Article

Cite This: Acc. Chem. Res. 2019, 52, 1234−1244 [Link]/accounts

Wildfires Alter Forest Watersheds and Threaten Drinking Water

Quality
Published as part of the Accounts of Chemical Research special issue “Water for Two Worlds: Urban and Rural
Communities”.
Amanda K. Hohner,*,† Charles C. Rhoades,‡ Paul Wilkerson,§ and Fernando L. Rosario-Ortiz*,§
†
Department of Civil and Environmental Engineering, Washington State University, Pullman, Washington 99164, United States
‡
USDA Forest Service, Rocky Mountain Research Station, 240 W. Prospect, Fort Collins, Colorado 80521, United States
§
Department of Civil, Environmental, and Architectural Engineering, University of Colorado, Boulder, Colorado 80309, United
States

CONSPECTUS: 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
continued...

Received: December 28, 2018

Published: May 6, 2019

© 2019 American Chemical Society 1234 DOI: 10.1021/[Link].8b00670

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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.

■ INTRODUCTION
Wildfires are a natural part of most forest ecosystems, but due
The wide range of short- and long-term postfire water
quality changes can lead to significant challenges for down-
to changing climatic and environmental conditions, wildfires stream water treatment plants that will have to confront
pose a greater threat to forest watersheds across the United variability in supply and treatability. An assortment of potential
States and globally. Higher temperatures and prolonged postfire water treatment implications may occur and vary in
droughts have extended fire season lengths worldwide during timing and magnitude for individual fires and water systems.
recent decades and generated larger, more severe wildfires.1,2 A Extreme postfire erosion can damage infrastructure, accumu-
century of wildfire suppression has increased tree densities3 late in reservoirs, and challenge coagulation, filtration, and
and unprecedented levels of tree mortality during recent bark solids handling processes.22,23 Elevated nutrients combined
beetle outbreaks4 have elevated dead fuel loads in many with greater light exposure and stream temperatures may lead
western North American forests. These conditions are to postfire algal blooms in reservoirs, which can adversely affect
aggravated by reduced forest management and growing aquatic life, release harmful toxins, and strain water treatment
residential and recreational development within the wildland- operations.22,24 Postfire increases in metal concentrations have
urban interface.5 Furthermore, projected increases in warming been documented,25,26 and may create taste and odor issues, or
and drying are predicted to increase wildfire potential in the toxicity concerns. Changes in the quantity and composition of
United States, South America, Australia, and parts of Asia, dissolved organic matter (DOM) exported from burned
Europe, and Africa.6−8 Recently, wildfires have claimed human watersheds can influence treatment process performance and
lives, destroyed property and infrastructure, and devastated the formation of disinfection byproducts (DBPs). DBPs
communities in the United States, Europe, and Australia.9−11 include probable human carcinogens such as trihalomethanes
These aggregate changes have prompted a growing awareness and haloacetic acids, that are regulated by the U.S. Environ-
of the need for communities, forest managers, and potable mental Protection Agency (EPA) in finished water,27 and
water providers to adapt to more destructive wildfires.12,13 currently unregulated nitrogen based DBPs (N-DBPs; e.g.,
Forested watersheds vulnerable to wildfire commonly haloacetonitriles). Though general understanding of wildfire
function as drinking water supplies for downstream commun- effects is advancing, drinking water providers require greater
ities in both rural and urban settings. Wildfires can drastically clarity regarding expected magnitude and duration of postfire
impact the vegetation, soils and watersheds that regulate changes in the chemical composition of source waters to
significant sources of water supplies for municipal and other anticipate the consequences of future wildfires. The objective
uses.14 Combustion and loss of forest vegetation and organic of this paper is to synthesize recent work completed by the
authors and other research teams that examines the links
soil cover during severe wildfires expose soils to short-term
between wildfire behavior and postfire soil and water changes
(e.g., months) sediment, nutrient, metal and organic matter
that influence water treatment processes and drinking water
losses, significantly altering the biogeochemical processes quality.

