Biodegradability of unheated and laboratory heated dissolved organic matter.

Following wildfires, partially combusted biomass remains on the forest floor and erosion from the landscape can release dissolved pyrogenic organic matter (dPyOM) to surface waters. Therefore, post-fire alterations to dissolved organic matter (DOM) in aquatic systems may play a vital role in DOM stability and biogeochemical cycles. Dissolved PyOM biodegradation remains poorly understood and is expected to vary with combustion temperature and fuel source. In this study laboratory heating and leaching of forest floor materials (soil and litter) were used to compare the biodegradability of unheated, low (250 °C), and moderate (450 °C) temperature leachates. Inoculation experiments were performed with river microbes. Dissolved organic carbon (DOC) and nitrogen (DON), inorganic nitrogen, and DOM optical properties were monitored for 38 days. Inoculation experiments showed significantly greater DOC biodegradation of low and moderate temperature samples (64% and 71%, respectively) compared to unheated samples (32%). The greater DOC biodegradation may be explained by lower molecular weight DOM composition of heated leachates which was supported by higher initial E2/E3 ratios (absorbance at 250 nm/365 nm). Further, the observed decrease in the E2/E3 ratio after incubation suggests biodegradation of smaller compounds. This trend was greater for heated samples than unheated DOM. Specific ultraviolet absorbance increased after incubation, suggesting biodegradation of aliphatic compounds. Inoculated moderate temperature samples showed the greatest DON degradation (74%), followed by low temperature (58%) and unheated (51%) samples. Overall, results suggest that low and moderate temperature dPyOM was more biodegradable than unheated DOM, which may have implications for aquatic biogeochemical cycling, ecosystem function, and water quality in fire-impacted watersheds.

Correction: Emerging investigator series: physicochemical properties of wildfire ash and implications for particle stability in surface waters.

Correction for 'Emerging investigator series: physicochemical properties of wildfire ash and implications for particle stability in surface waters' by Mrittika Hasan Rodela et al., Environ. Sci.: Processes Impacts, 2022, 24, 2129-2139, https://doi.org/10.1039/D2EM00216G.

Emerging investigator series: physicochemical properties of wildfire ash and implications for particle stability in surface waters.

The erosion of wildfire ash from the forest floor to nearby surface waters presents a concern due to potential contamination and alteration of water quality. Meanwhile, the properties of wildfire ash that drive ash particle stability in aquatic systems, mobilization downstream, and transport of contaminants are not well known. Physicochemical properties of ash samples from three wildfires were characterized to understand the relation of ash color and combustion completeness with particle stability and mobilization in aquatic systems. Generally, lighter colored ash, indicative of greater combustion temperatures, had higher pH, electrical conductivity, specific surface area, and zeta potential, and smaller particle size than darker ash and unburned soils. Zeta potential was used as an indication of particle surface charge. White ash had the greatest mean zeta potential (-31.8 ± -11.5 mV), followed by gray ash and dark gray ash. Black ash had similar zeta potential to unburned soils. However, with adjustment to the same pH range the ash and unburned soils had similar mean zeta potentials, although lighter ashes had high variability. Dark gray ash leached the highest organic carbon and nitrogen while white ash leached the lowest C and N, similar to unburned soils. The results suggest that high combustion temperature wildfire ash particles will have greater potential for mobilization downstream and may be more stable in both natural and engineered water systems. However, the high organic matter released from dark gray ashes will likely increase particle stability through steric repulsion. More stable particles have greater potential for downstream transport to aquatic ecosystems or water supplies and increase the possibility of post-fire contamination from ash.

Scientists' warning on extreme wildfire risks to water supply.

2020 is the year of wildfire records. California experienced its three largest fires early in its fire season. The Pantanal, the largest wetland on the planet, burned over 20% of its surface. More than 18 million hectares of forest and bushland burned during the 2019-2020 fire season in Australia, killing 33 people, destroying nearly 2500 homes, and endangering many endemic species. The direct cost of damages is being counted in dozens of billion dollars, but the indirect costs on water-related ecosystem services and benefits could be equally expensive, with impacts lasting for decades. In Australia, the extreme precipitation ("200 mm day -1 in several location") that interrupted the catastrophic wildfire season triggered a series of watershed effects from headwaters to areas downstream. The increased runoff and erosion from burned areas disrupted water supplies in several locations. These post-fire watershed hazards via source water contamination, flash floods, and mudslides can represent substantial, systemic long-term risks to drinking water production, aquatic life, and socio-economic activity. Scenarios similar to the recent event in Australia are now predicted to unfold in the Western USA. This is a new reality that societies will have to live with as uncharted fire activity, water crises, and widespread human footprint collide all-around of the world. Therefore, we advocate for a more proactive approach to wildfire-watershed risk governance in an effort to advance and protect water security. We also argue that there is no easy solution to reducing this risk and that investments in both green (i.e., natural) and grey (i.e., built) infrastructure will be necessary. Further, we propose strategies to combine modern data analytics with existing tools for use by water and land managers worldwide to leverage several decades worth of data and knowledge on post-fire hydrology.

