Framework for nontargeted investigation of contaminants released by wildfires into stormwater runoff: Case study in the northern San Francisco Bay area.

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.

Per- and polyfluoroalkyl substances (PFASs) in San Francisco Bay wildlife: Temporal trends, exposure pathways, and notable presence of precursor compounds.

Concentrations of perfluorooctane sulfonate (PFOS) in San Francisco Bay (SF Bay) wildlife have historically been among the highest reported globally. To track continuing exposures to PFASs and assess the impact of the 2002 phase-out of production of PFOS and related chemicals in the US, nine perfluoroalkyl carboxylic acids (PFCAs; C4-C12), three perfluoroalkyl sulfonic acids (PFSAs; C4, C6, C8) and perfluorooctane sulfonamide (PFOSA, a PFOS precursor) were measured in SF Bay cormorant eggs in 2012 and harbor seal serum sampled between 2009 and 2014. PFOS remained the dominant perfluoroalkyl acid (PFAA) in both cormorant eggs (36.1-466 ng/g) and seals (12.6-796 ng/g) from 2012 and 2014, respectively. Concentrations in seal and bird eggs from the South Bay have declined approximately 70% in both matrices. To elucidate potential pathways of exposure, prey fish, sediments and wastewater effluent were analyzed for PFASs, and in the case of sediment and effluent, a suite of PFAA precursors. PFOS was the dominant PFAA in prey fish and sediment. In effluent, different mixtures of PFAAs were measured, with PFOS, PFHxA, and PFOA detected in the highest concentrations. Polyfluoroalkyl phosphate diesters (PFCA-precursors) were observed at concentrations over an order of magnitude higher than PFCAs in sediment, highlighting their importance as a potential, on-going source of PFCAs to SF Bay wildlife. These findings suggest that the PFOS phase-out has resulted in reduced burdens to wildlife in SF Bay, but that exposure to diverse and incompletely characterized PFASs continues.

Declines in polybrominated diphenyl ether contamination of San Francisco Bay following production phase-outs and bans.

California has implemented unique consumer product flammability standards. Polybrominated diphenyl ether (PBDE) flame retardants were once widely incorporated into products to meet these standards, but concerns regarding toxicity and accumulation in humans and biota led to nationwide phase-outs and state bans. A decade of PBDE monitoring in San Francisco Bay has resulted in a data set that covers periods during and after PBDE use and consists of hundreds of measurements of water, sediment, and biota. While PBDEs remain widely detected in biota, levels have declined by nearly half in sport fish and 74-95% in bivalves and bird eggs. Concentrations of BDE-47 in sediment have dropped by over one-third from 2002 to 2012; in water, a decline is not yet evident. The dominant congener in sediment, DecaBDE component BDE-209, showed no temporal trend. U.S. production of DecaBDE ended in 2013; future monitoring may reveal declines. Overall, the data indicate that reduced production can result in relatively rapid reductions in the concentrations of some hydrophobic contaminants in biota and sediment, particularly when implemented after only a few decades of heavy use. Recent changes to California's flammability standards may lessen the use of other flame retardants and similarly reduce Bay contamination.

Perfluoroalkyl compounds (PFCs) in wildlife from an urban estuary.

Previous research has documented the bioaccumulation of perfluoroalkyl compounds (PFCs) in apex predators in remote locations but few studies have evaluated urban estuaries. To assess the importance of PFCs in San Francisco Bay, two apex predators in the San Francisco Bay, double-crested cormorants (Phalacrocorax auritus) and Pacific harbor seals (Phoca vitulina richardii), were sampled. Prey fish (Atherinops affinis and Menidia audens) were also evaluated to better understand potential sources of PFCs to the foodweb. Perfluorooctane sulfonate (PFOS) was the primary PFC detected in cormorant eggs, small fish and harbor seal serum. PFOS detected in San Francisco Bay seal serum was typically an order of magnitude higher than those at the reference site. PFOS concentrations were highest in seals and cormorant eggs from the highly urbanized southern portion of the Bay. PFOS in eggs from the southern part of the Bay remained relatively constant between 2006 and 2009 despite the phase-out of perfluorosulfonyl-based compounds nationally. In addition, these levels exceed the avian predicted no effects concentration of 1.0 µg mL(-1). Concentrations of the remaining PFCs measured were substantially lower than those of PFOS.