionally collected

566 under simulated playing conditions from late morning through afternoon on a summer day. A

567 sampling pump with sorptive media was placed on the fields for 4 days, with a sampling time

568 of 120 min each day. Ambient conditions like weather, temperature, wind, and traffic

569 conditions are documented. None of the 17 PAHs under study was detected in any of the

570 ambient air samples.

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571 The institute Mario Negri prepared pulmonary surfactant migration tests (Davoli et al., 2016)

572 to simulate inhalation effects. The study differentiates the ELT material by EU / non-EU origin

573 and date of production (ante 2010 and post 2010, REACH). The migration was analysed

574 using ELT material and artificial surfactant; the suspension was kept at 37 °C for 24 h under

575 continuous agitation of 60 beats/min Pavilonis et al., 2014). The migration in pulmonary

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576 surfactant was larger than the migration in artificial sweat also sampled in this report (see

577 4.3.). PAH release was about 0.18 % for all samples (EU/non-EU, ante 2010/post 2010) (see

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578 Table 5).

579 The Ecopneus study (Fornai, 2016) of artificial turf fields, which deals with results from four

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580 laboratories (one of which is the institute Mario Negri), also analysed migration in pulmonary

581 surfactant and performed field studies by checking the possible inhalation of PAHs by

582
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workers and players. Inhalation exposure was analysed by breathing zone sampling with
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583 personal sampling pumps for players and workers. The PAH release in pulmonary surfactant

584 was below 0.2 % in all samples (Table 5). Regarding inhalation, the authors conclude that
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585 the PAH concentration in the air above artificial turf playing fields is comparable to the air
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586 quality in the surrounding areas.

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587 The Ecopneus study, in collaboration with Waste and Chemicals (Persici, Lupi, 2016),

588 analysed the inhalation exposure of workers and players by sampling the PAHs in the
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589 personal breathing zones. A background correction for the surrounding air was performed.

590 As mentioned above (see 4.3), the measurements included the estimation of 22 PAHs
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591 (reduced to 11) analysed by extraction and HRGC/HRMS. Table 5 lists the BaP content of
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592 the air during installation of the artificial turf. The maximum BaP concentration during a

593 match rises to 13.7 ng/m3, while the level of BaP in the surrounding environment reaches

594 12.34 ng/m3. This results in no hazard risk (see Chapter 5).

595 Castellano and coworkers (2008) published preliminary studies dealing with the exposure of

596 artificial turf users to toxic and carcinogenic substances. The environmental and personal

597 sampling was done in Rome, Italy, using suction pumps. Extracts were analysed by GC/MS

598 and ICP-MS (inductively coupled plasma mass spectrometry) methods. An additional
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599 biological monitoring via urinary analyses using HPLC MS/MS was performed in this study.

600 The results are denoted in Table 5 and show PAH concentrations which are mostly lower

601 than the limit of detection. The concentrations varied from sampling station to sampling

602 station and from one day to another. The 1-hydroxypyrene values are lower than the

603 biological effect of 1.4 µmol/mol of creatine. Concluding their results the authors found no

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604 occupational exposure nor any additional exposure concerning PAHs other than an

605 environmental exposure in urban areas.

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606 The PAH concentration in air during the use of the artificial turf was investigated by Menichini

607 et al. (2011) which were referenced to background locations outside the field. Samples were

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608 collected static and as personal sampling with glass fibre filters for 2 – 3 hours during training

609 for three days. Analyses were performed after ultrasonic extraction using HRGC/LRMS (high

610
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resolution GC/low resolution MS). The concentration of PAHs in air was substantially
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611 constant and ranged in between < 0.01 ng/m3 and 0.4 ng/m3, where the latter value was

612 used to calculate a worst-case scenario (see Chapter 5). No significant difference to those
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613 concentrations detected at the background site could be found so that the authors found
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614 negligible contribution of PAH release from the rubber granulates. The PAH concentration in
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615 air at the fields is even lower than those of urban site.

616 Comparing PAH concentration in the air at artificial turfs with urban areas Schilirò et al.
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617 (2013) analysed filter samples (extraction, HRGC/LRMS) seasonal. Low PAH concentrations

618 were found in summer season and higher concentrations during the winter period. Especially
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619 Benzo[a]pyrene was present in all samples in winter whereas it could not be detected in
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620 summer. In mean, the concentration of BaP in winter amounts to 1.06 ng/m3 which is

621 comparable with the concentrations reported as the annual average of 1 ng/m3. Overall, the

622 concentrations of PAHs were comparable with urban levels no matter of the season. The

623 authors concluded that the contribution of PAHs released from granular rubber material was

624 likely negligible.

625 With regard to emissions on artificial turf, a review by Simon (2010) notes that grass fields

626 require the use of mowers and paint, both of which are not necessary when using artificial
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627 turf. In view of the fact that mowers need fuel, like motor vehicles in traffic, and paint might

628 also contain PAHs, it must be noted that outdoor grass fields also produce PAHs, although to

629 a minor extent.

630 The study by Mota et al. (2009) dealt with coated recycled rubber granulates. Coating was

631 performed in order to reduce the emission of leachates and substances in the air. Polyvinyl

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632 chloride (PVC) coating reduces emissions only slightly.

633 Celeiro et al. (2014) investigated the votalisation of PAHs in the vapor phase of recycled

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634 rubber playground surfaces in an indoor restaurant of a shopping centre by HS-SPME.

635 Acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene,

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636 benzo[a]anthracene and chrysene could be observed.

637 Nordgren and Preinfalk (2009) considered rubberized asphalt, taking into account field

638
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studies, literature data and laboratory tests. They expected the addition of rubber to result in
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639 emission of fewer particles. Field studies of inhalation risk were conducted measuring PAHs

640 in the workers’ inhalation zone. The highest PAH content was observed directly above the
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641 augers, but no value was found to be above the threshold. There is an increase in PAH
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642 release, when the asphalt mixture is strongly heated. The authors also found that aspects
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643 like wind direction and velocity influence the degree of inhalation exposure. They thus

644 recommend a temperature reduction in the production process.

