Wildland-urban interface wildfire increases metal contributions to stormwater runoff in Paradise, California.

The 2018 Camp Fire was a large late-year (November) wildfire that produced an urban firestorm in the Town of Paradise, California, USA, and destroyed more than 18 000 structures. Runoff from burned wildland areas is known to contain ash, which can transport contaminants including metals into nearby watersheds. However, due to historically infrequent occurrences, the effect of wildland-urban interface (WUI) fires, such as the Camp Fire, on surface water quality has not been well-characterized. Therefore, this study investigated the effects of widespread urban burning on surface water quality in major watersheds of the Camp Fire area. Between November 2018 and May 2019, 140 surface water samples were collected, including baseflow and stormflow, from burned and unburned watersheds with varying extent of urban development. Samples were analyzed for total and filter-passing metals, dissolved organic carbon, major anions, and total suspended solids. Ash and debris from the Camp Fire contributed metals to downstream watersheds via runoff throughout the storm season. Increases in concentration up to 200-fold were found for metals Cr, Cu, Ni, Pb, and Zn in burned watersheds compared to pre-fire values. Total concentrations of Al, Cd, Cu, Pb, and Zn exceeded EPA aquatic habitat acute criteria by up to 16-fold for up to five months after the fire. To assess possible transport mechanisms and bioavailability, a subset of 18 samples was analyzed using four filters with nominal pore sizes ranging from 0.22 to 1.2 µm to determine the particulate size distribution of metals. Trace and major metals (Al, Ba, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, and Zn) were found mostly associated with larger grain sizes (>0.45 µm), and some metals (Al, Cr, Fe, and Pb) also included a substantial colloidal phase (0.22 to 0.45 µm). This study suggests that fires in the wildland-urban interface increase metal concentrations, mainly through particulate driven transport. The metals with the largest increases are likely from anthropogenic disaster materials, though biomass ash also is a major contributor to water quality. The increase in metals following WUI burning may have adverse ecological impacts.

Wildfire impacts on surface water quality parameters: Cause of data variability and reporting needs.

Surface runoff mobilizes the burned residues and ashes produced during wildfires and deposits them in surface waters, thereby deteriorating water quality. A lack of a consistent reporting protocol precludes a quantitative understanding of how and to what extent wildfire may affect the water quality of surface waters. This study aims to analyze reported pre- and post-fire water quality data to inform the data reporting and highlight research opportunities. A comparison of the pre-and post-fire water quality data from 44 studies reveals that wildfire could increase the concentration of many pollutants by two orders of magnitude. However, the concentration increase is sensitive to when the sample was taken after the wildfire, the wildfire burned area, discharge rate in the surface water bodies where samples were collected, and pollutant type. Increases in burned areas disproportionally increased total suspended solids (TSS) concentration, indicating TSS concentration is dependent on the source area. Increases in surface water flow up to 10 m3 s-1 increased TSS concentration but any further increase in flow rate decreased TSS concentration, potentially due to dilution. Nutrients and suspended solids concentrations increase within a year after the wildfire, whereas peaks for heavy metals occur after 1-2 years of wildfire, indicating a delay in the leaching of heavy metals compared to nutrients from wildfire-affected areas. The concentration of polycyclic aromatic hydrocarbons (PAHs) was greatest within a year post-fire but did not exceed the surface water quality limits. The analysis also revealed inconsistency in the existing sampling protocols and provides a guideline for a modified protocol along with highlighting new research opportunities. Overall, this study underlines the need for consistent reporting of post-fire water quality data along with environmental factors that could affect the data so that the post-fire water quality can be assessed or compared between studies.

Wildland-urban interface fire ashes as a major source of incidental nanomaterials.

