Published research

• Improved method for tire and road wear particle mass concentration measurement
• Microfurnace pyrolysis evaluation included artificial and environmental sediment
• Enhancements included thermal desorption and chemical pretreatment
• Matrix effects successfully mitigated observed in complex environmental 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.

Tire and road wear particles (TRWP) account for an important part of the polymer particles released into the environment. There are scientific knowledge gaps as to the potential bioaccessibility of chemicals associated with TRWP to aquatic organisms. This study investigated the solubilization and bioaccessibility of seven of the most widely used tire-associated organic chemicals and four of their degradation products from cryogenically milled tire tread (CMTT) into fish digestive fluids using an in vitro digestion model based on Oncorhynchus mykiss. Our results showed that 0.06–44.1% of the selected compounds were rapidly solubilized into simulated gastric and intestinal fluids within a typical gut transit time for fish (3 h in gastric and 24 h in intestinal fluids). The environmentally realistic scenario of coingestion of CMTT and fish prey was explored using ground Gammarus pulex. Coingestion caused compound-specific changes in solubilization, either increasing or decreasing the compounds’ bioaccessibility in simulated gut fluids compared to CMTT alone. Our results emphasize that tire-associated compounds become accessible in a digestive milieu and should be studied further with respect to their bioaccumulation and toxicological effects upon passage of intestinal epithelial cells.

• Tire tread and TRWP quantification in the environment is challenging
• Reliable quantitative methods are critical for environmental risk assessment
• Utility and transferability of an established Py-GC-MS method is evaluated
• Three pyrolysis technologies: Curie point, microfurnace and resistive were compared
• Curie point and microfurnace are suitable for quantitative Py-GC-MS of tire tread

Transferable and reliable methods for tire and road wear particles (TRWP) environmental mass quantification are needed for environmental risk assessment. The comparative performance of three pyrolysis-gas chromatography-mass spectroscopy (Py-GC-MS) technologies with internal standard was assessed for pure polymers and three cryomilled tire tread (CMTT) samples with or without a standard artificial sediment matrix following ISO Technical Specification (TS) 21396:2017. The pyrolyzer technologies included Curie Point (CP; ferromagnetic induction), microfurnace (MF; ceramic heater), and resistive (R; platinum filament). The dimeric pyrolysis markers for tire tread polymer included: 4-vinylcyclohexene (4-VCH), a marker for styrene-butadiene rubber (SBR) and butadiene rubber (BR); dipentene (DP), a marker for natural rubber (NR) or isoprene; and 4-phenylcyclohexene (4-PCH), a marker specific to SBR not considered in the ISO TS. Comparing the performance of three pyrolysis technologies for quantifying six samples (two tread amount levels for three formulations), the average relative standard deviation in pure-CMTT measured in triplicate using 4-VCH and DP was 6.8% (MF), 26% (CP), and 60% (R) without matrix (100 or 1000 ug CMTT), and 19% (MF), 26% (CP) and 105% (R) with matrix (0.5% or 5% CMTT). The recovery of CMTT was greater than 50% for all MF and CP samples with good separation at the two amount levels. An increased frequency of CMTT recoveries >150% for MF and CP artificial sediment analysis suggests future consideration of pre-treatment (e.g., thermal desorption or labile organic digestion) in addition to the previously identified importance of polymer microstructure. The magnitude of variability observed with the resistive instrument indicates that further method development may be necessary to optimize thermal transfer. Overall, Curie point and microfurnace were found to be excellent candidate pyrolysis technologies for ongoing quantitative Py-GC-MS of TRWP in environmental method development, capable of a low likelihood of underestimating polymer mass with reasonable replicate precision.

• Knowledge on tire aging is partially applicable to tire and road wear particles (TRWPs)
• Suitability of various TRWP test materials for aging studies is evaluated
• Aging processes have a joint impact on TRWP properties and composition
• Quantitative understanding of TRWP aging is lacking
• Future research needs on TRWP aging are identified

The environmental fate of tire and road wear particles (TRWPs) receives increasing attention due to the per capita emission volumes of 0.2–5.5 kg/(cap year) and recent reports on the environmental hazard of TRWP constituents. It is expected that aging impacts TRWPs fate in the environment but detailed knowledge is quite limited, yet. Making use of information on tire aging, the available knowledge on environmental aging processes such as thermooxidation, photooxidation, ozonolysis, shear stress, biodegradation and leaching is reviewed here. Experimental techniques to simulate aging are addressed as are analytical techniques to determine aging induced changes of TRWPs, covering physical and chemical properties. The suitability of various tire wear test materials is discussed. Findings and methods from tire aging can be partially applied to study aging of TRWPs in the environment. There is a complex interplay between aging processes in the environment that needs to be considered in future aging studies. In addition to existing basic qualitative understanding of the aging processes, quantitative understanding of TRWP aging is largely lacking. Aging in the environment needs to consider the TRWPs as well as chemicals released. Next steps for filling the gaps in knowledge on aging of TRWPs in the environment are elaborated.

Tire and road wear particles (TRWP) have been shown to represent a large part of anthropogenic particles released into the environment. Nevertheless, the potential ecological risk of TRWP in the different environmental compartments and their potential toxic impacts on terrestrial and aquatic organisms remain largely under investigated. Several heavy metals compose TRWP, including Zn, which is used as a catalyst during the vulcanization process of rubber. This study investigated the solubilization potential of metals from cryogenically milled tire tread (CMTT) and TRWP in simulated gastric fluids (SFGASTRIC) and simulated intestinal fluids (SFINTESTINAL) designed to mimic rainbow trout (Oncorhynchus mykiss) gastrointestinal conditions. Our results indicate that the solubilization of heavy metals was greatly enhanced by gastrointestinal fluids compared to that by mineral water. After a 26 h in vitro digestion, 9.6 and 23.0% of total Zn content of CMTT and TRWP, respectively, were solubilized into the simulated gastrointestinal fluids. Coingestion of tire particles (performed with CMTT only) and surrogate prey items (Gammarus pulex) demonstrated that the animal organic matter reduced the amount of bioavailable Zn solubilized from CMTT. Contrastingly, in the coingestion scenario with vegetal organic matter (Lemna minor), high quantities of Zn were solubilized from L. minor and cumulated with Zn solubilized from CMTT.

Tire and road wear particles (TRWPs) are generated from friction between tires and the road and contain polymer tread with pavement encrustations. Single particle analysis (SPA) of tire source contribution in environmental samples has been limited by interferences in common spectroscopic polymer techniques. This study extends a density separation and chemical mapping protocol for road simulator generated TRWPs toward the identification and characterization of individual TRWPs in more complex road dust, road-dust-spiked artificial sediment, tunnel dust, and environmental settling pond sediment samples. TRWPs were identified by a combination of physical (elongated/round shape with variable amounts of mineral encrustation) and elemental surface characteristics [co-localization of (S + Zn/Na) ± (Si, K, Mg, Ca, and Al)]. Organic surface markers (C7H7+), overlapping FTIR spectra with tread reference material, and resistance to heat-induced deformation were selectively used to confirm particle identification. The TRWP size displayed an increasing average trend of 54, 158, and 267 μm by number (94, 224, and 506 μm by volume) in tunnel dust, road dust, and environmental sediment, respectively. TRWP size distributions within road dust 10× diluted with artificial sediment agreed with those of pure road dust. Our SPA methodologies determined the size distribution of TRWPs in environmental sample types with increasing sample complexity.