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645 Table 5: PAH concentrations in air and pulmonary surfactant

Ginsberg, Toal Ginsberg, Toal Marsili et al. Lioy, Weisel Davoli et al.
Editor of Study Dye et al. (2006) Dye et al. (2006) Applus (2017)
(2010) (2010) (2014) (2011) (2016)

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Air pollution of Air pollution of Indoor artificial Outdoor artificial ELT, 70 % truck Synthetic turfs, Unused infill, ELT for artificial
indoor artificial indoor artificial turf fields turf fields tyres, 30 % car evaporates of fiber, field infill, turf, pulmonary

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Object of Analysis turf halls, turf halls, gas tyres, PUF-filter rubber crumb of lung biofluid surfactant
airborne dust phase different age extraction migration
compounds

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PAHs ng/m³ ng/m³ µg/m³ µg/m³ ng/m³ ng/g mg/kg %
Acenaphthene 0.02 - 0.06 4.77 - 14.2 0,0174 0.03 - 0.32 <0.00 - <0.05
Acenaphthylene 0.04 - 0.19 6.24 - 78.1 0,0068 0,0066 0.03 - 0.21 <0.00 - <0.09

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Anthracene 0.04 - 0.05 0.77 - 1.86 0.02 - 0.46 <0.00 - <0.04

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Benzo[a ]anthracene 0.14 - 0.56 0.05 - 0.15 0,00011 < 0.02 0.14 - 0.49 <0.01 - <0.16 0.06 - 0.11
Benzo[a ]fluoranthene 0.23 - 0.44 0.01 - 0.03
Benzo[b ]fluoranthene 0,00021 < 0.09 <0.03 - <0.62

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0.06 - 0.12
Benzo[j ]fluoranthene 0.72 - 2.24 0.01 - 0.04
Benzo[k ]fluoranthene 0,00008 < 0.37 <0.03 - <0.69

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Benzo[g,h,i ]perylene 0.69 - 1.11 <0.01 - <0.02 0,00014 < 0.55 0.42 - 1.28
Benzo[a]fluorene 0.02 - 0.06 0.05 - 0.12

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Benzo[a ]pyrene 0.38 - 1.15 <0.01 - 0.02 0,00019 < 0.55 0.11 - 0.89 <0.04 - <0.74 0.05 - 0.09
Benzo[e ]pyrene 0.39 - 0.78 <0.01 - 0.03 0,00026 0.04 - 0.055
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Chrysene 0,00034 < 0.02 1.06 - 5.82 <0.02 - <0.54 0.3
Dibenzo[a,j ]anthracene
Dibenzo[a,h ]anthracene 0.06 - 0.13 <0.01 - <0.02 < 0.37 <0.04 - <0.98
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Indeno[1,2,3-c,d ]pyrene 0.42 - 1.11 <0.01 - <0.02 < 0.92

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Fluoranthene 0.48 - 0.67 1.66 - 2.81 0,0056 0,0068 0.1 - 1.14 <0.00 - <0.06
Fluorene 0.04 - 0.1 7.86 - 19.2 0,054 0.05 - 0.92 <0.00 - <0.03
Phenanthrene 0.33 - 0.52 14.0 - 25.0 0,032 0.64 - 6.93 <0.00 - <0.05
Pyrene 0.64 - 1.17 1.8 - 3.54 0,0118 0,0069 0.3 - 4.17 <0.00 - <0.05
Naphthalene 0.04 - 0.17 11.1 - 20.9 0,113 0.1 - 0.33 <0.00 - <0.02
Sum 4.89 - 10.84 120.64 - 363.74
646
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Persici, Lupi Castellano et al. Schiliro et al.

Editor of Study Fornai (2016) Fornai (2016) Fornai (2016) Nordgren (2009)
(2016) (2008) (2013)

ELT granulates, ELT granulates, ELT granulates, ELT for artificial Exposure, Comparison Rubberized

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artificial turf infill, artificial turf infill, artificial turf infill, turf, breathing artificial turf, artificial turf and asphalt
Object of Analysis pulmonary air quality air quality zone workers environmental urban area, filter
surfactant installing playing and personal sampling,

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sampling seasonal
PAHs % ng/m³ ng/m³ ng/m³ ng/m³ ng/m³ µg/m³

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Acenaphthene <0.1
Acenaphthylene <0.1
Anthracene <0.1 <LOD

U
Benzo[a ]anthracene 0.3 - 1.7 0.3 - 15 <0.1 <LOD - 2.13

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Benzo[a ]fluoranthene
Benzo[b ]fluoranthene 0.05 - 1.25 0.1 - 10 <0.1 <LOD - 4.00 ([b ]
Benzo[j ]fluoranthene + [k ])
0.02 - 0.5 0.1 - 4
<0.1

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Benzo[k ]fluoranthene 0.03 - 0.6 0.1 - 3.5
Benzo[g,h,i ]perylene <0.1 <LOD - 1.31

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Benzo[a]fluorene
Benzo[a ]pyrene 0.18 - 0.85 0.1 - 14 < 0.05 - 26.72 <0.1 <LOD - 1.75 0.03

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Benzo[e ]pyrene 0.2 - 0.9 0.1 - 7
Chrysene 0.25 - 1.4 0.2 - 26 <0.1 <LOD - 2.24
Dibenzo[a,j ]anthracene
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Dibenzo[a,h ]anthracene 0.02 - 0.7 0.1 - 1 <0.1 <LOD - 0.25
Indeno[1,2,3-c,d ]pyrene <0.1 <LOD - 1.03
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Fluoranthene <0.1 - 11,57 <LOD - 0.94

Fluorene <0.1
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Phenanthrene <0.1 - 16.44 <LOD - 0.24

Pyrene <0.1 - 16.8 <LOD - 1.32
Naphthalene <0.1 - 121.85 2.4
Sum 0.15 - 0.19 <0.1 - 125.7
LOD - Limit of detection
647
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648 5. Risk Assessment

649 In general, a basic load of recycled rubber material with PAHs is observed. The first step in

650 determining the hazard risk arising from PAHs was to verify their emission. The

651 aforementioned studies showed that quantifiable amounts can be observed for migration via

652 dermal contact or inhalation, both of which are assumed to be primary routes of exposure.

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653 Oral intake is deemed a secondary risk. This is noted in the Danish Ministry’s health

654 assessment (Kim et al., 1997), in the Ecopneus (Fornai, 2016) / Waste and Chemicals study

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655 (Persici, Lupi, 2016) and in the results from the institute Mario Negri (Davoli, 2016; Davoli et

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656 al., 2016).

657 The Danish Ministry study investigates PAH emissions from playground installations made of

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658 old tires (sandpits) (Nilsson et al., 2005). The oral intake of contaminated sand was
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659 calculated for young children and toddlers according to the EU’s Technical Guidance

660 Document (TGD, 2003). It is assumed that a toddler is able to incorporate up to 10 grams of
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661 polluted sand per day, resulting in an insignificant potential long-term risk in the case of all

662 PAHs analysed. The study also addresses the leaching of PAHs into the soil and
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663 groundwater, deeming it of minor significance.