■
which control water quality.15−18 Wildfires can also influence
water quality over longer time frames (e.g., >10 years) by WILDFIRE TRANSFORMATIONS ON THE
reducing plant nutrient demand and increasing soil nutrient LANDSCAPE
availability.19−21 Water quality consequences vary with wildfire
Wildfire extent and severity, the relative amount of vegetation
behavior (e.g., severity, extent, location) and the physical and and organic matter combusted, influence the magnitude and
hydrologic components of a watershed. Wildfire behavior is a duration of water quality responses. In North American forests,
complex response to weather (i.e., wind, temperature, relative high-severity wildfires combust most vegetation and soil
humidity), fuel (i.e., amount, spatial arrangement, moisture organic layers,28 and the dramatic changes in forest vegetation
content) and landscape (i.e., slope gradient and aspect) structure and soil conditions alter the watershed processes that
conditions. These factors influence the combustion temper- control streamflow, soil erosion, nutrient export, and down-
ature, oxygen level and duration, fire rate of spread, degree of stream water chemistry.29−31 In contrast, low-severity fire kills
canopy and surface fuel consumption, and production of few overstory trees and has minimal effect on belowground
pyrogenic material that all affect how watersheds respond plant structures, organic soil layers (e.g., litter and duff), and
following wildfire. The highly variable nature of wildfire watershed conditions. The vegetation and organic soil32,33
behavior combined with spatially complex patterns in remaining after less severe wildfires typically limit postfire
vegetation, landscape, hydrologic, and other factors contribute changes in water quality and facilitate watershed recovery.34
to large uncertainty surrounding the postfire effects on surface Soil heating during wildfires causes physical and chemical
water composition and drinking water treatment. changes in soil layers that determine wildfire effects on the
1235 DOI: 10.1021/[Link].8b00670
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surrounding ecosystem. For instance, wildfires create a water 550 °C for both organic and mineral soils. Though soils can
repellent layer of hydrophobic compounds35,36 that increase exceed 550 °C during wildfires, above this temperature DOM
surface runoff.37 While wildfires may consume organic soil export to surface waters would be minimal.
layers, carbon-rich input from charred vegetation can be Of particular interest is the observation that the apparent
incorporated into the soil profile.38 Following fires, ash is the solubility of the soil organic matter (SOM) increased at low-
particulate residue composed of mineral and charred organic moderate temperatures (≤350 °C).42 Water extractable
materials that have been chemically and physically altered organic C and organic N (i.e., WEOC = DOC/total soil C
during combustion.39 Ash is readily entrained and mobilized and WEON = dissolved organic nitrogen (DON)/total soil N,
by overland runoff and transported downslope and down- respectively) in mineral soil layers peaked between 250 and
stream, impacting water quality. 350 °C (Figure 2). Another study performed by Santos et al.
The authors quantified the relationship between combustion observed similar trends where the amount of DOC leached
temperature, atmospheric carbon losses, and compositional from soils peaked at 250 °C.43 In the current study, for the
changes that influence DOM export from organic (O horizon) organic soil layers, WEOC and WEON decreased dramatically
and mineral (A horizon) soil layers across a range of above 150 °C, indicating that in this soil layer water-soluble C
temperatures (150−550 °C). Soil layers were heated for 2 h and N forms are more susceptible to combustion losses at low
under oxic conditions intended to simulate wildfire con- temperatures. Overall, these findings suggest that low-
ditions40 and to systematically evaluate the effect of temper- moderate temperature heating during wildfires may increase
ature on soil properties. In addition to temperature, oxygen the amount of C and N leached from soils, despite losses to the
availability and duration of heating also vary during wildfires atmosphere. The increased transport of organic carbon and
and were considered in work by others.41 Combustion of C nitrogen via overland and subsurface flow paths significantly
and N increased with heating temperature, and the residual alters downstream water chemistry.
amount in the solid phase decreased (Figure 1). C and N The increased solubility of SOM at low-moderate temper-
losses from the O horizon occurred at temperatures as low as atures could be the aggregate effect of physical changes in soil
structure and chemical changes that influence SOM
150 °C and complete gaseous losses occurred between 450 and
composition. A study by Jian et al.44 showed that increasing
temperature disrupts soil aggregates due to rapid vaporization
of pore water, thus exposing physically protected SOM to
leaching. However, results from the current study suggest that
changes in SOM chemistry are also responsible for enhanced
release of DOC and DON from soils after heating.42 Work by
Cawley and co-workers42 indicates that, after heating soils at
225−350 °C, the water extracted organic matter included
higher proportions of condensed aromatic structures, such as
black carbon and black nitrogen (Figure 3). Black carbon can
form during high temperature biomass combustion and is
characterized by a highly condensed aromatic structure.45
Black carbon exports to surface waters have been observed
after wildfires.46 Black nitrogen is characterized by small,
dense, heteroaromatic N compounds that form during the
heating and transformation of peptides,47 and is important to
the chemical composition of postfire char.48 Changes in
chemical composition and overall export of DOM from
wildfire impacted watersheds can influence water treatment
and the reactivity to form DBPs. Although there is still lack of
clarity on chemical and physical mechanisms which explain the
aforementioned discussion, the variability and range of wildfire
impacts on water quality are evidenced by postfire monitoring
studies.

