In U.S. Pacific Northwest coho salmon (Oncorhynchus kisutch), stormwater exposure annually causes unexplained acute mortality when adult salmon migrate to urban creeks to reproduce. By investigating this phenomenon, we identified a highly toxic quinone transformation product of N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine (6PPD), a globally ubiquitous tire rubber antioxidant. Retrospective analysis of representative roadway runoff and stormwater-affected creeks of the U.S. West Coast indicated widespread occurrence of 6PPD-quinone (<0.3 to 19 micrograms per liter) at toxic concentrations (median lethal concentration of 0.8 ± 0.16 micrograms per liter). These results reveal unanticipated risks of 6PPD antioxidants to an aquatic species and imply toxicological relevance for dissipated tire rubber residues.
Stormwater runoff has been suggested to be a significant pathway of microplastics to aquatic habitats; yet, few studies have quantified microplastics in stormwater. Here, we quantify and characterize urban stormwater runoff from 12 watersheds surrounding San Francisco Bay for anthropogenic debris, including microplastics. Depth-integrated samples were collected during wet weather events. All stormwater runoff contained anthropogenic microparticles, including microplastics, with concentrations ranging from 1.1 to 24.6 particles/L. These concentrations are much higher than those in wastewater treatment plant effluent, suggesting urban stormwater runoff is a major source of anthropogenic debris, including microplastics, to aquatic habitats. Fibers and black rubbery fragments (potentially tire and road wear particles) were the most frequently occurring morphologies, comprising ∼85% of all particles across all samples. This suggests that mitigation strategies for stormwater should be prioritized. As a case study, we sampled stormwater from the inlet and outlet of a rain garden during three storm events to measure how effectively rain gardens capture microplastics and prevent it from contaminating aquatic ecosystems. We found that the rain garden successfully removed 96% of anthropogenic debris on average and 100% of black rubbery fragments, suggesting rain gardens should be further explored as a mitigation strategy for microplastic pollution.
The physical and chemical properties of microplastics and their environmental distributions may provide clues about their sources and inform their fate. We demonstrate the value of extensive monitoring of microplastics in an urban bay, San Francisco Bay. Surface water, fish, sediment, stormwater runoff, and treated wastewater were sampled across the bay and adjacent national marine sanctuaries (NMS). We found microplastics and other anthropogenic microdebris ("microdebris") in all sample types. Concentrations were higher in the bay than in the NMS, and within the bay, concentrations were higher during the wet season than during the dry season. The fate of microdebris varied depending on their morphologies and densities: fibers were dominant in fish, black rubbery fragments were common in sediment, as were fibers, while buoyant fragments and fibers were widely observed in surface waters. Notably, we found large amounts of black rubbery fragments, an emerging contaminant, in stormwater. Moreover, stormwater was a significant pathway of microdebris, with concentrations roughly 140 times greater than those found in wastewater, which was dominated by fibers. Overall, we demonstrate the value of multimatrix regional monitoring to evaluate the sources and fate of microplastics, which can inform effective mitigation for other urban bays around the world.
Water-quality policy documents throughout the world often identify urban stormwater as a large and controllable impact to sensitive ecosystems, yet there is often limited data to characterize concentrations and loads especially for rare and more difficult to quantify pollutants. In response, concentrations of suspended sediments and silver, mercury and selenium including speciation, and other trace elements were measured in dry and wet weather stormwater flow from a 100% urban watershed near San Francisco. Suspended sediment concentrations ranged between 1.4 and 2700 mg/L and varied with storm intensity. Turbidity was shown to correlate strongly with suspended sediments and most trace elements and was used as a surrogate with regression to estimate concentrations during unsampled periods and to compute loads. Mean suspended sediment yield was 31.5 t/km(2)/year. Total mercury ranged between 1.4 and 150 ng/L and was, on average, 92% particulate, 0.9% methylated, and 1.2% acid labile. Total mercury yield averaged 5.7 μg/m(2)/year. Total selenium ranged between non-detect and 2.9 μg/L and, on average, the total load (0.027 μg/m(2)/year) was 61% transported in dissolved phase. Selenate (Se(VI)) was the dominant species. Silver concentrations ranged between non-detect and 0.11 μg/L. Concentrations and loads of other trace elements were also highly variable and were generally similar to other urban systems with the exceptions of Ag and As (seldom reported) and Cr and Zn which exhibited concentrations and loads in the upper range of those reported elsewhere. Consistent with the semi-arid climatic setting, >95% of suspended sediment, 94% of total Hg, and 85-95 % of all other trace element loads were transported during storm flows with the exception of selenium which showed an inverse relationship between concentration and flow. Treatment of loads is made more challenging in arid climate settings due to low proportions of annual loads and greater dissolved phase during low flow conditions. This dataset fills an important local data gap for highly urban watersheds of San Francisco Bay. The field and interpretative methods, the uniqueness of the analyte list, and resulting information have general applicability for managing pollutant concentrations and loads in urban watersheds in other parts of the world and may have particularly useful application in more arid climates.
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