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664 On the basis of the data provided by Plesser and Lund (2004), Källqvist and Kopangen

665 (2005) assessed the environmental risk of chemical leaching via water from artificial turf
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666 fields. They followed standard procedures used in chemical risk assessment in the EU. Here,

667 the amount of chemicals leached into the water is modest and the environmental impact thus
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668 only local. PAHs are not mentioned as the substances contributing most to this impact.
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669 As for dermal exposure and inhalation, most studies concluded that the PAH level detected

670 falls below national limit values. There are, nevertheless, several studies dealing with the risk

671 of PAH emissions to human health and their hazardous effects.

672 Ruffino et al. (2013) calculated the cumulative carcinogenic risk on the basis of five artificial

673 turf fields in Italy and proved it to be lower than 1x10-6 which is the risk allowed for the

674 general population by the European Chemicals Agency ECHA in 2012. They conclude that

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675 the inhalation of atmosphere dusts and gases from vehicular traffic gives risk values of one

676 order of magnitude higher than those due to playing soccer on an artificial turf field.

677 Menichini et al. (2011) calculated a worst-case scenario based on the highest PAH

678 concentration of 0.4 ng/m3. Therefore, they obtained an excess lifetime cancer risk of 1x10-6

679 for an intense 30 year activity.

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680 The study carried out at Mario Negri (Davoli et al., 2016) investigated the risk to human

681 health posed by dermal contact and inhalation. The study employed a urinary 1-

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682 hydroxypyrene test, which is based on solid phase extraction and HPLC-MS/MS analysis

683 with an isotope dilution approach. It analysed the pyrene metabolite (hydroxypyrene), which

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684 can be found in urine, as a PAH marker. For this reason, it selected workers installing

685 artificial turf and people playing on it and monitored them for an extended period before and

686
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after installation / activity. Results are expressed as a relative increment versus the previous
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687 day. Taking personal behaviour - smoking, for example - into account, it was not possible to

688 establish any obvious correlation between installation of the field or playing on it and the PAH
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689 exposure of workers and players. Therefore, no risk could be concluded.

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690 Rooij and Jongeneelen (2010) also performed a real-life exposure study with athletes playing
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691 on synthetic turf fields, analysing their urine. They found minimally increased PAH levels and

692 concluded a negligible risk in the uptake of PAHs.

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693 Another study at Mario Negri (Davoli, 2016) calculated a worst-case scenario on the basis of

694 the results stemming from dermal and pulmonary surfactant migration tests and personal
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695 sampling. Children, adults, athletes and workers are considered here and the risk for cancer
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696 is calculated taking the daily dose, body weight and the life time of the person into account.

697 The authors found no risk to human health, with a hazard quotient of 10-10 – 10-7 and a

698 cancer risk at the same level.

699 The risk assessment in the Ecopneus study (Fornai, 2016) was performed both, at the Mario

700 Negri institute (see above) and by Waste and Chemicals (see below). Waste and Chemicals

701 (Persici, Lupi, 2016) calculated the carcinogenic risk due to inhalation of and dermal

702 exposure to benzo[a]pyrene. It concluded that the incremental carcinogenic risk during
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703 installation is significantly lower than the risk allowed for the general population (1 x 10-6).

704 The risk for players is even lower. The risk associated with dermal exposure was extremely

705 low for both players and workers. Although the risk of inhalation exposure is higher than that

706 of dermal contact, the incremental risk due to inhalation is lower than the recommended limit

707 value by one order of magnitude.

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708 The review of Johns (2008) on potential health risks associated with playing on synthetic turf

709 fields on Bainbridge Island ends up with a minimal human health risk though he found an

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710 excess cancer risk for inhalation at indoor fields for teenagers at long term exposure. Dermal

711 contact and incidential ingestion are several orders below the risk threshold for children and

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712 teenagers.

713 TRCs study (Vetrano, 2009) dealing with the air quality of artificial turf, considering the

714
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ageing effect, concluded that the data gathered do not support the need to conduct a human
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715 health risk assessment for the inhalation exposure route.

716 Concerning an ageing effect Marsili and coworkers reveal that the PAH release into the air
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717 by rubber crumb is not decreasing with time although the PAH concentration of the rubber
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718 crumb itself decreases over time (Marsili et al., 2014) (see also Chapter 3). However,
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719 calculating a worst case scenario for PAH inhalation all values are considered as acceptable

720 and the authors conclude that rubber crumb derived from recycled tires should be considered
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721 as non-hazardous special waste. Especially regarding high temperature exposure they found

722 that synthetic turf is not safe for public health.

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723 The review of the human health and ecological safety of exposure to recycled tire rubber
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724 found at playgrounds and synthetic turfs by Cardno ChemRisk (2013) concludes that

725 adverse health effects are not likely for children and athletes. This was received by taking

726 into account inhalation, ingestion and direct contact. Similarly, no adverse ecological or

727 environmental outcomes from leachates are likely.

728 The risk assessment focussed on inhalation exposure at indoor and outdoor artificial turf

729 fields of Ginsberg and Toal (2010) results in a cancer risk which is only slightly above de

730 minimis level for all scenarios, even at indoor fields for children, which had the highest
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731 exposure. The calculation was performed under conservative assumptions using the highest

732 results ever found in any sample and PAHs are minor contributors to cancer risk.

733 6. Conclusion

734 As most of the recycled rubber stems from shredded ELTs, it is obvious that PAHs can be

735 detected in consumer goods made from recycled rubber. This is because PAHs originate

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736 from highly aromatic oils and carbon black, which are constituents of tires.

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737 The PAHs from ELTs are released into the environment and reach humans via leaching (soil,

738 ground water, rivers), oral intake, dermal exposure and inhalation. The reviewed studies

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739 show that dermal contact or inhalation is assumed to be a primary route of exposure,

740 whereas oral intake and environmental pollution are regarded as secondary risks (Fornai,

741

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2016; Liu et al., 2000; Nilsson et al., 2005; Davoli, 2016, Davoli et al., 2016; Hofstra, 2007;
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742 Kolitzus, 2006; Persici, Lupi, 2016, Gomes et al. 2010; Lioy, Weisel, 2011; Johns, 2008;

743 Cardno ChemRisk, 2013).

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744 Nevertheless, the concentrations of toxic PAHs stemming from consumer goods made from

745 recycled rubber material that could potentially harm humans is of the same order as that of
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746 urban pollution. Even if products made from recycled rubber were not used, abrasion
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747 products and pollutants would still be found in the urban environment (Adachi, Tainosho,

748 2005). They originate from construction materials like asphalt, concrete and road paint,
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749 automobiles (tire dust, brake dust, body rust and tail pipe exhaust), industrial input (power

