Separation and quantification of tire and road wear particles in road dust samples: Bonded-sulfur as a novel marker.

Tire road wear particles (TRWPs) are a large source of microplastics in the environment, while the quantification of TRWPs is still challenging due to the complex interferences and the uncertainties and inconsistencies among different methods. This study developed a TRWPs quantification method using optimized pretreatments and bonded-sulfur as marker. Road dust samples (n = 48) were collected, pretreatments including density separation, digestion and extraction were optimized to remove interferences of the bonded-sulfur (minerals, sulfur-containing proteins, hydrosoluble/hydrophobic sulfur-containing substances). Presence of TRWPs in the samples was confirmed by microscopy and scanning electron microscopyenergy dispersive spectrometry. Bonded-sulfur in the samples were quantified by inductively coupled plasmamass spectrometry (ICPMS). Additionally, bonded-sulfur in tire wear particles (TWPs) abraded from tires of top 10 best-selling brands were measured to calculate conversion factor (1.1 ×104 µg/g) for the quantification of TRWPs in real samples. TRWPs contents were 5.40 × 104 µg/g11.02 × 104 µg/g and 2.36 × 104 µg/g5.30 × 104 µg/g in samples from heavy and light traffic roads, respectively. The method provided better recoveries (88-107%, n = 18) and repeatability (RSD=2.0-7.9%, n = 3) compared to methods using rubber, benzothiazole and organic zinc as markers. Furthermore, stability of the bonded-sulfur was validated by Raman and ICPMS. Thus, this accurate and stable quantification method could promote research on TRWPs.

Environmental profiles, hazard identification, and toxicological hallmarks of emerging tire rubber-related contaminants 6PPD and 6PPD-quinone.

N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD) is commonly used in rubber compounds as antioxidants to protect against degradation from heat, oxygen, and ozone exposure. This practice extends the lifespan of rubber products, including tires, by preventing cracking, aging, and deterioration. However, the environmental consequences of waste generated during rubber product use, particularly the formation of 6PPD-quinone (6PPD-Q) through the reaction of 6PPD with ozone, have raised significant concerns due to their detrimental effects on ecosystems. Extensive research has revealed the widespread occurrence of 6PPD and its derivate 6PPD-Q in various environmental compartments, including air, water, and soil. The emerging substance of 6PPD-Q has been shown to pose acute mortality and long-term hazards to aquatic and terrestrial organisms at concentrations below environmentally relevant levels. Studies have demonstrated toxic effects of 6PPD-Q on a range of organisms, including zebrafish, nematodes, and mammals. These effects include neurobehavioral changes, reproductive dysfunction, and digestive damage through various exposure pathways. Mechanistic insights suggest that mitochondrial stress, DNA adduct formation, and disruption of lipid metabolism contribute to the toxicity induced by 6PPD-Q. Recent findings of 6PPD-Q in human samples, such as blood, urine, and cerebrospinal fluid, underscore the importance of further research on the public health and toxicological implications of these compounds. The distribution, fate, biological effects, and underlying mechanisms of 6PPD-Q in the environment highlight the urgent need for additional research to understand and address the environmental and health impacts of these compounds.

Non-targeted screening and photolysis transformation of tire-related compounds in roadway runoff.

Roadway runoff serves as a crucial pathway for transporting contaminants of emerging concern (CECs) from urban environments to receiving water bodies. Tire-related compounds originating from tire wear particles (TWPs) have been frequently detected, posing a potential ecological threat. Yet, the photolysis of tire-related compounds within roadway runoff remains inadequately acknowledged. Addressing this deficit, our study utilized high-resolution mass spectrometry (HRMS) to characterize the chemical profile of roadway runoff across eight strategically selected sites in Guangzhou, China. 219 chemicals were identified or detected within different confidence levels. Among them, 29 tire-related contaminants were validated with reference standards, including hexa(methoxymethyl)melamine (HMMM), 1,3-diphenylguanidine (DPG), dicyclohexylurea (DCU), and N-cyclohexyl-2-benzothiazol-amine (DCMA). HMMM exhibited with the abundance ranging from 2.30 × 104-3.10 × 106, followed by DPG, 1.69 × 104-8.34 × 106. Runoff sample were exposed to irradiation of 500 W mercury lamp for photodegradation experiment. Photolysis results indicated that tire-related compounds with a low photolysis rate, notably DCU, DCMA, and DPG, are more likely to persist within the runoff. The photolytic rates were significantly correlated with the spatial distribution patterns of these contaminants. Our findings underscore TWPs as a significant source of pollution in water bodies, emphasizing the need for enhanced environmental monitoring and assessment strategies.

Abiotic oxidative transformation of 6-PPD and 6-PPD quinone from tires and occurrence of their products in snow from urban roads and in municipal wastewater.

