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.

Tree foliage as a net accumulator of highly toxic methylmercury.

Tree canopies are known to elevate atmospheric inputs of both mercury (Hg) and methylmercury (MeHg). While foliar uptake of gaseous Hg is well documented, little is known regarding the temporal dynamics and origins of MeHg in tree foliage, which represents typically less than 1% of total Hg in foliage. In this work, we examined the foliar total Hg and MeHg content by following the growth of five individual trees of American Beech (Fagus grandifolia) for one growing season (April-November, 2017) in North Carolina, USA. We show that similar to other studies foliar Hg content increased almost linearly over time, with daily accumulation rates ranging from 0.123 to 0.161 ng/g/day. However, not all trees showed linear increases of foliar MeHg content along the growing season; we found that 2 out of 5 trees showed elevated foliar MeHg content at the initial phase of the growing season but their MeHg content declined through early summer. However, foliar MeHg content among all 5 trees showed eventual increases through the end of the growing season, proving that foliage is a net accumulator of MeHg while foliar gain of biomass did not "dilute" MeHg content.

Burn Intensity Drives the Alteration of Phenolic Lignin to (Poly) Aromatic Hydrocarbons as Revealed by Pyrolysis Gas Chromatography-Mass Spectrometry (Py-GC/MS).

High-intensity wildfires alter the chemical composition of organic matter, which is expected to be distinctly different from low-intensity prescribed fires. Herein, we used pyrolysis gas chromatography/mass spectrometry (Py-GC/MS), in conjunction with solid-state 13C nuclear magnetic resonance (NMR) and Fourier transform infrared (FT-IR) spectroscopy, to assess chemical alterations from three wildfires and a long-term frequent prescribed fire site. Our results showed that black ash formed under moderate intensity burns contained less aromatic (ArH), polyaromatic hydrocarbon (PAH), and nitrogen-containing compounds (Ntg) but more lignin (LgC) and phenol compounds (PhC), compared to white ash formed under high intensity burns. Both 13C NMR and FT-IR confirmed a higher relative percentage of carboxyl carbon in white ash, indicating the potential for higher water solubility and more mobile carbon, relative to black ash. Compared to wildfires, ash from low-intensity prescribed fire contained less ArH, PAH, and Ntg and more LgC and PhC. Controlled laboratory burning trials indicated that organic matter alteration was sensitive to the burn temperature, but not related to the fuel type (pine vs fir) nor oxygen absence/presence at high burn temperatures. This study concludes that higher burn temperatures resulted in higher (poly)aromatic carbon/nitrogen and lower lignin/phenol compounds.

Impacts of Forest Fire Ash on Aquatic Mercury Cycling.

Mercury (Hg) is a ubiquitous contaminant in the environment and its methylated form, methylmercury (MeHg), poses a worldwide health concern for humans and wildlife, primarily through fish consumption. Global production of forest fire ash, derived from wildfires and prescribed burns, is rapidly increasing due to a warming climate, but their interactions with aqueous and sedimentary Hg are poorly understood. Herein, we compared the differences of wildfire ash with activated carbon and biochar on the sorption of aqueous inorganic Hg and sedimentary Hg methylation. Sorption of aqueous inorganic Hg was greatest for wildfire ash materials (up to 0.21 µg g-1 or 2.2 µg g-1 C) among all of the solid sorbents evaluated. A similar Hg adsorption mechanism for activated carbon, biochar made of walnut, and wildfire ash was found that involves the formation of complexes between Hg and oxygen-containing functional groups, especially the -COO group. Notably, increasing dissolved organic matter from 2.4 to 70 mg C L-1 remarkably reduced Hg sorption (up to 40% reduction) and increased the time required to reach Hg-sorbent pseudo-equilibrium. Surprisingly, biochar and wildfire ash, but not activated carbon, stimulated MeHg production during anoxic sediment incubation, possibly due to the release of labile organic matter. Overall, our study indicates that while wildfire ash can sequester aqueous Hg, the leaching of its labile organic matter may promote production of toxic MeHg in anoxic sediments, which has an important implication for potential MeHg contamination in downstream aquatic ecosystems after wildfires.

Examination of mercury contamination from a recent coal ash spill into the Dan River, North Carolina, United States.