750
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stations, incineration plants, domestic fuel) or atmospheric deposition (Adachi, Tainosho,

751 2005; German Federal Environment Agency, 2012). In general, Hamilton and Harrison note
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752 a typical PAH level in the urban environment or near highways of 2 ng/m³ benzo[a]pyrene

753 and 10 ng/m³ fluoranthene (Hamilton, Harrison, 1991). In this context, the Act Global study

754 (Tilford, 2015) sums up a total PAH concentration that is not higher than other more

755 prevalent environmental sources, like asphalt driveways or smoked meat. The same is

756 concluded by Menichini et al. (2011), Ginsberg and Toal (2010) and Schilirò et al. (2013) who

757 found PAH concentration in air at artificial turf fields which is comparable with urban levels or

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758 even lower than those of urban sites. Applus’ oral presentation (Applus Medio Ambiente,

759 2017) also shows the results for PAH emissions to be similar to the emission generated by

760 motor vehicle traffic.

761 Besides, several risk assessment studies show that there is no serious risk potential arising

762 from consumer goods made from recycled rubber and obtain results which are considered as

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763 acceptable in case of the main risk, which is the inhalation of PAHs (e. g. Fornai, 2016;

764 Nilsson et al., 2005; Davoli, 2016; Davoli et al., 2016; Persici, Lupi, 2016; Vetrano, 2009;

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765 Ruffino et al., 2013; Marsili et al., 2014; Cardno ChemRisk, 2013; Ginsberg and Toal, 2010).

766 Furthermore, since the REACH regulation aimed at eliminating aromatic oils in the tire

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767 industry took effect in 2010 (Annex XVII, entry 50 of Reg. (EC) 1907/2006 REACH), an

768 evident reduction of PAHs in granules from recycled rubber from end-of-life tires has been

769
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observed (Fornai, 2016). REACH limits the overall PAH content to 10 mg/kg (German
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770 Federal Environment Agency, 2012). The study (Fornai, 2016) predicts a further progressive

771 reduction in the next few years with the gradual reduction in the number of “old” tires.
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772
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773 Funding
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774 This research did not receive any specific grant from funding agencies in the public,

775 commercial, or not-for-profit-sectors.

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776 7. Literature

777 Adachi, K., Tainosho, Y., 2005. Single particle characterization of size-fractionated road sediments.

778 Appl. Geochem. 20, 849-859.

779 Adams, C., Lamborn, M., Shuler, S., 1985. Asphalt-Rubber Binder Laboratory Performance. Report

780 FHWA/TX-8571, 347-1F, Texas Department of Highways and Public Transportation.

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781 Applus Medio Ambiente and Instituto de Biomecanica de Valencia, 2017. Study of the Incidence of

782 Recycled Rubber from Tires in Environment and Human Health. Oral presentation.

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783 www.isss-sportsurfacescience.org/downloads/documents/muw7lmt0wh_ibv.pdf of 23.05.2017.

784 Barrero-Moreno, J., Senaldi, C., Bianchi, I., Geiss, O., Tirendi, S., Folgado de Lucena, A., Barahona,

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785 F., Mainardi, G., Leva, P. Aguar-Fernandez, P., 2018. Migration of polycyclic aromatic

786 hydrocarbons (PAHs) from plastic and rubber articles. Joint Research Centre, Technical

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787 Report.
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788 Bartsch, N., Heidler, J., Vieth, B., Hutzler, C., Luch, A., 2016. Skin permeation of polycyclic aromatic

789 hydrocarbons: A solvent-based in vitro approach to assess dermal exposures against

790 benzo[a]pyrene and dibenzopyrenes. J. Occup. Environ. Hyg. 13, 969-979.

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791 Bundesamt für Gesundheit, BAG, Schweiz, 2006. Gesundheitsgefährdung durch Kunstrasen.
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792 Faktenblatt.

793 Cardno ChemRisk, 2013. Review of the Human Health & Ecological Safety of Exposure to Recycled
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794 Tire Rubber found at Playgrounds and Synthetic Turf Fields. Prepared for: Rubber

795 Manufacturers Association, Washington, DC. http://www.rma.org/download/scrap-

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796 tires/Environmental%20Issues/literature_review_0813.pdf.

797 Castellano, P., Proietto, A. R., Gordiani, A., Ferrante, R., Tranfo, G., Paci, E., Pigini, D., 2008.
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798 Assessment of exposure to chemical agents in infill material for artificial turf soccer pitches:
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799 Development and implementation of a survey protocol. Prev. Today 4, 25-42.

800 Celeiro, M., Lamas, J. P., Garcia-Jares, C., Dagnac, T., Ramos, L., Llompart, M., 2014. Investigation

801 of PAH and other hazardous contaminant occurance in recycled tyre rubber surfaces. Case-

802 study: Restaurant playground in an indoor shopping centre. Int. J. Environm. Analyt. Chem.

803 94, 1264-1271.

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804 CEN, CENELEC, 2018. CEN and CENELEC Revised Work Programme under M/556 as Regards

805 Compliance with Maximum Content Criteria of Polycyclic Aromatic Hydrocarbons in Rubber

806 and Plastic Components of Articles Placed on the Market.

807 Crone, T. J., Tolstoy, M., 2010. Magnitude of the 2010 Gulf of Mexico oil leak. Science 330, 634.

808 Davoli, E., 2016. Human Health and the Safety of Exposure to Recycled Tire Rubber Research Project

809 (Preliminary Report). Instituto di Ricerche Farmacologiche Mario Negri.

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810 Davoli, E., Bianchi, G., Re Depaolini, A., 2016. Exposure to Recycled Tire Rubber Human Health &

811 Safety. Instituto di Ricerche Farmacologiche Mario Negri.

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812 Dye, C., Bjerke, A., Schmidbauer, N., Mano, S., 2006. Measurements of air pollution in indoor artificial

813

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turf halls. Norwegian Pollution Control Authority/Norwegian Institute for Air Research, State

814 Programme for Pollution Monitoring. http://www.isss-

815 sportsurfacescience.org/downloads/documents/SI1HPZNZPS_NILUEngelsk.pdf.

816
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ECHA, 2018. European Chemicals Agency. Guideline on the Scope of Restriction Entry 50 of Annex
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817 XVII to REACH: Polycyclic Aromatic Hydrocarbons in Articles Supplied to the General Public.

818 ETRMA, 2015. European Tire & Rubber manufacturers’ association. End-of-life Tire Report.
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819 FIFA, UEFA, 2006. An Open Letter concerning the potential cancer risk from certain granulate infills

820 from artificial turf. FIFA and UEFA.