Use of optical properties for evaluating the presence of pyrogenic organic matter in thermally altered soil leachates.

The increased frequency and severity of wildfires in forested watersheds has the potential to significantly impact the quantity and quality of water extractable organic matter (WEOM) exported from these ecosystems. This study examined the optical properties of WEOM from laboratory heated soil in order to understand physicochemical changes occurring in the organic matter as a result of heating, as well as test the usefulness of optical parameters for assessing the presence of pyrogenic organic matter. WEOM absorbance and fluorescence spectral shape and intensity varied systematically as a function of soil heating temperature. Notably, absorbance and fluorescence intensity, specific ultraviolet absorbance, apparent fluorescence quantum yield, specific fluorescence emission intensity, and maximum fluorescence emission wavelength exhibited consistent changes with heating temperature and indicated that WEOM in heated soil leachates was lower in molecular weight and more aromatic than in unheated samples. The lower molecular weight in heated soil WEOM was corroborated with size-exclusion chromatography measurements. This work increases the understanding of the molecular changes occurring in WEOM as a result of wildfire and indicates that optical measurements (i.e., absorbance and fluorescence) could be used for watershed monitoring of post-fire pyrogenic organic matter.

Wildfires Alter Forest Watersheds and Threaten Drinking Water Quality.

Wildfires are a natural part of most forest ecosystems, but due to changing climatic and environmental conditions, they have become larger, more severe, and potentially more damaging. Forested watersheds vulnerable to wildfire serve as drinking water supplies for many urban and rural communities. The highly variable nature of wildfire behavior combined with spatially complex patterns in vegetation, landscape, and hydrologic factors create uncertainty surrounding the postfire effects on water supplies. Wildfires often cause dramatic changes in forest vegetation structure and soil conditions, and alter the watershed processes that control streamflow, soil erosion, nutrient export, and downstream water chemistry. The authors' work centers on field and laboratory studies to advance knowledge of postfire changes in soil and water chemical composition that influence drinking water treatment. High intensity postfire rainstorms typically increase runoff that erodes ash and soil from burned landscapes and dramatically elevates turbidity, nutrient, and dissolved organic carbon (DOC) levels in surface waters, which can cause short-term challenges for water providers. There is also growing evidence that water quality impacts can persist after high severity fires due to slow vegetative recovery, and nitrogen and DOC have remained elevated for 15 years following high severity fire. Low-moderate temperatures during wildfire may also influence water quality. Research by the authors showed that the solubility of organic matter, and C and N released from soils increased following soil heating at temperatures ≤ 350 °C. Further, the water extracted organic matter from soils heated at 225-350 °C included higher proportions of condensed aromatic structures, such as black carbon and black nitrogen. Short-term postfire water quality degradation following high intensity rainstorms can force water treatment plants to shut down or can significantly challenge treatment process performance. Extreme turbidity and high DOC in poststorm water, coupled with compositional organic matter changes, reduced the coagulation efficiency of postfire water supplies. Field and lab-based studies documented the formation of small, aromatic soluble compounds during wildfire that contribute to inefficient DOC removal from postfire stormwater. Due to increased postfire DOC concentrations, and poor treatability of poststorm runoff, toxic disinfection byproduct (DBP) formation increased during water treatment. Exceedance of drinking water standards for the carbonaceous DBPs, trihalomethanes and haloacetic acids, may present a critical management concern for water providers following wildfires. Further, postfire formation of nitrogen compounds and increased nitrogenous DBP precursors for haloacetonitriles and chloropicrin were discovered. N-DBPs pose a public health concern due to their toxicity, and water providers should be aware of potential increases in N-DBP formation following fire. Evidence from the authors' studies demonstrates that even partially burned watersheds and wildfires burning at moderate temperature can have significant, lasting effects on C and N exports, source water quality, drinking water treatability, and DBP formation. Both short- and long-term postfire water quality impacts can create challenges for drinking water providers as they confront variability in supply and treatability. Communities, forest managers, and potable water providers will need to adapt to more frequent, destructive wildfires and anticipate greater variability in water quality.

