ABSTRACT
In urban to peri-urban watersheds such as those surrounding San Francisco Bay, stormwater runoff is a major pathway by which contaminants enter aquatic ecosystems. We evaluated the occurrence of 154 organic contaminants via liquid chromatography coupled to tandem mass spectrometry, including organophosphate esters (OPEs), bisphenols, per- and polyfluoroalkyl substances (PFASs), and a suite of novel urban stormwater tracers (SWCECs; i.e., vehicle-derived chemicals, pesticides, pharmaceuticals/personal care products, benzothiazoles/benzotriazoles). Time-averaged composite sampling focused on storms in highly developed watersheds over four wet seasons, with complementary sampling in less-urban reference watersheds, near-shore estuarine sites, and the open Bay. Of the targeted contaminants, 68 (21 SWCECs, 29 OPEs, 3 bisphenols, 15 PFASs) were detected in ≥10 of 26 urban stormwater samples. Median concentrations exceeded 500 ng L-1 for 1,3-diphenylguanidine, hexa(methoxymethyl)melamine, and caffeine, and exceeded 300 ng L-1 for 2-hydroxy-benzothiazole, 5-methyl-1H-benzotriazole, pentachlorophenol, and tris(2-butoxyethyl) phosphate. Median individual PFAS concentrations were <10 ng L-1, with highest concentrations for PFHxA (180 ng L-1), PFOA (110 ng L-1), and PFOS (81 ng L-1). In six of eight urban stormwater samples analyzed for 6PPD-quinone (a tire rubber-derived transformation product), concentrations exceeded coho salmon acute toxicity thresholds, suggesting (sub)lethal impacts for sensitive species. Observed concentrations were generally significantly higher in highly developed watersheds relative to reference watersheds, but not statistically different in near-shore estuarine sites, suggesting substantial transient exposure potential at stormwater outfalls or creek outflows. Results emphasized the role of stormwater in contaminant transport, the importance of vehicles/roadways as contaminant sources, and the value of monitoring broad multi-analyte contaminant suites to enable comprehensive source and toxicity evaluations.
Subject(s)
Bays , Environmental Monitoring , Fluorocarbons , Organophosphates , Phenols , Water Pollutants, Chemical , San Francisco , Water Pollutants, Chemical/analysis , Bays/chemistry , Phenols/analysis , Organophosphates/analysis , Fluorocarbons/analysis , Rain/chemistry , Esters/analysisABSTRACT
About 3 billion new tires are produced each year and about 800 million tires become waste annually. Global dependence upon tires produced from natural rubber and petroleum-based compounds represents a persistent and complex environmental problem with only partial and often-times, ineffective solutions. Tire emissions may be in the form of whole tires, tire particles, and chemical compounds, each of which is transported through various atmospheric, terrestrial, and aquatic routes in the natural and built environments. Production and use of tires generates multiple heavy metals, plastics, PAH's, and other compounds that can be toxic alone or as chemical cocktails. Used tires require storage space, are energy intensive to recycle, and generally have few post-wear uses that are not also potential sources of pollutants (e.g., crumb rubber, pavements, burning). Tire particles emitted during use are a major component of microplastics in urban runoff and a source of unique and highly potent toxic substances. Thus, tires represent a ubiquitous and complex pollutant that requires a comprehensive examination to develop effective management and remediation. We approach the issue of tire pollution holistically by examining the life cycle of tires across production, emissions, recycling, and disposal. In this paper, we synthesize recent research and data about the environmental and human health risks associated with the production, use, and disposal of tires and discuss gaps in our knowledge about fate and transport, as well as the toxicology of tire particles and chemical leachates. We examine potential management and remediation approaches for addressing exposure risks across the life cycle of tires. We consider tires as pollutants across three levels: tires in their whole state, as particulates, and as a mixture of chemical cocktails. Finally, we discuss information gaps in our understanding of tires as a pollutant and outline key questions to improve our knowledge and ability to manage and remediate tire pollution.
ABSTRACT
Wildfires can be extremely destructive to communities and ecosystems. However, the full scope of the ecological damage is often hard to assess, in part due to limited information on the types of chemicals introduced to affected landscapes and waterways. The objective of this study was to establish a sampling, analytical, and interpretive framework to effectively identify and monitor contaminants of emerging concern in environmental water samples impacted by wildfire runoff. A nontargeted analysis consisting of comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC × GC/TOF-MS) was conducted on stormwater samples from watersheds in the City of Santa Rosa and Sonoma and Napa Counties, USA, after the three most destructive fires during the October 2017 Northern California firestorm. Chemicals potentially related to wildfires were selected from the thousands of chromatographic features detected through a screening method that compared samples from fire-impacted sites versus unburned reference sites. This screening led to high confidence identifications of 76 potentially fire-related compounds. Authentic standards were available for 48 of these analytes, and 46 were confirmed by matching mass spectra and GC × GC retention times. Of these 46 compounds, 37 had known commercial and industrial uses as intermediates or ingredients in plastics, personal care products, pesticides, and as food additives. Nine compounds had no known uses or sources and may be oxidation products resulting from burning of natural or anthropogenic materials. Preliminary examination of potential toxicity associated with the 46 compounds, conducted via online databases and literature review, indicated limited data availability. Regional comparison suggested that more structural damage may yield a greater number of unique, potentially wildfire-related compounds. We recommend further study of post-wildfire runoff using the framework described here, which includes hypothesis-driven site selection and nontargeted analysis, to uncover potentially significant stormwater contaminants not routinely monitored after wildfires and inform risk assessment. Integr Environ Assess Manag 2021;17:1179-1193. © 2021 SETAC.