Coal ash spills occasionally occur due to the accidental failure of surface impoundments, and toxic metal-laden ash can pose a serious health threat to adjacent aquatic ecosystems. Here, we performed an investigation into longitudinal variations of mercury (Hg) contamination in the Dan River (North Carolina, United States) about 17 and 29 months after a February 2014 coal ash spill incident, in which the reported Hg concentrations in the spilled coal ash (210 ng/g) were 1-2 orders of magnitude higher than the river sediments (2-61 ng/g). We examined total Hg (THg) and methyl Hg (MeHg) in sediments from 0 to 65 km downstream of the spill, and found that most of the variations of THg and MeHg in surface sediments (0-16 cm) could be well accounted by the organic matter content and appeared to be not contaminated by Hg derived from coal ash. In examining MeHg bioaccumulation in invertebrates (aquatic and riparian) and fish in the Dan River and fish in a reservoir downstream of Dan River, we found no evidence of elevated MeHg bioaccumulation due to the 2014 coal ash spill. Thus, we concluded that Hg contamination from the coal ash spill is largely absent in the Dan River for both surface sediments and biota within the first three years of spill (until 2017), even though the majority of coal ash may be buried deeper in the sediment in the river channel and/or the downstream reservoir. Alternatively, the Hg associated with the coal ash is largely not bioavailable for extensive microbial Hg methylation. The findings provide useful insights into remediation strategies for this incident and other coal ash spills.

Effects of triclosan on the RedoximiRs/Sirtuin/Nrf2/ARE signaling pathway in mosquitofish (Gambusia affinis).

Triclosan (TCS) has been widely used in daily life for its broad-spectrum antibacterial property and subsequently detected frequently in aquatic waterborne. Environmental relevant concentrations of TCS in water (ng-µg/L) may pose potential unexpected impact on non-target aquatic organisms. In the present work, we investigated the transcriptional responses of Nrf2 as well as its downstream genes, sirtuins and redox-sensitive microRNAs (RedoximiRs) in livers of the small freshwater fish mosquitofish (Gambusia affinis) which were exposed to environmental relevant concentrations of TCS (0.05 µg/L, 0.5 µg/L and 5 µg/L for 24 h and 168 h). Results showed there were similar up-regulations in Nrf2 and its target genes (e. g. NQO1, CAT and SOD) at transcriptional, enzymatic and protein levels, reflecting oxidative stress of TCS to mosquitofish. Meanwhile, up-regulations of Sirt1, Sirt2 and down-regulations of miR-34b, miR-200b-5p and miR-21 could modulate antioxidant system via the Nrf2/ARE signaling pathway by the post-transcriptional regulations. Some oxidative stress-related biomarkers displayed in concentration-dependent manners (e. g. NQO1 mRNA, CAT mRNA) and/or time-dependent manners (e. g. GSH contents). This study indicated that the RedoximiRs/Sirtuin/Nrf2/ARE signaling pathway played a crucial role in mosquitofish exposed to TCS, and there might be potentially profound effects for TCS on the aquatic ecological safety.

Effects of simvastatin on the PXR signaling pathway and the liver histology in Mugilogobius abei.

Simvastatin is one of the most commonly cholesterol-lowering prescribed drugs all over the world. With the increase of consumption of these pharmaceuticals and subsequent their discharge into the aquatic environment in recent years, they are present at detectable levels in most sewage effluents. Unfortunately, limited information is provided about their potential impacts on aquatic organisms, especially on the detoxification-related metabolism in fish. In the present study, one local native benthic fish (Mugilogobius abei) in southern China was employed as test species and exposed to SV (0.5 µg L-1, 5 µg L-1, 50 µg L-1 and 500 µg L-1) for 72 h. The transcriptional expression of nucleus transcriptional factor pregnane X receptor (PXR) and its downstream targeted genes including multixenobiotics resistance protein or permeability glycoprotein (P-gp), cytochrome 1A (CYP1A), cytochrome P450 3A (CYP3A), glutathione-S-transferase (GST) and the expression of associated microRNA such as miR-27, miR-34 and miR-148 in Mugilogobius abei were investigated. Result showed that the expressions of P-gp, CYP 1A, CYP 3A, GST and PXR were induced to some extend under simvastatin exposure for 72 h. A positive correlation was observed between PXR and CYP1A, CYP3A and P-gp. While for microRNA, a negative relationship was found between miR-34a and CYP3A, CYP1A. The expression of miR-148a was significantly induced under the exposure of SV (50 µg L-1), which was positive related to the transcriptional expression of PXR. For enzyme activity, erythromycin N-demethylase (ERND) significantly increased at 24 h and the activity of catalase (CAT) and superoxide dismutase (SOD) exhibited different trends. CAT was slightly inhibited at 24 h exposure but SOD was significantly induced in high concentration. Glutathione-S-transferase (GST) activity was significant inhibited after 72 h exposure. The reductive small molecule glutathione (GSH) content showed obvious decrease, while the quantity of malondialdehyde (MDA) increased significantly in high concentrations of SV exposure. GSH and MDA showed a typical negative correlation to some degree. Moreover, simvastatin caused histological changes in the liver tissues of M. abei, especially the size of adipocyte significantly decreased. The present study indicated that environmentally relevant concentration SV may affect the PXR signaling pathway in M. abei and pose potential ecological risks to non-target organisms like fish.

