Urban runoff mortality syndrome in zooplankton caused by tire wear particles.

Stormwater runoff from roadways is a global threat to water quality, aquatic organisms, and ecosystems. Tire tread wear particles (TWP) from roadway runoff may lead to urban runoff mortality syndrome (URMS) in some aquatic organisms. We tested the hypothesis that urban runoff from roadways can kill zooplankton. Both roadway runoff and TWP leachate were acutely lethal to a model species, the water flea Daphnia pulex. Life table experiments further revealed the lowered survival rates, intrinsic rate of increase, average life span, and net productive rate of D. pulex when exposed to roadway runoff and TWP leachate. The tire rubber antioxidant N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD) mainly contributed to the TWP toxicity. The toxicity of TWP and 6PPD extracted varied with time in nature. Cladocerans and rotifers were more sensitive to TWP and 6PPD than copepods. These results demonstrate the presence of URMS in zooplankton, which may cascade through food webs and affect aquatic ecosystems.

Transformation Products of Tire Rubber Antioxidant 6PPD in Heterogeneous Gas-Phase Ozonation: Identification and Environmental Occurrence.

6PPD, a tire rubber antioxidant, poses substantial ecological risks because it can form a highly toxic quinone transformation product (TP), 6PPD-quinone (6PPDQ), during exposure to gas-phase ozone. Important data gaps exist regarding the structures, reaction mechanisms, and environmental occurrence of TPs from 6PPD ozonation. To address these data gaps, gas-phase ozonation of 6PPD was conducted over 24-168 h and ozonation TPs were characterized using high-resolution mass spectrometry. The probable structures were proposed for 23 TPs with 5 subsequently standard-verified. Consistent with prior findings, 6PPDQ (C18H22N2O2) was one of the major TPs in 6PPD ozonation (∼1 to 19% yield). Notably, 6PPDQ was not observed during ozonation of 6QDI (N-(1,3-dimethylbutyl)-N'-phenyl-p-quinonediimine), indicating that 6PPDQ formation does not proceed through 6QDI or associated 6QDI TPs. Other major 6PPD TPs included multiple C18H22N2O and C18H22N2O2 isomers, with presumptive N-oxide, N,N'-dioxide, and orthoquinone structures. Standard-verified TPs were quantified in roadway-impacted environmental samples, with total concentrations of 130 ± 3.2 µg/g in methanol extracts of tire tread wear particles (TWPs), 34 ± 4 µg/g-TWP in aqueous TWP leachates, 2700 ± 1500 ng/L in roadway runoff, and 1900 ± 1200 ng/L in roadway-impacted creeks. These data demonstrate that 6PPD TPs are likely an important and ubiquitous class of contaminants in roadway-impacted environments.