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821 Fornai, D., 2016. Characterization of Rubber Recycled from ELTs and Assessment of the Risks
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822 Associated with Dermal and Inhalation Exposure. Ecopneus.

823 Geiss, O., Senaldi, C., Bianchi, I., Lucena, A., Tirendi, S., Barrero-Moreno, J., 2018. A fast and
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824 selective method for the determination of 8 carcinogenic polycyclic aromatic hydrocarbons in

825 rubber and plastic materials. J. Chromatogr. A 1566, 13-22.

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826 German Federal Environment Agency, 2012. Polycyclic Aromatic Hydrocarbons. German Federal
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827 Environment Agency, Umweltbundesamt.

828 Ginsberg, G., Toal, B., 2010. Human Health Risk Assessment of Artificial Turf Fields Based Upon

829 Results from Five Fields in Conneticut. Conneticut Department of Public Health (CDPH).

830 http://www.ct.gov/deep/lib/deep/artificialturf/dph_artificial_turf_report.pdf.

831 Gomes, J., Mota, H., Bordado, J., Cadete, M., Sarmeto, G., Ribeiro, A., Fernandes, J., Pampulin, V.,

832 Custodio, M., Veloso, I., 2010. Toxicological assessment of coated versus uncoated rubber

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833 granulates obtained from used tires for use in sports facilities. J. Air Waste Manag. Assoc. 60,

834 741-746.

835 Grimmer, G., Jacob, J., Naujack, K.-W., 1997. Atmospheric emission of polycyclic aromatic

836 hydrocarbons in sampling areas of the German environmental specimen bank. Method for the

837 precise measurement of gaseous and particle-associated polycyclic aromatic hydrocarbons in

838 the sub-nanogram range using deuterated internal standards. Chemosphere 34, 2213-2226.

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839 Guiseppi-Elie, A., Thomas, K., Zambrana, J., Irvin-Barnwell, E., Ragin-Wilson, A., Hooker, E., 2017.

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Hofstra, U., 2007. Environmental and Health Risks of Rubber Infill – Rubber Crumb from Car Tires as
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853 synthetic turf fields in Bainbridge Island. Seattle, WA: Windward Environmental LLC.

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855 Norwegian Institute for Water Research, Oslo.

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856 Kalbe, U., Krüger, O., Wachtendorf, V., Berger, W., 2012. Umweltverträglichkeit von Kunststoff- und

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858 Sportwissenschaften.

859 Kim, P. M., DeBoni, U., Wells, P. G., 1997. Peroxidase-dependent bioactivation and oxidation of DNA

860 and protein in benzo[a]pyrene-initiated micronucleus formation. Free Radical Bio. Med. 23,

861 579-596.

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862 König, H., 2009. www.orgc.tu-graz.at/hoegroup/naturst/tox_von_KW.pdf (accessed 01 September

863 2009).

864 Kolitzus, H. J., 2006. Investigation and Assessment of Synthetic Sports Surfaces in Switzerland

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866 Koshla, N. P., Trogdon, J. T., 1990. Use of Ground Rubber in Asphalt Paving Mixtures. Technical

867 Report, Department of Civil Engineering, North Carolina State University, Raleigh.

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868 Lioy, P., Weisel, C., 2011. Crumb Infill and Turf Characterization for Trace Elements and Organic

869 Materials. Report prepared for NJDEP, Bureau of Recycling and Planning.

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870 Liu, H. S., Mead, J. L., Stager, R. G., 2000. Environmental effects of recycled rubber in light-fill

871

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applications. Rubber Chem. Technol. 73, 551-564.

872 Llompart, M., Sanchez-Praso, L., Lamas, J. P., Garcia-Jares, C., Roca, E., Dagnac, T., 2013.

873 Hazardous organic chemicals in rubber recycled tire playgrounds and pavers. Chemosphere

874 90, 423-431.

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875 Marsili, L., Coppola, D., Bianchi, N., Maltese, S., Bianchi, M., Fossi, M. C., 2014. Release of polycyclic

876 aromatic hydrocarbons and heavy metals from rubber crumb in synthetic turf fields:
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877 Preliminary hazard assessment for athletes. J. Environmental Analytical Toxicology 5.

878 Menichini, E., Abate, V., Attias, L., De Luca, S., di Domenico, A., Fochi, I., Forte, G., Iacovella, N.,
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879 Iamicelli, A. L., Izzo, P., Merli, F., Bocca, B., 2011. Artificial-turf playing fields: Contents of
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882 Moretto, R., 2007. Environmental and Health Assessment of the Use of Elastomer Granulates (Virgin

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884 Mota, H. I., Gomes, J. F. P., Bordado, J. C. M., Pereira, M. M., Felisberto, G. M. S., Ribeiro, A.,
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885 Pampulim, V. M., Veloso, I., Custódio, M. L. B., 2009. Coated rubber granulates obtained from

886 used tires for use in sport facilities: A toxicological assessment. Cienc. Tecnol. Mat. 21, 26-30.

887 Nehdi, M., Khan, A., 2001. Cementitious composites containing recycled tire rubber: An overview of

888 engineering properties and potential applications. Cement, Concrete, and Aggregates 23, 3-

889 10.

890 Nilsson, N. H., Feilberg, A., Pommer, K., 2005. Emissions and Evaluation of Health Effects of PAHs

891 and Aromatic Amines from Tires. Danish Ministry - Danish Technological Institute.

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892 Nilsson, N. H., Malmgren-Hansen, B., Thomsen, U. S., 2008. Mapping, Emissions and Environmental

893 and Health Assessment of Chemical Substances in Artificial Turf. Danish Ministry of

894 Environment.

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896 Analytical Methods (NMAM), Fourth Edition.

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898 Swedish Road Administration.

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900 metals and SVOCs in artificial turf field materials and fiber. Risk Anal. 34, 44-55.

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903 Waste and Chemicals prepared for Ecopneus.

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Plesser, T. S. W., Lind, O. J., 2004. Potential Health and Environmental Effects Linked to Artificial Turf
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905 Systems - Final Report. Norwegian Building Research Institute

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907 Stuttgart.