Origin, Reactivity, and Bioavailability of Mercury in Wildfire Ash.

Wildfires are expected to become more frequent and intensive at the global scale due to climate change. Many studies have focused on the loss of mercury (Hg) from burned forests; however, little is known about the origins, concentration, reactivity, and bioavailability of Hg in residual ash materials in postfire landscapes. We examine Hg levels and reactivity in black ash (BA, low burn intensity) and white ash (WA, high burn intensity) generated from two recent northern California wildfires and document that all ash samples contained measurable, but highly variable, Hg levels ranging from 4 to 125 ng/g dry wt. ( n = 28). Stable Hg isotopic compositions measured in select ash samples suggest that most Hg in wildfire ash is derived from vegetation. Ash samples had a highly variable fraction of Hg in recalcitrant forms (0-75%), and this recalcitrant Hg pool appears to be associated with the black carbon fraction in ash. Both BA and WA were found to strongly sequester aqueous inorganic Hg but not gaseous elemental Hg under controlled conditions. During anoxic ash incubation with natural surface water, we find that Hg in most ash samples had a minimal release and low methylation potential. Thus, the formation of wildfire ash can sequester Hg into relatively nonbioavailable forms, attenuating the potentially adverse effects of Hg erosion and transport to aquatic environments along with eroded wildfire ash.

Regulation of pregnane-X-receptor and microRNAs on detoxification-related genes expressions in Mugilogobius abei under the exposure to diclofenac.

Diclofenac (DCF) has been recognized as an emerging contaminant in aquatic environments. Though many studies have investigated the toxic effects of DCF in human and mammals, limited information is available for the responses of genes associated with detoxification metabolisms in non-target aquatic organisms such as fish. In the present study, a small benthic fish Mugilogobius abei, was chosen as the test organism and the effects of DCF on detoxification-related genes at transcriptional level in M. abei were investigated. Partial cDNAs of pregnane-X-receptor (pxr), cytochrome P450 3A (cyp 3a) and alpha-gst were cloned firstly. The responses of cyp 1a, cyp 3a, alpha-gst and p-gp genes and associated microRNAs expressions were measured under different concentrations of DCF exposure (0.5, 5, 50, 500 µg/L) for 24 h and 168 h. Induction of cyp 1a, cyp 3a, alpha-gst, p-gp and pxr mRNA expressions was observed under DCF exposure for different time. Positive concentration-response relationships between DCF concentrations and cyp 1a as well as alpha-gst mRNA expression were observed under DCF exposure for 24 h. The similar trend between pxr mRNA expression and cyp 3a gene expression suggested the role of pxr in regulation of its downstream detoxification genes involved in DCF detoxification in M. abei. The negative correlation between miR-27a and p-gp expression under DCF exposure for 24 h indicated the role of miRNA in post transcriptional regulation on detoxification-related genes mRNAs in M. abei exposed to DCF. Overall, DCF exposure, even at environmental levels, may interrupt the responses of the detoxification genes in M. abei, which may affect the response of the exposed organism to other pollutants. This work provides implications on the bio-monitoring and risk assessment of DCF in aquatic ecosystems by using of local native fish species.

Effects of diclofenac on the expression of Nrf2 and its downstream target genes in mosquito fish (Gambusia affinis).

Diclofenac (DCF) is one of widely used non-steroidal anti-inflammatory drugs. Recently, this drug has been universally detected in aquatic environment. However, its potential adverse effects and oxidative stress toxic mechanisms on fish remain unclear. In the present study, we first cloned the crucial partial sequences of some key oxidative stress related genes, which include NF-E2-related factor 2 (Nrf2), NAD(P)H: quinoneoxidoreductase (NQO1), glutamate-cysteine ligase catalytic subunit (GCLC), Cu-Zn superoxide dismutase (SOD2), catalase (CAT), alpha-glutathione S-transferase (GSTA), and UDP-glucuronosyltransferases (UGT) in mosquito fish (Gambusia affinis). We also deduced amino acids of Nrf2 and then constructed the phylogenetic trees of Nrf2, NQO1 and GCLC, respectively. Results showed that a high identity percentage was founded between G. affinis and other bony fish species, such as Xiphophorus maculates and Poecilia reticulate. The transcriptional expression of these genes and partly related enzymes activities were then investigated under the included environmental relevant concentration DCF exposure (0µmolL-1, 1.572×10-3µmolL-1, 1.572×10-2µmolL-1, 0.1572µmolL-1 and 1.572µmolL-1) for 24h and 168h. The expression of Nrf2 was inhibited at 24h but induced at 168h, exhibiting a significant time and/or dose-effect relationship under DCF exposure. Similar observation was found in its downstream target genes. However, Nrf2-mediated antioxidant enzymes activities displayed differently under the same concentration of DCF exposure for the same time. Under DCF exposure for 168h, the genes exhibited dramatic induction trend, but there were no significant changes in enzyme activities and MDA content. Overall, mRNA responses were more sensitive than enzyme changes in mosquito fish under DCF exposure.