Although metal and metalloid concentrations in wildfire ashes have been documented, the nature and concentrations of incidental nanomaterials (INMs) in wildland-urban interface (WUI) fire ashes have received considerably less attention. In this study, the total metal and metalloid concentrations of 57 vegetation, structural, and vehicle ashes and underlying soils collected at the WUI following the 2020 fire season in northern California - North Complex Fire and LNU Lightning Complex Fire - were determined using inductively coupled plasma-time of flight-mass spectrometry after microwave-assisted acid digestion. The concentrations of Ti, Zn, Cu, Ni, Pb, Sn, Sb, Co, Bi, Cr, Ba, As, Rb, and W are generally higher in structural/vehicle-derived ashes than in vegetation-derived ashes and soils. The concentrations of Ca, Sr, Rb, and Ag increased with increased combustion completeness (e.g., black ash < gray ash < white ash), whereas those of C, N, Zn, Pb, and In decreased with increased combustion completeness. The concentration of anthropogenic Ti - determined by mass balance calculations and shifts in Ti/Nb above the natural background ratios - was highest in vehicle ash (median: 30.8 g kg-1, range: 4.5-41.0 g kg-1) followed by structural ash (median: 5.5 g kg-1, range: of 0-77.4 g kg-1). Various types of carbonaceous INM (e.g., amorphous carbon, turbostratic-like carbon, and carbon associated with zinc oxides) and metal-bearing INMs (e.g., Ti, Cu, Fe, Zn, Mn, Pb, and Cr) with sizes between few nanometers to few hundreds of nanometers were evidenced in ashes using transmission electron microscopy, including energy dispersive X-ray spectroscopy. Overall, this study demonstrates the abundance of a variety of metals and metalloids in the form of INMs in WUI fire ashes. This study also highlights the need for further research into the formation, transformation, reactivity, fate, and effects of INMs during and following fires at the WUI.

Wildfires: Identification of a new suite of aromatic polycarboxylic acids in ash and surface water.

Ash and surface water samples collected after wildfires in four different geographical locations (California, Colorado, Kansas and Alberta) were analyzed. The ash samples were leached with deionized water, and leachates were concentrated by solid phase extraction and analyzed by liquid chromatography/time-of-flight mass spectrometry. In addition, three surface water samples and a lysimeter water sample were collected from watersheds recently affected by fire in California and Colorado, and analyzed in similar fashion. A suite of benzene polycarboxylic acids (BPCAs), with two and three carboxyl groups and their corresponding isomers were identified for the first time in both ash leachates and water samples. Also found was a pyridine carboxylic acid (PCA), 3,5-pyridine dicarboxylic acid. Furthermore, putative identifications were made for other carboxylated aromatic acids: quinolinic, naphthalenic, and benzofuranoic acid carboxylates. The wildfire ashes, a controlled wood ash, and post-fire surface water samples suggest that burned woody material, along with surface plant-material and heated o-horizon soil organic matter, contribute to both BPCAs and PCAs in runoff. This study is the first of its kind to identify this suite of aromatic acids in wildfire ash and surface water samples. These data make an important contribution to the nature of dissolved organic matter from wildfire and are useful to better understand the impact of wildfire on water quality and drinking water sources.

Mercury in western North America: A synthesis of environmental contamination, fluxes, bioaccumulation, and risk to fish and wildlife.

