Recycled tire rubber materials in the spotlight. Determination of hazardous and lethal substances.

One way of recycling end-of-life tires is by shredding them to obtain crumb rubber, a microplastic material (<0.5 mm), used as infill in artificial turf sports fields or as playground flooring. There is emerging concern about the health and environmental consequences that this type of surfaces can cause. This research aims to develop an analytical methodology able to determine 11 compounds of environmental and health concern, including antiozonants such as N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine (6PPD) or N, N´-diphenyl-1,4-phenylenediamine (DPPD), and vulcanization and crosslinking agents, such as N-cyclohexylbenzothiazole-2-sulfenamide (CBS), 1,3-di-o-tolylguanidine (DTG) or hexamethoxymethylmelamine (HMMM) from tire rubber. Ultrasound assisted extraction followed by liquid chromatography coupled to tandem mass spectrometry (UAE-LC-MS/MS) is validated demonstrating suitability. The methodology is applied to monitor the target compounds in forty real crumb rubber samples of different origin including, football pitches, outdoor and indoor playgrounds, urban pavements, commercial samples, and tires. Several alternative infill materials, such as sand, cork granulates, thermoplastic elastomers and coconut fibres, are also collected and analysed. All the target analytes are identified and quantified in the crumb rubber samples. The antiozonant 6PPD is present at the highest concentrations up to 0.2 % in new synthetic fields. The tire rubber-derived chemical 6PPD-quinone (2-((4-methylpentan-2-yl)amino)-5-(phenylamino)cyclohexa-2,5-diene-1,4-dione), recently linked to acute mortality in salmons, is found in all types of crumb rubber samples attaining concentrations up to 40 μg g-1 in football pitches. The crosslinking agent HMMM is detected in most of the playing surfaces, at concentrations up to 36 μg g-1 . The tested infill alternatives are free of most of the target compounds. To the best of our knowledge, this study is the largest study considering the target compounds in tire rubber particles and the first to focus on these compounds in playgrounds including the analysis of HMMM, 6PPD-quinone and DTG in crumb rubber used as an infill material.