908 RIVM, 2017. National Institue for Public Health and the Environment. Annex XV Restriction Report –
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909 Proposal for a Restriction: PAHs in Synthetic Turf Infill Granules and Mulches.
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910 Rooij, J., Jongeneelen, F., 2010. Hydroxypyrene in urine of football players after playing on artificial

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912 Ruffino, B., Fiore, S., Zanetti, M. C., 2013. Environmental sanitary risk analysis procedure applied to

913 artificial turf sports fields. Environmental Sci Pollut Res 20, 4980-4992.
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914 Schilirò, T., Traversi, D., Degan, R., Pignata, C., Alessandria, L., Scozia, D., Bono, R., Gilli, G., 2013.
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915 Artificial turf football fields: Environmental and mutagenicity assessment. Arch Environ Contam

916 Tixicol 64, 1-11.

917 Simon, R., 2010. Review of the Impacts of Crumb Rubber in Artificial Turf Applications. University of

918 California, Berkeley and Laboratory for Manufacturing and Sustainability College of

919 Engineering prepared for Manufacturing Excellence.

920 Tilford, R. W., 2005. Act Global Crumb Rubber Safety Study. Prepared for Act Global.

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921 Twin City Corporation, 1990. Waste-Tires in Sub-Grade Bed, a Report to the Environmental Study of

922 the Use of Shredded Waste Tires for Roadway Sub-Grade Support. Waste Tire Management

923 Unit, Site Response Section, Groundwater and Solid Waste Division, Minnesota Control

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926 Prepared for New York City Department of Health and Mental Hygiene by TRC.

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927 Wang, H., Xu, H., Xuan, X., 2009. Review of Waste Tire Reuse & Recycling in China. Adv. Nat. Sci. 2,

928 31-39.

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929 Wengert, S., 2007. Gesundheitsgefährdung durch Schadstoffe im Kunstrasen?. Magglingen,

930

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Eidgenössisches Department des Innern, Bundesamt für Gesundheit 18

931 Zhang, J. J., Han, I.-K., Zhang, L., Crain, W., 2008. Hazardous chemicals in synthetic turf materials

932 and their bioaccessibility in digestive fluids. J. Expo. Sci. Environ. Epidemiol. 18, 600-607.

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List of figures and tables

Fig. 1: Bay structures of selected polycyclic aromatics based on NIOSH (NIOSH,

1998)

Table 1: IARC classification of PAHs

Table 2: PAH concentrations in rubber material intended for recycling purposes

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Table 3: PAH concentrations in leaching experiments

Table 4: Dermal uptake of PAHs

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Table 5: PAH concentrations in air and pulmonary surfactant

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Table 1: IARC calssification of PAHs

Number of
PAH Carcinogenicity Mutagenicity
rings
Naphthalene 2 3 -
Acenaphthene 2+ 3 ?
Fluorene 2+ 3 -
Phenanthrene 3 3 ?
Anthracene 3 3 -
Fluoranthene 3+ 3 +
Pyrene 4 3 +

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Cyclopenta[c,d ]pyrene 4+ 3 +
Benzo[a ]anthracene 4 2A +
Chrysene 4 3 +

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Triphenylene 4 3 +
Benzo[b ]fluoranthene 4+ 2B +
Benzo[j ]fluoranthene 4+ 2B +
Benzo[k ]fluoranthene 4+ 2B +

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Benzo[e ]pyrene 5 3 +
Benzo[a ]pyrene 5 2A +
Perylene 5 3 +
Indeno[1,2,3-c,d ]pyrene 5+ 2B +

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Dibenzo[a,h ]anthracene 6 2A +
Benzo[g,h,i ]perylene 6 3 +
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Anthanthrene 6 3 +
Coronene 6+ 3 +
Dibenzo[a,i ]pyrene 6 2B +
Dibenzo[a,e ]pyrene 6 2B +
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Dibenzo[a,h ]pyrene 6 2B +
Dibenzo[a,l ]pyrene 6 2B +
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Carcinogenicity (IARC classification)

Group 3 Components that are not classifiable to their carcinogenicity to humans
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Group 2B Components that are possibly carcinogenic to humans

Group 2A Components for which there is high evidence of carcinogenity in experimental animals

Mutagenicity
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- negativ
+ positiv
? questionable
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Table 2: PAH concentrations in rubber material intended for recycling purposes

Barrero-
Nilsson et al. Nilsson et al. Davoli et al. Marsili et al. Plesser, Lund Kalbe et al. Zhang et al. Mota et al. Gomes et al. Llompart et al. Celeiro et al. Lioy, Weisel Menichini
Editor of Study Tilford (2015) Davoli (2016) Fornai (2016) Hofstra (2007) Applus (2017) Moreno et al.
(2005) (2005) (2016) (2014) (2004) (2012) (2008) (2009) (2010) (2013) (2014) (2011) (2011)
(2018)
ELT as playing Tractor tyre ELT for ELT for shock- ELT for shock- ELT Experiments 70 % truck Synthetic Artificial turf, SBR granulates Artificial turf, Sport facilities Coated rubber Recycled tire Playground Recycled Unused infill, Different
tools, impact used as artificial turf absorbing absorbing granulates for on rubber infill tyres, 30 % turfs, rubber granulates bioaccessibilit granules and playgrounds, surfaces, rubber fiber, field infill rubber
Object of Analysis absorbing sandpit infill surfaces and surfaces and artificial turf of artificial turf car tyres, crumb, y by digestive uncoated raw pavers indoor granules, granules,
playground artificial turf artificial turf infill & literature artificial turf different age fluids material coated, artificial turf
study uncoated, tiles fields

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PAHs mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg ng/g mg/kg mg/kg mg/kg mg/kg mg/kg µg/g µg/g mg/kg mg/kg mg/kg
Acenaphthene < 1.42 352 - 10150 < 0.08 - 0.32 n. d. - 0.16 0.04 0.04 - <0.08 0.045 - 12.8 2.0 - 2.5 <0.01 - <0.03
Acenaphthylene < 1.42 < 0.08 - 1 0.27 0.27 - 0.38 0.037 - 13.4 0.79 - 1.6 <0.01 - 2.48
Anthracene < 1.42 7.6 - 283 < 0.08 - 0.76 n. d. - 0.17 0.13 0.13 - 0.19 0.14 - 4.72 8. 5 - 11 <0.01 - <0.02

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Benzo[a ]anthracene n. d. - 1.2 2.8 2.24 0.42 0.7 5.4 - 1613 < 0.08 - 1.9 n. d. - 1.26 1.31 0.82 - 1.31 0.12 - 2.02 12 - 30 0.05 - 0.32 <0.02 - <0.08 0.001 - 0.51
Benzo[a ]fluoranthene
Benzo[b ]fluoranthene 2.48 0.9 1150 - 15715 < 0.08 - 3.9 n. d. - 3.39 <0.08 <0.08 1.67 - 4.32 10 - 18 0.19 - 0.43 <0.09 - <0.30 0.001 - 2.30
0.3 - 3.0 (b+j+k) 8.0 (b+j+k) ([b ] + [k ])
Benzo[j ]fluoranthene