■ POSTFIRE VARIABILITY IN WATER QUALITY

The landscape, vegetation, and soil changes that determine
postfire water quality reflect fire extent, severity, and watershed
specific factors. The authors studied the short-term changes in
source water quality the first year after the 2012 High Park Fire
which burned the Cache la Poudre (CLP) watershed in
northern Colorado.23 The CLP River provides drinking water
to over 300 000 municipal consumers and serves as a
significant water supply for regional agricultural users.
Comparison of streamwater from an unburned, upstream
Figure 1. Carbon (top panel) and nitrogen (bottom panel) remaining reference site and a municipal water intake within the burned
in organic and mineral soil horizons after heating. Soil samples were area revealed significant changes following the fire (Figure 4).
collected from a watershed west of Boulder, Colorado, USA. CTRL = Turbidity, total phosphorus (TP), and total nitrogen (TN)
control. increased by an order of magnitude the first year following the
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Figure 2. Water extractable organic carbon (WEOC, left) and nitrogen (WEON, right) for both organic and mineral soil horizons. The water
extractable fraction is calculated from the dissolved organic carbon (DOC) or dissolved organic nitrogen (DON) leached per unit total soil C and
N, respectively, remaining after heating. CTRL = control.

Figure 3. High resolution mass spectroscopy results showing the percent assigned formulas for unheated, low (225 °C) and moderate (350 °C)
temperature soil leachates. HG soils were collected from the 2012 Hewlett Gulch Fire burn area in the Cache la Poudre watershed in northern
Colorado. PBR soils were collected from an unburned soil site from the same watershed. Reproduced with permission from ref 42. Copyright 2016
American Chemical Society.

fire. Total organic carbon (TOC) concentrations also catchments burned at high severity (Figure 5). Notably,
increased and were much more variable after the fire. DOC remained elevated for 15 years51 compared to the
Turbidity, TP, TN, and TOC all reached extremely high sediment erosion responses that largely subsided within the
levels following postfire rainstorms.23 first 5 postfire years.50 These patterns create substantial
The magnitude of water quality responses often increase variability in postfire water chemistry that generate short and
with the proportion of a watershed exposed to high severity long-term challenges for water treatment systems.

■
wildfire. For example, two research watersheds at the San
Dimas Experimental Forest in southern California that were POSTFIRE VARIABILITY IN WATER TREATMENT
burned at high severity released 7-times more nitrate than
watersheds burned at lower severity.49 Similarly, during the Severe wildfires cause extremely high fluctuations in source
first 5 years after Colorado’s Hayman Fire, individual water quality that can challenge water treatment operations,
watersheds that sustained high severity wildfire on >45% of process selection, and long-term planning. High intensity,
their area had nitrate and turbidity roughly 3-fold the levels postfire rainstorms are the greatest concern for drinking water
measured in basins with ≤10% burned under such treatment plants, specifically small, single source systems
conditions.50 Plant nutrient demand remained low due to without the ability to bypass highly turbid water. When intense
slow vegetation recovery in areas burned at high severity, so storms fall on recently burned landscapes they dramatically
stream total dissolved nitrogen (TDN) levels have remained increase surface runoff that erodes ash and soil and degrades
elevated for 15 years after the Hayman Fire (Figure 5),51 water quality.53,54 Turbidity and DOM are the key variables
though postfire total suspended sediment (TSS) levels have that drive treatment operations, and abrupt and extreme
abated. In contrast, the unburned and partially charred organic postfire spikes in these parameters may necessitate additional
material retained on the forest floor following less severe treatment, or cause a plant to shut down.55 Smaller and
wildfires represent sustained inputs of carbon to streams sustained seasonal increases in turbidity or DOM may require
resulting in higher DOC concentrations, compared to greater coagulant dosing, and result in shorter filter run times
1237 DOI: 10.1021/[Link].8b00670
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Figure 4. Paired differences in streamwater concentrations at an unburned, upstream reference site and near a municipal water intake within the
High Park Fire (2012) burn area before and the first year after the fire. Samples were collected biweekly or monthly from May to October; n = 10−
11 per year, per site. The dashed line indicates a difference of zero between the burned site and reference site. Reproduced with permission from ref
23. Copyright 2016 Elsevier.