Western North America is a region defined by extreme gradients in geomorphology and climate, which support a diverse array of ecological communities and natural resources. The region also has extreme gradients in mercury (Hg) contamination due to a broad distribution of inorganic Hg sources. These diverse Hg sources and a varied landscape create a unique and complex mosaic of ecological risk from Hg impairment associated with differential methylmercury (MeHg) production and bioaccumulation. Understanding the landscape-scale variation in the magnitude and relative importance of processes associated with Hg transport, methylation, and MeHg bioaccumulation requires a multidisciplinary synthesis that transcends small-scale variability. The Western North America Mercury Synthesis compiled, analyzed, and interpreted spatial and temporal patterns and drivers of Hg and MeHg in air, soil, vegetation, sediments, fish, and wildlife across western North America. This collaboration evaluated the potential risk from Hg to fish, and wildlife health, human exposure, and examined resource management activities that influenced the risk of Hg contamination. This paper integrates the key information presented across the individual papers that comprise the synthesis. The compiled information indicates that Hg contamination is widespread, but heterogeneous, across western North America. The storage and transport of inorganic Hg across landscape gradients are largely regulated by climate and land-cover factors such as plant productivity and precipitation. Importantly, there was a striking lack of concordance between pools and sources of inorganic Hg, and MeHg in aquatic food webs. Additionally, water management had a widespread influence on MeHg bioaccumulation in aquatic ecosystems, whereas mining impacts where relatively localized. These results highlight the decoupling of inorganic Hg sources with MeHg production and bioaccumulation. Together the findings indicate that developing efforts to control MeHg production in the West may be particularly beneficial for reducing food web exposure instead of efforts to simply control inorganic Hg sources.

Estimating mercury emissions resulting from wildfire in forests of the Western United States.

Understanding the emissions of mercury (Hg) from wildfires is important for quantifying the global atmospheric Hg sources. Emissions of Hg from soils resulting from wildfires in the Western United States was estimated for the 2000 to 2013 period, and the potential emission of Hg from forest soils was assessed as a function of forest type and soil-heating. Wildfire released an annual average of 3100±1900kg-Hgy(-1) for the years spanning 2000-2013 in the 11 states within the study area. This estimate is nearly 5-fold lower than previous estimates for the study region. Lower emission estimates are attributed to an inclusion of fire severity within burn perimeters. Within reported wildfire perimeters, the average distribution of low, moderate, and high severity burns was 52, 29, and 19% of the total area, respectively. Review of literature data suggests that that low severity burning does not result in soil heating, moderate severity fire results in shallow soil heating, and high severity fire results in relatively deep soil heating (<5cm). Using this approach, emission factors for high severity burns ranged from 58 to 640µg-Hgkg-fuel(-1). In contrast, low severity burns have emission factors that are estimated to be only 18-34µg-Hgkg-fuel(-1). In this estimate, wildfire is predicted to release 1-30gHgha(-1) from Western United States forest soils while above ground fuels are projected to contribute an additional 0.9 to 7.8gHgha(-1). Land cover types with low biomass (desert scrub) are projected to release less than 1gHgha(-1). Following soil sources, fuel source contributions to total Hg emissions generally followed the order of duff>wood>foliage>litter>branches.

Analysis of trenbolone acetate metabolites and melengestrol in environmental matrices using gas chromatography-tandem mass spectrometry.

Studies demonstrate that exposure to steroid hormones in receiving waters can adversely impact reproduction of aquatic organisms. In particular, exogenous steroid hormones widely used as growth promoters in animal agriculture are of high concern, yet no gas chromatography-tandem mass spectrometry (GC/MS/MS) analytical methods for the detection of these compounds in complex environmental matrices is described in the literature. This study utilizes analytical methods based upon N-methyl-N-(trimethylsilyl)trifluoro-acetamide-iodine (MSTFA-I(2)) derivatization for the analysis of metabolites of trenbolone acetate (TBA), including 17α-trenbolone, 17ß-trenbolone, and trendione, and melengestrol acetate in receiving waters and surface soils associated with animal agriculture. Results suggest method detection levels of 0.5-1 ng/L for the trenbolone metabolites, while detection of melengestrol is qualitative only. Isotope dilution methods employing d3-17ß-trenbolone were used to improve steroid quantification. Method recoveries in spiked samples collected from a variety of representative receiving waters generally ranged from 80-120% with consistent and low standard deviation (generally<10%) for replicate analysis. Analysis of a storm water runoff sample from a commercial confined animal feeding operation (CAFO) that used TBA implants detected 17ß-trenbolone and trendione at concentrations of 31 and 52 ng/L, respectively. Analysis of surface soils at a commercial CAFO using TBA implants detected 17α-trenbolone at concentrations between 4-6 ng/g dry weight. Method development efforts suggested that the concentration of I(2) in MSTFA, the removal of I(2) from sample extracts after derivatization, and the use of Florisil clean-up to reduce organic matter matrix were vital aspects of steroid hormone quantification at low (<30ng/L) concentrations in complex environmental matrices.

