Suspect Screening and Chemical Profile Analysis of Storm-Water Runoff Following 2017 Wildfires in Northern California.

The combustion of structures and household materials as well as firefighting during wildfires lead to releases of potentially hazardous chemicals directly into the landscape. Subsequent storm-water runoff events can transport wildfire-related contaminants to downstream receiving waters, where they may pose water quality concerns. To evaluate the environmental hazards of northern California fires on the types of contaminants in storm water discharging to San Francisco Bay and the coastal marine environment, we analyzed storm water collected after the northern California wildfires (October 2017) using a nontargeted analytical (NTA) approach. Liquid chromatography quadrupole time-of-flight mass spectrometric analysis was completed on storm-water samples (n = 20) collected from Napa County (impacted by the Atlas and Nuns fires), the city of Santa Rosa, and Sonoma County (Nuns and Tubbs fires) during storm events that occurred in November 2017 and January 2018. The NTA approach enabled us to establish profiles of contaminants based on peak intensities and chemical categories found in the storm-water samples and to prioritize significant chemicals within these profiles possibly attributed to the wildfire. The results demonstrated the presence of a wide range of contaminants in the storm water, including surfactants, per- and polyfluoroalkyl substances, and chemicals from consumer and personal care products. Homologs of polyethylene glycol were found to be the major contributor to the contaminants, followed by other widely used surfactants. Nonylphenol ethoxylates, typically used as surfactants, were detected and were much higher in samples collected after Storm Event 1 relative to Storm Event 2. The present study provides a comprehensive approach for examining wildfire-impacted storm-water contamination of related contaminants, of which we found many with potential ecological risk. Environ Toxicol Chem 2022;41:1824-1837. © 2022 SETAC.

Long-term variation in concentrations and mass loads in a semi-arid watershed influenced by historic mercury mining and urban pollutant sources.

Urban watersheds are significantly anthropogenically-altered landscapes. Most previous studies cover relatively short periods, without addressing concentrations, loads, and yields in relation to annual climate fluctuations, and datasets on Ag, Se, PBDEs, and PCDD/Fs are rare. Intensive storm-focused sampling and continuous turbidity monitoring were employed to quantify pollution at two locations in the Guadalupe River (California, USA). At a downstream location, we determined loads of suspended sediment (SS) for 14yrs., mercury (HgT), PCBs, and total organic carbon (TOC) (8yrs), total methylmercury (MeHgT) (6yrs), nutrients, and trace elements including Ag and Se (3yrs), DDTs, chlordanes, dieldrin, and PBDEs (2yrs), and PCDD/Fs (1yr). At an upstream location, we determined loads of SS for 4yrs. and HgT, MeHgT, PCBs and PCDD/Fs for 1yr. These data were compared to previous studies, climatically adjusted, and used to critically assess the use of small datasets for estimating annual average conditions. Concentrations and yields in the Guadalupe River appear to be atypical for total phosphorus, DDTs, dieldrin, HgT, MeHgT, Cr, Ni, and possibly Se due to local conditions. Other pollutants appear to be similar to other urban systems. On average, wet season flow varied by 6.5-fold and flow-weighted mean (FWM) concentrations varied 4.4-fold, with an average 7.1-fold difference between minimum and maximum annual loads. Loads for an average runoff year for each pollutant were usually less than the best estimate of long-term average. The arithmetic average of multiple years of load data or a FWM concentration combined with mean annual flow was also usually below the best estimate of long-term average load. Mean annual loads using sampled years were also less than the best estimate of long-term average by a mean of 2.2-fold. Climatic adjustment techniques are needed for computing estimates of long-term average annual loads.

Concentrations and loads of suspended sediment and trace element pollutants in a small semi-arid urban tributary, San Francisco Bay, California.

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.

Concentrations and loads of PCBs, dioxins, PAHs, PBDEs, OC pesticides and pyrethroids during storm and low flow conditions in a small urban semi-arid watershed.

Urban runoff has been identified in water quality policy documents for San Francisco Bay as a large and potentially controllable source of pollutants. In response, concentrations of suspended sediments and a range of trace organic pollutants were intensively measured in dry weather and storm flow runoff from a 100% urban watershed. Flow in this highly urban watershed responded very quickly to rainfall and varied widely resulting in rapid changes of turbidity, suspended sediments and pollutant concentrations. Concentrations of each organic pollutant class were within similar ranges reported in other studies of urban runoff, however comparison was limited for several of the pollutants given information scarcity. Consistently among PCBs, PBDEs, and PAHs, the more hydrophobic congeners were transported in larger proportions during storm flows relative to low flows. Loads for Water Years 2007-2010 were estimated using regression with turbidity during the monitored months and a flow weighted mean concentration for unmonitored dry season months. More than 91% of the loads for every pollutant measured were transported during storm events, along with 87% of the total discharge. While this dataset fills an important local data gap for highly urban watersheds of San Francisco Bay, the methods, the uniqueness of the analyte list, and the resulting interpretations have applicability for managing pollutant loads in urban watersheds in other parts of the world.

Polychlorinated biphenyls in the exterior caulk of San Francisco Bay Area buildings, California, USA.