Persulfate activation by glucose for in situ chemical oxidation.

Sodium persulfate has become the most popular oxidant source for the in situ chemical oxidation (ISCO) treatment of organic contaminants in the subsurface. The most common persulfate activators, iron chelates and base, are often ineffective in initiating the generation of reactive oxygen species in field applications. In this study, glucose was investigated as a persulfate activator in systems containing varying concentrations of sodium hydroxide using nitrobenzene as a hydroxyl radical probe and hexachloroethane as a reductant + nucleophile probe. Glucose activation of persulfate increased as a function of sodium hydroxide addition, but was still effective at circumneutral pH regimes. Use of central composite rotatable experimental designs showed that hydroxyl radical and reductant + nucleophile generation rates increased as a function of persulfate at near-neutral pH regimes. Glucose activation of persulfate has the advantages over other activation pathways of more options and flexibility for effective process chemistry and of minimizing or eliminating the mass of sodium hydroxide added to the subsurface. The results of this research can be applied in the field by first evaluating glucose activation compared to base and iron chelate activation of persulfate in laboratory treatability studies.

Molecular and Spectroscopic Characterization of Water Extractable Organic Matter from Thermally Altered Soils Reveal Insight into Disinfection Byproduct Precursors.

To characterize the effects of thermal-alteration on water extractable organic matter (WEOM), soil samples were heated in a laboratory at 225, 350, and 500 °C. Next, heated and unheated soils were leached, filtered, and analyzed for dissolved organic carbon (DOC) concentration, optical properties, molecular size distribution, molecular composition, and disinfection byproduct (DBP) formation following the addition of chlorine. The soils heated to 225 °C leached the greatest DOC and had the highest C- and N-DBP precursor reactivity per unit carbon compared to the unheated material or soils heated to 350 or 500 °C. The molecular weight of the soluble compounds decreased with increasing heating temperature. Compared to the unheated soil leachates, all DBP yields were higher for the leachates of soils heated to 225 °C. However, only haloacetonitrile yields (µg/mgC) were higher for leachates of the soils heated to 350 °C, whereas trihalomethane, haloacetic acid and chloropicrin yields were lower compared to unheated soil leachates. Soluble N-containing compounds comprised a high number of molecular formulas for leachates of heated soils, which may explain the higher yield of haloacetonitriles for heated soil leachates. Overall, heating soils altered the quantity, quality, and reactivity of the WEOM pool. These results may be useful for inferring how thermal alteration of soil by wildfire can affect water quality.

Drinking water treatment response following a Colorado wildfire.

Wildfires can greatly alter the vegetation, soils, and hydrologic processes of watersheds serving as drinking water supplies, which may negatively influence source water quality and treatment. To address wildfire impacts on treatment, a drinking water intake below a burned watershed and an upstream, unburned reference site were monitored following the High Park wildfire (2012) in the Cache la Poudre watershed of northern Colorado, USA. Turbidity, nutrients, dissolved organic matter (DOM) character, coagulation treatability, and disinfection byproduct formation were evaluated and compared to pre-fire data. Post-fire paired spatial differences between the treatment plant intake and reference site for turbidity, nitrogen, and phosphorus increased by an order of magnitude compared to pre-fire differences. Fluorescence index (FI) values were significantly higher at the intake compared to the reference site (Δ = 0.04), and higher than pre-fire years, suggesting the wildfire altered the DOM character of the river. Total trihalomethane (TTHM) and haloacetonitrile (HAN4) formation at the intake were 10.1 µg L-1 and 0.91 µg L-1 higher than the reference site. Post-fire water was amenable to conventional treatment at a 10 mg L-1 higher average alum dose than reference samples. The intake was also monitored following rainstorms. Post-rainstorm samples showed the maximum observed FI values (1.52), HAN4 (3.4 µg mgC-1) and chloropicrin formation yields (3.6 µg mgC-1), whereas TTHM and haloacetic acid yields were not elevated. Several post-rainstorm samples presented treatment challenges, and even at high alum doses (65 mg L-1), showed minimal dissolved organic carbon removal (<10%). The degraded water quality of the post-rainstorm samples is likely attributed to the combined effects of runoff from precipitation and greater erosion following wildfire. Wildfire impacts cannot be separated from rainfall effects due to the lack of post-rainstorm samples from the reference site. Results suggest for this study region, wildfire may have consequences for influent water quality, coagulant dosing, and DBP speciation.