and increased solids processing, but the effects are less severe area (water intake) were statistically higher than the reference
than postfire rainstorms. site (+ 0.038), and higher than prefire data.23 In a different
Postfire changes in DOM composition influence coagulation study, the authors also observed an increase in FI and blue-
efficiency22,23 and DBP precursor reactivity and speciation.56,57 shifted emission spectra for leachates of soils heated at a
The authors studied the relations between DOM alterations moderate temperature (350 °C).42 Similarly, Wang et al.
and drinking water treatability for the first year following the (2015) reported higher FI for burned detritus extracts from the
2012 High Park Fire.23 The efficacy of conventional treatment Rim Fire compared to unburned detritus,56 providing addi-
(i.e., coagulation/flocculation/sedimentation/filtration) with tional evidence for post-fire changes in DOM chemistry.
aluminum sulfate (alum) for DOM removal, and carbonaceous There is also parallel evidence for an increase in hydro-
and nitrogenous DBP formation upon chlorination were phobic, aromatic compounds that are preferentially removed
evaluated. Postfire rainstorms created turbidity (>4000 ntu) by coagulation. For example, a higher SUVA254 (4.5 ± 0.9 L/
and DOC spikes (>18 mgC/L) and significant treatment mg·m), consistent with more aromatic DOM,59 was observed
challenges that resulted in closure of the water intake.23,58 for postfire storm samples. The higher raw water SUVA254
Higher alum doses (e.g., 65 mg/L) were applied to the should favor DOC removal.63−66 However, SUVA254 primarily
rainstorm samples to optimize treatment, yet in spite of that, captures DOM chromophores that absorb light at 254 nm,
DOC removal was limited to nearly half of that removed from while this work shows that smaller, aromatic, soluble
the nonstorm samples (i.e., 34% vs 60% removal) (Figure 6). compounds that evade coagulation are likely also formed
Substantial aromatic DOM (i.e., high specific ultraviolet during wildfire. The level of DOM aromaticity appears to be
absorbance at 254 nm: SUVA254) remained in the treated regulated by combustion temperature, with more aromatic
stormwater.59 Consequently, due to the high residual DOC DOM released from ash formed at high temperature.56
and high aromatic content, formation of the C-based DBPs Coagulation efficiency was reduced by high turbidity and
total trihalomethanes (TTHMs) and five regulated haloacetic DOC, combined with DOM compositional changes (i.e., shift
acids (HAA5s) exceeded maximum contaminant levels for in molecular weight, changes in polarity), in stormwater after
nearly all post rainstorm treated water samples.23 the High Park Fire.23
Greater abundance of lower molecular weight compounds To complement previous work, and further investigate the
may contribute to inefficient DOC removal from postfire effects of forest floor heating on changes in DOM character
stormwater due to the hydrophilic nature of the DOM and coagulation treatment, organic and mineral soil layers were
composition compared to higher molecular weight, hydro- heated in the laboratory at 225 °C to simulate wildfire.67,68
phobic humic substances.60,61 The DOM sampled in postfire Field and laboratory studies have shown low-temperature
rainstorms had a higher fluorescence index (FI) (Figure 7), heating may have greater consequences for DOC transport to
correlated with a lower molecular weight DOM composition,62 source waters than higher temperatures when more organic
which is more challenging to remove by coagulation.60,63 matter is combusted. Unheated (control) and heated soil
Further, the FI values of samples collected from the burned layers were leached and treated with aluminum sulfate
1238 DOI: 10.1021/[Link].8b00670
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Figure 5. Seasonal mean nitrate, total dissolved nitrogen (TDN), dissolved organic carbon (DOC), and total suspended sediment (TSS)
concentrations from four catchments burned by the 2002 Colorado Hayman Fire and two nearby, unburned catchments. Burn Extent classes as
follows: High Extent: >60% burned, Low Extent: 30−60% burned, and unburned. Means were derived from 2015 and 2016 monthly samples for
two catchments per Burn Extent class (n = 12 for each season). The dashed line on the TDN panel denotes the proposed TN threshold
concentrations for least-impaired reference streams in the Western Forest Region.52 Reproduced with permission from ref 51. Copyright 2018
Springer Nature.