Extensive evidence of the adverse impacts of polychlorinated biphenyls (PCBs) to wildlife, domestic animals, and humans has now been documented for over 40 years. Despite the ban on production and new use of PCBs in the United States in 1979, a number of fish consumption advisories remain in effect, and there remains considerable uncertainty regarding ongoing environmental sources and management alternatives. Using a blind sampling approach, 25 caulk samples were collected from the exterior of ten buildings in the San Francisco Bay Area and analyzed for PCBs using congener-specific gas chromatography-mass spectrometry (GC-MS) and chlorine using portable X-ray fluorescence (XRF). PCBs were detected in 88% of the caulk samples collected from the study area buildings, with 40% exceeding 50 ppm. Detectable PCB concentrations ranged from 1 to 220,000 ppm. These data are consistent with previous studies in other cities that have identified relatively high concentrations of PCBs in concrete and masonry buildings built between 1950 and 1980. Portable XRF was not a good predictor of the PCB content in caulk and the results indicate that portable XRF analysis may only be useful for identifying caulk that contains low concentrations of Cl (≤ 10,000 ppm) and by extension low or no PCBs. A geographic information system-based approach was used to estimate that 10,500 kg of PCBs remain in interior and exterior caulk in buildings located in the study area, which equates to an average of 4.7 kg PCBs per building. The presence of high concentrations in the exterior caulk of currently standing buildings suggests that building caulk may be an ongoing source of PCBs to the San Francisco Bay Area environment. Further studies to expand the currently small international dataset on PCBs in caulking materials in buildings of countries that produced or imported PCBs appear justified in the context of both human health and possible ongoing environmental release.

A regional mass balance of methylmercury in San Francisco Bay, California, USA.

The San Francisco Bay (California, USA) is a water body listed as impaired because of Hg contamination in sport fish for human consumption, as well as possible effects on resident wildlife. A legacy of Hg mining in local watersheds and Hg used in Au mining in the Sierra Nevada (USA) has contributed to contamination seen in the bay, with additional more recent and ongoing inputs from various sources. Methylmercury is the species of Hg most directly responsible for contamination in biota, so better understanding of its sources, loads, and processes was sought to identify the best means to reduce impacts. A regional scale model of San Francisco Bay was developed to characterize major methylmercury inputs and processes. The model was used to evaluate the potential impact of uncertainties in estimates for methylmercury loading pathways and environmental processes, identify major data gaps, and explore management prospects for reducing methylmercury contamination. External loading pathways considered in the mass balance include methylmercury loads entering via atmospheric deposition to the bay surface, and discharges from the Sacramento/San Joaquin Delta, local watersheds, municipal wastewater, and fringing wetlands. Internal processes considered include exchange between bed and suspended sediments and the water column, in situ production and demethylation, biological uptake, and losses via hydrologic transport to the ocean through the Golden Gate. In situ sediment methylation and demethylation were dominant sources and losses determining ambient steady-state concentrations in the model, with changes in external loads and export causing smaller changes. Better information on methylation and demethylation is thus most critical to improving understanding of methylmercury balances and management.

Mercury concentrations and loads in a large river system tributary to San Francisco Bay, California, U.S.A.

In order to estimate total mercury (HgT) loads entering San Francisco Bay, U.S.A., via the Sacramento-San Joaquin River system, unfiltered water samples were collected between January 2002 and January 2006 during high flow events and analyzed for HgT. Unfiltered HgT concentrations ranged from 3.2 to 75 ng/L and showed a strong correlation (r2 = 0.8, p < 0.001, n=78) to suspended sediment concentrations (SSC). During infrequent large floods, HgT concentrations relative to SSC were approximately twice as high as observed during smaller floods. This difference indicates the transport of more Hg-contaminated particles during high discharge events. Daily HgT loads in the Sacramento-San Joaquin River at Mallard Island ranged from below the limit of detection to 35 kg. Annual HgT loads varied from 61 +/- 22 kg (n=5) in water year (WY) 2002 to 470 +/- 170 kg (n=25) in WY 2006. The data collected will assist in understanding the long-term recovery of San Francisco Bay from Hg contamination and in implementing the Hg total maximum daily load, the long-term cleanup plan for Hg in the Bay.

A mass budget of polybrominated diphenyl ethers in San Francisco Bay, CA.

A mass budget of polybrominated diphenyl ethers (PBDEs) in San Francisco Bay is developed as a first step towards understanding the local sources and transport processes controlling PBDE fate in a highly urbanized estuary. Extensive monitoring of PBDEs in estuarine water and sediment, freshwater tributaries, air, and wastewater effluents and sludges were integrated with a mass budget model to provide a synthetic view of these emerging contaminants. The Bay inventories of BDE 47 and BDE 209 in 2006 were estimated to be 33+/-3 kg and 153+/-45 kg, respectively. Empirically derived estimates of annual inputs of BDE 47 and BDE 209 from all quantifiable external sources ranged from 11 to 28 kg/y and 22 to 24 kg/y, respectively. BDE 47 loads were dominated by wastewater while runoff from local tributaries represented the largest contributor to BDE 209 loads. Model results suggest the Bay PBDE inventory is highly sensitive to changes in external loads, with degradation and outflow being the major processes governing PBDE fate. The mass budget presented provides a framework for integrating future monitoring and modeling efforts.