Occurrence of trenbolone acetate metabolites in simulated confined animal feeding operation (CAFO) runoff.

Metabolites of androgenic synthetic growth promoters used at confined animal feeding operations (CAFOs) pose a demonstrated ecological risk. To evaluate the transport of trenbolone acetate (TBA) metabolites from beef cattle CAFOs, rainfall simulation experiments were conducted at the University of California, Davis, research CAFO. Steroid concentrations in solid and aqueous samples from the research CAFO and solids samples from a commercial CAFO were analyzed by gas chromatography-tandem mass spectrometry. The data indicate that 17α-trenbolone (17α-TBOH), 17ß-trenbolone (17ß-TBOH), and trendione (TBO), the three primary TBA metabolites, occur in soils and runoff. Soils at the research CAFO contained up to 8.2 (±1.1) ng/g-dw of 17α-TBOH and 1.2 (±0.1) ng/g-dw of 17ß-TBOH, with slightly higher (~20 ng/g-dw) 17α-TBOH concentrations observed in commercial CAFO soils. In simulated runoff, 17α-TBOH concentrations of 1-350 ng/L and TBO concentrations from 1-170 ng/L were observed. The metabolite 17ß-TBOH intermittently occurred in runoff samples at 5-26 ng/L and may be correlated to anaerobic soils. Metabolite concentrations observed in CAFO runoff correspond to 5-15% of potential maximum steroid concentrations predicted by mass balances. First order transformation rates of 0.028/day (25 day half-life) were estimated for 17α-TBOH in CAFO soils. Results suggest that ecologically relevant concentrations of TBA metabolites can be mobilized from CAFO surfaces in storm runoff and may lead to receiving water concentrations at or above ecological effects thresholds for a very limited number of discharge scenarios.

Fate of endogenous steroid hormones in steer feedlots under simulated rainfall-induced runoff.

Steroid hormones pose potential risks to fish and other aquatic organisms at extremely low concentrations. To assess the factors affecting the release of endogenous estrogenic and androgenic steroids from feedlots during rainfall, runoff, and soil samples were collected after simulated rainfall on a 14-steer feedlot under different rainfall rates and aging periods and analyzed for six steroid hormones. While only 17α-estradiol, testosterone, and progesterone were detected in fresh manure, 17ß-estradiol, estrone, and androstenedione were present in the surficial soil after two weeks. In the feedlot surficial soil, concentrations of 17α-estradiol decreased by approximately 25% accompanied by an equivalent increase in estrone and 17ß-estradiol. Aging of the feedlot soils for an additional 7 days had no effect on estrogen and testosterone concentrations, but androstenedione concentrations decreased substantially, and progesterone concentrations increased. Androstenedione and progesterone concentrations in the surficial soil were much higher than could be accounted for by excretion or conversion from testosterone, suggesting that other potential precursors, such as sterols, were converted after excretion. The concentration of androgens and progesterone in the soil were approximately 85% lower after simulated rainfall, but the estrogen concentrations remained approximately constant. The decreased masses could not be accounted for by runoff, suggesting the possibility of rapid microbial transformation upon wetting. All six steroids in the runoff, with the exception of 17ß-estradiol, were detected in both the filtered and particle-associated phases at concentrations well above thresholds for biological responses. Runoff from the aged plots contained less 17α-estradiol and testosterone, but more estrone, androstenedione, and progesterone relative to the runoff from the unaged plots, and most of the steroids had a lower particle-associated fraction.