coagulation. The leachates had similar raw water turbidity and removal for the control samples (Figure 8). That is, 0.03 and
DOC concentrations, but the heat-altered DOM was less 0.09 mg of DOC removed/mg of alum for the heated and
amenable to coagulation, and even at optimal alum dosing only control samples, respectively. It is evident that low temperature
24 ± 4.8% DOC removal was achieved compared to 55 ± 6.7% heating imparted clear changes in DOM composition that
1239 DOI: 10.1021/[Link].8b00670
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Figure 6. Raw water (streamwater) DOC concentrations of samples collected from a water intake during baseflow and spring snowmelt conditions
and following rainstorms in the High Park Fire burn area the first postfire year. Treated water aluminum sulfate (alum) coagulant doses, DOC, and
SUVA254 (specific ultraviolet absorbance at 254 nm) are shown. Data are means (n = 6) with standard deviation. Data from ref 23.

heating findings confirm the post rainstorm observations after

the High Park Fire.23 Wildfire changes to DOM chemistry
should also be considered along with greater DOC and
sediment loads drinking water treatment facilities may
experience following fire.

■ WILDFIRE EFFECTS ON DISINFECTION

BYPRODUCT PRECURSOR REACTIVITY
A shift in DOM composition from wildfire heating may
influence DBP formation and speciation during water treat-
ment. Following the High Park Fire, post rainstorm samples
had elevated haloacetonitrile (HAN) and chloropicrin
precursor reactivity, whereas TTHM and HAA5 reactivity
was similar to nonstorm samples.23 To further explore postfire
sources of DBP precursors, charred sediments that were
Figure 7. Seasonally varying fluorescence index (FI) values of pre- eroded by rainstorms from the High Park Fire burn area and
and postfire (2013) samples collected from a water intake within the
High Park Fire burn area and an unburned, upstream reference site.
mobilized to the riverbank were collected.57 The sediments
Prefire FI data were collected for both sites in 2008 and 2009. were leached in source water and low carbon tap water (LCT)
Samples were also collected from the water intake following with minimal background organic matter (DOC < 0.3 mgC/L).
rainstorms in the burn area. Reproduced with permission from ref Sediment masses were added to leach between 2 and 5 mgC/L
23. Copyright 2016 Elsevier. DOC. TTHM and HAA5 formation showed similar trends for
the source waters with no sediments added (baseline waters)
and sediment leachates (Figure 9), which indicates the wildfire
adversely affected the coagulation response. Although the heat- did not significantly alter C-DBP precursor reactivity.
altered DOM was more aromatic (i.e., higher SUVA254), size However, N-DBP precursors were affected by the fire, and
exclusion chromatography-UV analysis showed a clear shift sediment leachates formed higher N-DBPs per unit carbon
toward lower molecular weight DOM.67 Optical indices (E2/ than baseline waters (Figure 9). The LCT leachates showed
E3 and Sr) are inversely related to DOM size.69,70 Work by the the highest overall N-DBP precursor reactivity. It appeared
authors67 and others41 related increases in E2/E3 and Sr that DOM leached from wildfire affected sediments was more
following heating to a smaller DOM composition. Wang et al. reactive for N-DBP formation when background organic
found that, in addition to combustion temperature, oxygen matter was negligible. Competition from DBP precursors
availability influenced DOM chemistry, with higher SUVA254 present in the source water may have restricted the reactivity of
released from DOM formed under oxic conditions compared the DOM leached from the sediments. Another study by Wang
to DOM released after anoxic combustion. The laboratory et. al (2015) leached organic soil layers from the California
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Figure 8. Decimal fraction of DOC remaining (DOC/DOC0) and specific ultraviolet absorbance (SUVA254) versus applied aluminum sulfate
(alum) dose for control and heated samples from municipal watersheds in Colorado (Westminster, WM and Denver, DW) and New York (NY).
Alum doses are reported as Al2(SO4)318H2O. Data from ref 67.