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0.9 0.3 0.06 - 0.15
Benzo[k ]fluoranthene 2.48 0.17 0.2 68 - 3616 < 0.08 - 1.5 n. d. - 7.29 <0.08 <0.08 0.27 - 1.69 n. d. - 2.2 0.05 - 0.24 <0.10 - <0.34
Benzo[g,h,i ]perylene 2.1 - 10.7 21.5 < 1.42 240 - 903 < 0.08 - 5.8 n. d. - 7.75 <0.08 <0.08 0.22 - 11.9 0.01 - 29.2
Benzo[a ]fluorene n. d.
Benzo[a ]pyrene 0.4 - 2.6 8.1 < 1.42 1.3 1.0 - 1.63 1-3 52 - 663 0.12 - 3.1 0.06 - 8.58 1.19 <0.08 - 1.19 0.42 - 4.66 6.4 - 17 0.95 - 1.49 <0.11 - <0.37 <0.001 - 10.7

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Benzo[e ]pyrene 0.9 - 9.6 10.3 2.86 3.2 1.08 - 1.60
Chrysene 1.4 - 12.3 4.1 6.62 0.74 1.0 244 - 3422 < 0.08 - 4.2 n. d. - 7.55 2.83 2.12 - 2.83 0.13 - 9.16 18 - 62 0.10 - 0.49 <0.08 - <0.27 0.01 - 5.01
Dibenzo[a,j ]anthracene n. d.

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Dibenzo[a,h ]anthracene n. d. - 1.3 < 1.42 0.17 0.1 73 - 573 < 0.08 - 0.44 n. d. - 3.52 <0.08 <0.08 0.97 - 0.97 0.08 - 0.17 <0.14 - <0.49 <0.001 - 0.36
Indeno[1,2,3-c,d ]pyrene 0.2 - 2.0 4.4 < 1.42 < 0.08 - 1.4 n. d. - 0.4 <0.08 <0.08 0.31 - 2.77 n .d - 5.8 0.001 - 1.08
Fluoranthene 2.1 - 16.0 37.4 10.8 710 - 3740 0.12 - 11 n. d. - 25.4 4.5 3.74 - 5.98 0.17 - 8.24 25 - 33 <0.01 - <0.03
Fluorene < 1.42 427 - 11026 < 0.08 - 0.68 n. d. - 0.77 0.12 0.12 - 0.18 0.056 - 47.7 8.5 - 11 <0.01 - <0.02

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Phenanthrene 4.0 38 - 1560 0.43 - 5.9 n. d. - 4.35 1.41 1.23 - 1.58 0.082 - 25.5 42 - 52 <0.01 - <0.02
Pyrene 11.4 - 34.0 75.6 17.5 1909 - 10281 0.16 - 37 n. d. - 13.5 14.42 13.95 - 21.10 0.77 - 29.5 34 - 51 <0.01 - <0.02 0.02 - 14.2
Naphthalene < 1.42 223 - 2040 0.19 - 0.72 n. d. - 0.86 0.16 0.13 - 0.35 0.06 - 24.2 0.43 - 0.52 <0.00 - 0.27
Sum 172.7 5 - 10 5 - 13 20 - 40 192 8021 - 58211 1 - 76 1 - 77 0.4 - 38.15 26.77 23.15 - 34.17 1.25 - 178 170 - 295 2.58 - 4.66 0.04 - 45.1

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n. d. - not detected

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Table 3: PAH concentrations in leaching experiments
Mota et al. Mota et al. Gomes et al. Plesser, Lund Kalbe et al. Celeiro et al.
Editor of Study Kolitzus (2006) Moretto (2007)
(2009) (2009) (2010) (2004) (2012) (2014)

Sports Uncoated Coated rubber Coated rubber Artificial turf, Complete Artificial turf, Playground
surfaces, rubber granules granules and granulates, artificial turf lysimeter surfaces,
Object of Analysis lysimeter tests granules uncoated raw leaching in system, indoor
material deionised leaching
water
PAHs µg/L mg/kg mg/kg mg/kg µg/L µg/L µg/L ng/mL
Acenaphthene <0.003 <0.001 <0.001 - <0.003 0.03 15
Acenaphthylene <0.003 <0.001 <0.001 - <0.003 0.27 26

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Anthracene <0.003 <0.001 <0.001 - <0.003 0.03 211
Benzo[a ]anthracene <0.003 <0.001 <0.001 - <0.003 <0.01 681
Benzo[a ]fluoranthene

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Benzo[b ]fluoranthene <0.003 <0.001 <0.001 - <0.003
Benzo[j ]fluoranthene
Benzo[k ]fluoranthene <0.003 <0.001 <0.001 - <0.003
Benzo[g,h,i ]perylene <0.003 <0.001 <0.001 - <0.003

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Benzo[a ]fluorene
Benzo[a ]pyrene <0.003 <0.001 <0.001 - <0.003
Benzo[e ]pyrene
Chrysene <0.003 <0.001 <0.001 - <0.003

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Dibenzo[a,j ]anthracene
Dibenzo[a,h ]anthracene <0.003 <0.001 <0.001 - <0.003
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Indeno[1,2,3-c,d ]pyrene <0.003 <0.001 <0.001 - <0.003
Fluoranthene <0.003 <0.001 <0.001 - <0.003 0.06 243
Fluorene <0.003 <0.001 <0.001 - <0.003 0.04 111
Phenanthrene <0.003 <0.001 <0.001 - <0.003 0.16 709
Pyrene <0.003 <0.001 <0.001 - <0.003 0.13 222
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Naphthalene <0.005 <0.001 <0.001 - <0.005 0.15 5.2

Sum 0.1 - 0.3 <0.05 <0.016 <0.016 - <0.050 0.87 0.5 - 6 < 0.1 2223
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Table 4: Dermal uptake of PAHs

Nilsson et al. Davoli et al. Persici, Lupi Lioy, Weisel
Editor of Study Fornai (2016) Hofstra (2007)
(2005) (2016) (2016) (2011)

ELT as playing ELT for artificial ELT granulates, ELT for artificial Rubber infill of Unused infill,
tools, artificial turf, release in sweat migration turf, pads for artificial turf, fiber, field
Object of Analysis sweat artificial sweat test dermal uptake estimated infill, sweat
uptake from biofluid
migration data extraction

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PAHs ng/cm² % % ng/cm² ng/kg bw mg/kg
Acenaphthene <0.00 - <0.11
Acenaphthylene <0.01 - <0.17