The antiozonant N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (6-PPD) is added to tires to increase their lifetime and is emitted with tire and road wear particles into the environment. Recently, one of its transformation products (TPs), 6-PPD quinone (6-PPDQ), has gained attention due to its toxicity towards coho salmon. In this study, the abiotic oxidative transformation of 6-PPD is investigated by a series of ozonation experiments in the lab followed by analysis of TPs using liquid chromatography-high resolution-mass spectrometry (LC-HRMS). A total of 38 TPs were detected and tentatively identified, which were formed either directly from 6-PPD or via 6-PPDQ as intermediate. A suspect screening by LC-HRMS showed 32 of these TPs to occur in snow collected from urban roads as surrogate of road-runoff, where 6-PPDQ, 4-aminodiphenylamine (4-ADPA), TP 213, and TP 249 were the most prominent besides 6-PPD. More than 90% of the total load of 6-PPD and its TPs was found in the particulate fraction of snow. Thus, retaining the particulate fraction of road runoff before its discharge into surface water would substantially reduce the emission of 6-PPD and many of its TPs. Some TPs prevailed in the water phase of the snow due to their higher polarity. A total of 13 TPs were detected by suspect screening in the dissolved phase of a wastewater treatment plant (WWTP) influent. Their total load was markedly enhanced during a day of snowmelt (approx. 1100 g/d) and rainfall (approx. 2000 g/d) compared to dry weather (approx. 190 g/d). 6-PPD and 6-PPDQ contributed to less than 1% to this total load in the water phase (estimated concentrations of max 0.1 µg/L). The elimination of the estimated total loads of 6-PPD related TPs from the water phase in WWTP ranged from 22 to 67% depending on weather conditions. Eventually TP 249, 4-ADPA and TP 259_2 dominated in WWTP effluent (estimated concentration from 0.5 up to 2 µg/L). Thus TP 249 and TP 259_2 are, likely, the most specific and stable TPs of 6-PPD to be determined in the environment.

Microplastics (MPs) in urban roadside snowbanks: Quantities, size fractions and dynamics of release.

The microplastics (MP) pollution has been receiving high attention in recent years, because of the massive amounts of plastics it contributes to the environment. Tyre wear and road wear particles (TWP and RWPs) were identified as major sources of MPs, but the observed data on these particles in urban snow deposits and snowmelt is scarce. To contribute to remediation of this situation, a study designed to quantify TWPs and RWPs in urban roadside snowbanks, and assess the MP occurrence in three size fractions, was conducted in the Luleå and Umeå municipalities in Northern Sweden. TWPs and RWPs were determined in three size fractions: 50-100 µm, 100-300 µm, and ≥300 µm, and their release from melting snow was investigated in the laboratory under controlled conditions. Among the MPs identified in snow and the associated snowmelt samples, a majority consisted of both types of particles (T&RWPs) with an average of 20,000 ± 48,000 number/L, whereas other MPs (fibres, fragments, flakes, and films of plastic) were much less plentiful with an average concentration of 24 ± 16 number/L. The largest proportion of T&RWPs was detected in the size fraction 50-100 µm (around 80%), and the smallest proportion was in the fraction ≥300 µm (about 2%). Of the T&RWPs, about 85% were black bitumen particles (RWPs), composed of bitumen, mineral material and polymer modifiers, and 15% were tyre wear particles (TWPs) composed of rubber. The laboratory snow melting experiments demonstrated that urban snow stored MPs, which were eventually released during snowmelt. The ultimate fate of released MPs would depend on snowmelt drainage; it may either drain away from the road pavement and infiltrate into the ground, or enter the road gutter and be conveyed to storm sewers discharging to the receiving waters.

Effect of treadwear grade on the generation of tire PM emissions in laboratory and real-world driving conditions.

Tires generally wear out due to the friction between the tire and the road surface. Minimizing tire wear could reduce the non-exhaust particulate matter (PM) emissions from tires. Typically, tire treadwear grade can be used as an indicator of PM emissions from tires. Tires that wear out quickly will produce higher PM emissions than more durable tires. In this study, the effect of treadwear grade on the generation of tire PM emissions was investigated through laboratory and on-road driving measurements. In the laboratory measurements, a tire wear simulator installed in an enclosed chamber was used to eliminate artifacts caused by interfering particles during the generation and measurement of tire wear particles. For realistic on-road driving measurements, a mobile sampling vehicle was employed to sample road dust. The road dust was chemically analyzed using pyrolysis gas chromatography-mass spectrometry (GC-MS) to characterize the tire-road wear particles. Both measurements showed that the higher treadwear grade generated lower tire PM emissions due to the high strength of the rubber, except for the UTQG 700 tire. The UTQG 700 tire, which had the highest treadwear grade, produced higher PM emissions than the UTQG 350 and 500 tires because it readily formed the fine particles due to lamellar peeling rather than tearing or curling of tire treads. Notably, tire nanoparticles were observed in laboratory measurements due to the volatilization and nucleation of the sulphur (S) and zinc (Zn) compounds in the tire tread due to the frictional heat between the tire and paved road surface.