Refinement of a microfurnace pyrolysis-GC-MS method for quantification of tire and road wear particles (TRWP) in sediment and solid matrices.

Tire and road wear particles (TRWP) are produced by abrasion at the interface of the pavement and tread surface and contain tread rubber with road mineral encrustations. Quantitative thermoanalytical methods capable of estimating TRWP concentrations are needed to assess the prevalence and environmental fate of these particles. However, the presence of complex organic constituents in sediment and other environmental samples presents a challenge to the reliable determination of TRWP concentrations using current pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) methodologies. We are unaware of a published study evaluating pretreatment and other method refinements for microfurnace Py-GC-MS analysis of the elastomeric polymers in TRWP including polymer-specific deuterated internal standards as specified in ISO Technical Specification (ISO/TS) 20593:2017 and ISO/TS 21396:2017. Thus, potential method refinements were evaluated for microfurnace Py-GC-MS, including chromatography parameter modification, chemical pretreatment, and thermal desorption for cryogenically-milled tire tread (CMTT) samples in an artificial sediment matrix and a sediment field sample. The tire tread dimer markers used for quantification were 4-vinylcyclohexene (4-VCH), a marker for styrene-butadiene rubber (SBR) and butadiene rubber (BR), 4-phenylcyclohexene (4-PCH), a marker for SBR, and dipentene (DP), a marker for natural rubber (NR) or isoprene. The resultant modifications included optimization of GC temperature and mass analyzer settings, along with sample pretreatment with potassium hydroxide (KOH) and thermal desorption. Peak resolution was improved while minimizing matrix interferences with overall accuracy and precision consistent with those typically observed in environmental sample analysis. The initial method detection limit for an artificial sediment matrix was approximately 180 mg/kg for a 10 mg sediment sample. A sediment and a retained suspended solids sample were also analyzed to illustrate the applicability of microfurnace Py-GC-MS towards complex environmental sample analysis. These refinements should help encourage the adoption of pyrolysis techniques for mass-based measurements of TRWP in environmental samples both near and distant from roadways.