Gene response of CYP360A, CYP314, and GST and whole-organism changes in Daphnia magna exposed to ibuprofen.

The fate and ecological impact of non-steroidal anti-inflammatory drugs (NSAIDs) in aquatic environments has gained increasingly concern recently. However, limited information is provided about the toxicity mechanism of NSAIDs to aquatic invertebrates. In the present study, we investigated the expression of CYP360A, CYP314, and GST genes involved in the detoxification process and the responses of their associated enzymes activity, as well as whole-organism changes in Daphnia magna exposed to environmentally relevant concentrations of ibuprofen (IBU). Results showed that the total amount of eggs produced per female, total number of brood per female, and body length were significantly decreased under IBU exposure, suggesting the effects of chronic IBU exposure on growth and reproduction of D. magna cannot be ignored. In gene expression level, the CYP360A gene, homologue to CYP3A in mammalian, showed inhibition at low concentration of IBU (0.5µg·L(-1)) and induction at high concentration of IBU (50µg·L(-1)). GST gene also exhibited a similar performance to CYP3A. CYP314 displayed inhibition for short time exposure (6h) and induced with prolonged exposure time (48h) at low concentration of IBU (0.5µg·L(-1)). Erythromycin N-demethylase (ERND) and aminopyrine N-demethylase (APND) related to cytochrome oxidase P450 (CYPs) were inhibited for short time exposure (6h) to IBU and then activated with prolonged exposure time (48h) at low concentration of IBU (0.5µg·L(-1)), while EROD showed a dose-dependent pattern under IBU exposure. As for antioxidative system, induction of glutathione S-transferase (GST), superoxide dismutase (SOD), and catalase (CAT) was observed in short-term exposure to IBU. Meanwhile, methane dicarboxylic aldehyde (MDA) content increased with the increasing IBU concentration and the delayed exposure time, displaying obvious dose- and time-dependent pattern. In summary, IBU significantly altered some physiological and biochemical parameters and genes expressions associated with detoxification metabolism in D. magna, the integrated approach combining the response in molecule levels with the performance of the whole organism can help elucidate the toxic effects of IBU and provide more insight into the exact mechanism of toxicity in aquatic organisms.

Effects of triclosan on the detoxification system in the yellow catfish (Pelteobagrus fulvidraco): expressions of CYP and GST genes and corresponding enzyme activity in phase I, II and antioxidant system.

Triclosan (TCS), a broad-spectrum antibacterial agent widely used in pharmaceuticals and personal case products (PPCPs), has been universally detected in aquatic ecosystem in recent years. Unfortunately, there is limited information about its potential impacts on responses of genes and enzymes related to fish detoxification. In the present work, we cloned CYP3A and alpha-GST of yellow catfish (Pelteobagrus fulvidraco) and tested the transcriptional expression of CYP1A, CYP3A and GST as well as the alterations of their corresponding enzymes, including ethoxyresorufin-O-deethylase (EROD), aminopyrine N-demethylase (APND), erythromycin N-demethylase (ERND), glutathione S-transferase (GST) and catalase (CAT), and also the oxidative product malondialdehyde (MDA) content in the liver of P. fulvidraco exposed to TCS. Amino acids of CYP3A and GST were deduced and phylogenetic tree was constructed respectively. High identity percent was exhibited between P. fulvidraco and other species, such as other fish, birds and mammals. Results indicated that TCS significantly elevated CYP1A and GST but decreased CYP3A expression, EROD activity and MDA content at lower concentrations of TCS at 24h. Moreover, CYP3A and GST were significantly inhibited at 72 h but induced at 168 h at lower concentrations. However, CYP3A was always induced at the highest concentration during the exposure period. Furthermore, CYP3A, GST, GST enzyme and MDA content exhibited a dose-effect relationship to some extent, but no significant responses were observed in ERND, APND and CAT except for individual treatments. Taken together, EROD was the most sensitive to TCS exposure as compared to other enzymes. Meanwhile, mRNA responses were more sensitive in yellow catfish.