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Anthracene <0.00 - <0.08
Benzo[a ]anthracene 0.006 - 0.095 <0.01 - <0.32
Benzo[a ]fluoranthene

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Benzo[b ]fluoranthene <0.04 - <1.23
0.009 - 0.016
Benzo[j ]fluoranthene
Benzo[k ]fluoranthene 0.005 - 0.008 <0.04 - <1.38
Benzo[g,h,i ]perylene

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Benzo[a ]fluorene
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Benzo[a ]pyrene 0.001 - 0.002 0 - 0.19 <0.05 - <1.46
Benzo[e ]pyrene 0.001 - 0.002
Chrysene 0.005 - 0.0155 <0.03 - <1.07
Dibenzo[a,j ]anthracene
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Dibenzo[a,h ]anthracene <0.06 - <1.97

Indeno[1,2,3-c,d ]pyrene
Fluoranthene 0.029 - 0.277 <0.00 - <0.12
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Fluorene <0.00 - <0.07

Phenanthrene <0.00 - <0.10
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Pyrene 0.032 - 0.487 <0.00 - <0.10

Naphthalene <0.00 - <0.03
Sum 0.002 - 0.006 0.12
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Table 5: PAH concentrations in air and pulmonary surfactant

Dye et al. Dye et al. Ginsberg, Toal Ginsberg, Toal Marsili et al. Lioy, Weisel Davoli et al. Persici, Lupi Castellano et Schiliro et al. Nordgren
Editor of Study Applus (2017) Fornai (2016) Fornai (2016) Fornai (2016)
(2006) (2006) (2010) (2010) (2014) (2011) (2016) (2016) al. (2008) (2013) (2009)

Air pollution of Air pollution of Indoor artificial Outdoor ELT, 70 % truck Synthetic turfs, Unused infill, ELT for artificial ELT granulates, ELT granulates, ELT granulates, ELT for artificial Exposure, Comparison Rubberized
indoor artificial indoor artificial turf fields artificial turf tyres, 30 % car evaporates of fiber, field infill, turf, pulmonary artificial turf artificial turf artificial turf turf, breathing artificial turf, artificial turf asphalt

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Object of Analysis turf halls, turf halls, gas fields tyres, PUF-filter rubber crumb of lung biofluid surfactant infill, pulmonary infill, air quality infill, air quality zone workers environmental and urban area,
airborne dust phase different age extraction migration surfactant installing playing and personal filter sampling,
compounds sampling seasonal
PAHs ng/m³ ng/m³ µg/m³ µg/m³ ng/m³ ng/g mg/kg % % ng/m³ ng/m³ n g/m³ ng/m³ ng/m³ µg/m³

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Acenaphthene 0.02 - 0.06 4.77 - 14.2 0.0174 0.03 - 0.32 <0.00 - <0.05 <0.1
Acenaphthylene 0.04 - 0.19 6.24 - 78.1 0.0068 0.0066 0.03 - 0.21 <0.00 - <0.09 <0.1
Anthracene 0.04 - 0.05 0.77 - 1.86 0.02 - 0.46 <0.00 - <0.04 <0.1 <LOD
Benzo[a ]anthracene 0.14 - 0.56 0.05 - 0.15 0.00011 < 0.02 0.14 - 0.49 <0.01 - <0.16 0.06 - 0.11 0.3 - 1.7 0.3 - 15 <0.1 <LOD - 2.13

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Benzo[a ]fluoranthene 0.23 - 0.44 0.01 - 0.03
Benzo[b ]fluoranthene 0.00021 < 0.09 <0.03 - <0.62 0.05 - 1.25 0.1 - 10 <0.1 <LOD - 4.00
0.06 - 0.12 ([b ] + [k ])
Benzo[j ]fluoranthene 0.72 - 2.24 0.01 - 0.04 0.02 - 0.5 0.1 - 4
<0.1
Benzo[k ]fluoranthene 0.00008 < 0.37 <0.03 - <0.69 0.03 - 0.6 0.1 - 3.5

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Benzo[g,h,i ]perylene 0.69 - 1.11 <0.01 - <0.02 0.00014 < 0.55 0.42 - 1.28 <0.1 <LOD - 1.31
Benzo[a]fluorene 0.02 - 0.06 0.05 - 0.12

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Benzo[a ]pyrene 0.38 - 1.15 <0.01 - 0.02 0.00019 < 0.55 0.11 - 0.89 <0.04 - <0.74 0.05 - 0.09 0.18 - 0.85 0.1 - 14 < 0.05 - 26.72 <0.1 <LOD - 1.75 0.03
Benzo[e ]pyrene 0.39 - 0.78 <0.01 - 0.03 0.00026 0.04 - 0.055 0.2 - 0.9 0.1 - 7
Chrysene 0.00034 < 0.02 1.06 - 5.82 <0.02 - <0.54 0.3 0.25 - 1.4 0.2 - 26 <0.1 <LOD - 2.24
Dibenzo[a,j ]anthracene

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Dibenzo[a,h ]anthracene 0.06 - 0.13 <0.01 - <0.02 < 0.37 <0.04 - <0.98 0.02 - 0.7 0.1 - 1 <0.1 <LOD - 0.25
Indeno[1,2,3-c,d ]pyrene 0.42 - 1.11 <0.01 - <0.02 < 0.92 <0.1 <LOD - 1.03
Fluoranthene 0.48 - 0.67 1.66 - 2.81 0.0056 0.0068 0.1 - 1.14 <0.00 - <0.06 <0.1 - 11,57 <LOD - 0.94

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Fluorene 0.04 - 0.1 7.86 - 19.2 0.054 0.05 - 0.92 <0.00 - <0.03 <0.1
Phenanthrene 0.33 - 0.52 14.0 - 25.0 0.032 0.64 - 6.93 <0.00 - <0.05 <0.1 - 16.44 <LOD - 0.24
Pyrene 0.64 - 1.17 1.8 - 3.54 0.0118 0.0069 0.3 - 4.17 <0.00 - <0.05 <0.1 - 16.8 <LOD - 1.32

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Naphthalene 0.04 - 0.17 11.1 - 20.9 0.113 0.1 - 0.33 <0.00 - <0.02 <0.1 - 121.85 2.4
Sum 4.89 - 10.84 120.64 - 363.74 0.15 - 0.19 <0.1 - 125.7
LOD - Limit of detection
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Highlights

Most recycled rubber is stemming from end-of-life tires.

Around half of the recycled rubber is used to produce artificial turf and similar.

PAHs can be detected in consumer goods made from recycled rubber.

Dermal contact or inhalation is the primary route of PAH exposure.

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Reviewed risk assessment studies show no serious risk potential.

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