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Development and validation of an online SPE-HPLC-MS/MS for tire-derived pollutants of environmental concern (6PPD and 6PPD-Q): Detection and rainfall-driven dynamics in an urban river-estuary continuum
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Researchers developed and validated a sensitive chemical analysis method to detect 6PPD-Quinone — a toxic tire rubber chemical that is lethal to coho salmon — in surface water at trace concentrations, and applied it to monitor an urban Florida river over two years. The compound was found in all 40 water samples collected, with concentrations spiking strongly after rainfall events as tire wear particles washed off roads. This method fills an important monitoring gap, since 6PPD-Q is increasingly recognized as a major environmental hazard from road runoff and no prior data existed for Florida waterways.
Microplastics such as tire wear particles and their associated tire-derived chemicals are emerging contaminants in urban surface waters. N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD) and its toxic transformation product 6PPD-Quinone (6PPD-Q) are widely detected in roadway runoff but remain difficult to quantify at environmentally relevant concentrations due to their low abundance, matrix interferences, and susceptibility to degradation during sample processing. Here, we developed and validated an online solid-phase extraction high-performance liquid chromatography tandem mass spectrometry (SPE-HPLC-MS/MS) method for sensitive and robust determination of 6PPD and 6PPD-Q in surface waters. The method provided low detection limits and strong resistance to matrix effects, enabling routine monitoring at trace levels. The method was applied to surface waters from the lower Hillsborough River (Florida, USA) collected across ten sampling events between 2023 and 2024. 6PPD-Q was detected in all samples (0.29-11.60 ng/L; mean 1.82 ± 2.02 ng/L), whereas 6PPD occurred less frequently (ND-1.62 ng L; mean 0.20 ± 0.39 ng/L). Concentrations of 6PPD and 6PPD-Q were strongly correlated (r = 0.66, p < 0.001) and exhibited clear rainfall-driven and seasonal patterns, indicating stormwater-mediated transport and transformation. Observed concentrations were within the lower range of values reported globally for urban surface waters. To our knowledge, this study provides the first dataset of 6PPD and 6PPD-Q in Florida waters. These results demonstrate the utility of online SPE-HPLC-MS/MS for tracking tire-derived contaminants in urbanized watersheds and emphasize the need for continued regional and global monitoring given their environmental persistence and ecotoxicological significance.
More Papers Like This
The Tire Wear Compounds 6PPD-Quinone and 1,3-Diphenylguanidine in an Urban Watershed
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Researchers re-analyzed archived water samples from an urban Canadian river and detected the tire-wear chemical 6PPD-quinone at concentrations exceeding the lethal threshold for coho salmon during storm events, confirming that tire-derived contaminants enter urban waterways in kilogram-scale loads during rainfall.
Presence of 6PPD-quinone in runoff water samples from Norway using a new LC–MS/MS method
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A new LC-MS/MS method was developed and validated to detect 6PPD-quinone, a tire additive byproduct highly toxic to salmon, in Norwegian runoff water samples, finding concentrations above the lethal threshold for coho salmon in all samples except those from a treatment plant.
Reclaimed water in road cleaning: An unrecognized risk for toxic 6PPD-Q formation from tire wear waste
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Researchers found that washing roads with reclaimed water instead of rainwater accelerates the aging of tire wear particles and significantly increases conversion of the tire additive 6PPD into its more toxic transformation product 6PPD-quinone, suggesting that urban water reuse practices may inadvertently amplify the release of a compound acutely lethal to coho salmon.
Multiresidue microextraction–GC-MS/MS for emerging tire rubber contaminants in urban waters
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Scientists developed a new, easy-to-use lab method to detect chemicals leaching from tire rubber (like playground surfaces and roads) into urban water. Using this method, they found two potentially harmful chemicals, 6PPD and its byproduct 6PPD-quinone—both linked to toxicity in aquatic life—in every water sample tested. This matters because tire-derived chemicals are increasingly showing up in the water around us, and having a reliable way to track them is a key first step toward understanding how much we and wildlife are actually exposed to.
Concentrations of Tire Additive Chemicals and Tire Road Wear Particles in an Australian Urban Tributary
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Researchers measured tire wear particles and their chemical additives in stormwater runoff during severe storms in an Australian urban area. During storms, concentrations of tire-related chemicals spiked more than 40 times, including the compound 6PPD-quinone, which is toxic to aquatic life even at low levels. This study is relevant to human health because tire wear is one of the largest sources of microplastics in cities, and the chemicals they release can contaminate waterways that supply drinking water.
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