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.

Using High-Resolution Mass Spectrometry to Identify Organic Contaminants Linked to Urban Stormwater Mortality Syndrome in Coho Salmon.

Urban stormwater is a major threat to ecological health, causing a range of adverse, mostly sublethal effects. In western North America, urban runoff is acutely lethal to adult coho salmon ( Oncorhynchus kisutch) that spawn each fall in freshwater creeks. Although the mortality syndrome is correlated to urbanization and attributed to road runoff contaminant(s), the causal agent(s) remain unknown. We applied high-resolution mass spectrometry to isolate a coho mortality chemical signature: a list of nontarget and identified features that co-occurred in waters lethal to coho spawners (road runoff from controlled exposures and urban receiving waters from two field observations of symptomatic coho). Hierarchical cluster analysis indicated that tire wear particle (TWP) leachates were most chemically similar to the waters with observed toxicity, relative to other vehicle-derived sources. Prominent road runoff contaminants in the signature included two groups of nitrogen-containing compounds derived from TWP, polyethylene glycols, octylphenol ethoxylates, and polypropylene glycols. A (methoxymethyl)melamine compound family, previously unreported in North America, was detected in road runoff and urban creeks at concentrations up to ∼9 and ∼0.3 µg/L, respectively. The results indicate TWPs are an under-appreciated contaminant source in urban watersheds and should be prioritized for fate and toxicity assessment.

Functionalized polymer-iron oxide hybrid nanofibers: Electrospun filtration devices for metal oxyanion removal.

Via a single-pot electrospinning synthesis, we developed a functionalized polymer-metal oxide nanofiber filter for point of use (POU) water treatment of metal oxyanions (e.g., arsenate and chromate). Polyacrylonitrile (PAN) functionalization was accomplished by inclusion of surface-active, quaternary ammonium salts (QAS) [cetyltrimethylammonium bromide (CTAB) or tetrabutylammonium bromide (TBAB)] that provide strong base ion exchange sites. Embedded iron oxide [ferrihydrite (Fh)] nanoparticles were used for their established role as metal sorbents. We examined the influence of QAS and Fh loading on composite properties, including nanofiber morphology, surface area, surface chemical composition, and the accessibility of embedded nanoparticles to solution. Composite performance was then evaluated using kinetic, isotherm, and pH-edge sorption experiments with arsenate and chromate, and benchmarked to unmodified PAN nanofibers and freely dispersed Fh nanoparticles. We also assessed the long-term stability of QAS in the composite matrix. For composites containing QAS or Fh nanoparticles, increasing QAS/Fh nanoparticle loading generally yielded increasing metal oxyanion uptake. The optimized composite (PAN 7 wt%, Fh 3 wt%, TBAB 1 wt%) exhibited two distinct sites for simultaneous, non-competitive metal binding (i.e., iron oxide sites for arsenate removal via sorption and well-retained QAS sites for chromate removal via ion exchange). Moreover, surface-segregating QAS enriched Fh abundance at the nanofiber surface, allowing immobilized nanoparticles to exhibit reactivity comparable to that of unsupported (i.e., suspended or freely dispersed) nanoparticles. To simulate POU application, the optimized composite was tested in a dead-end, flow-through filtration system for arsenate and chromate removal at environmentally relevant concentrations (e.g., µg/L) in both idealized and simulated tap water matrices. Performance trends indicate that dual mechanisms for uptake are maintained in kinetically limited regimes. Although chromate removal via ion exchange is more susceptible to interfering counter-ions, arsenate removal in simulated tap water indicates that ∼130 g of the composite could produce an individual's annual supply of drinking water (assuming an influent contaminated with 100 µg As/L, which is 10 times the current MCL).