Figure 9. DBP formation vs DOC concentration for TTHM, HAA5, HAN4, and chloropicrin. Baseline waters were collected from source water
supplies for two utilities. Wildfire-affected sediments were added to source waters (Source Water Leachates) and low carbon tap water (LCT
Leachates). Solid symbols represent raw waters and open symbols indicate treated waters. Linear trend lines show when a significant (p < 0.05)
correlation was observed. Reproduced with permission from ref 57. Copyright 2017 The Royal Society of Chemistry.

1241 DOI: 10.1021/[Link].8b00670

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Rim Fire and observed an increase in HAN and N-Nitroso-

dimethylamine (NDMA) reactivity for white (high severity)
■ AUTHOR INFORMATION
Corresponding Authors
and black ash (moderate severity) extracts compared to
unburned organic soil layers.56 *E-mail: ahohner@[Link].
*E-mail: [Link]@[Link].
The observed increase in N-DBP precursors may be
explained by wildfire alterations to the landscape. Lower ORCID
plant nutrient demand increases soil N that may release N- Fernando L. Rosario-Ortiz: 0000-0002-3311-9089
DBP precursors to surface waters, while partially charred soils Funding
and vegetative debris can be significant sources of organic
nitrogen, depending on the level of combustion.47,68,71 The authors are grateful for financial support from the Joint
Fire Sciences Program (JFSP# 14-1-06-11) and the US Forest
Following rainstorms in the High Park Fire burn area, samples
Service, National Fire Plan (2016−2019). This work was
were enriched in organic nitrogen, which suggests smaller,
further supported by the Colorado Department of Public
more hydrophilic organic moieties in the postfire runoff,72 and Health and Environment, the Water Research Foundation
likely reactive N-DBP precursors.73 A shift in DBP speciation (Project numbers 4590 and 4524), the Environmental
toward more nitrogenous precursors was consistently observed Protection Agency (Grant # R835865) and the National
for the High Park Fire post rainstorm samples and sediment Science Foundation (Award #1512705).
leachates, and for other fires.56
Notes
Laboratory studies demonstrate that heat-alterations to
DOM may enhance N-DBP reactivity. The authors observed The authors declare no competing financial interest.
higher C- and N-DBP precursor reactivity for soils heated at Biographies
225 °C under oxic conditions, and enhanced haloacetonitrile
(HAN) reactivity for soils heated at 350 °C.42 Similarly, Wang Amanda K. Hohner is an assistant professor in the Department of
et al. reported increased HAN reactivity following heating at Civil and Environmental Engineering at Washington State University.
400 °C under oxic conditions, but observed a decrease in HAN Dr. Hohner’s primary area of expertise is the evaluation of the effects
of extreme events and watershed disturbances on the resiliency of
reactivity for samples heated at the same temperature under
potable water systems.
anoxic conditions.41 Wildfire formation of reactive nitrogen
compounds is supported by an increase in black nitrogen from Charles C. Rhoades is a research biogeochemist with the USDA
low-moderate temperature heating (Figure 3), however further Forest Service at the Rocky Mountain Research Station in Fort
research on black nitrogen and N-DBP precursors is warranted. Collins, Colorado. Dr. Rhoades studies the consequences of forest
N-DBPs are currently not regulated, but may be more of a disturbance and land management on the watershed processes that
health concern than regulated C-DBPs.74,75 Evidence from regulate water quality and soil and ecosystem productivity.
these studies indicates that nitrogenous DBP formation in Paul Wilkerson is a graduate student in the Environmental
drinking water could be elevated following wildfire. Engineering Program at the University of Colorado, Boulder. Paul’s

■
main interest is in the study of how wildfires impact soil chemistry
FUTURE OUTLOOK and ultimately water quality.
Fernando L. Rosario-Ortiz is a Professor at the Department of Civil,
More extreme and frequent wildfires create a new set of
Environmental and Architectural Engineering and with the Environ-
unknowns about postfire conditions with significant con-
mental Engineering Program at the University of Colorado, Boulder.
sequences for water supply and treatability. There is need to
Prof. Rosario-Ortiz studies different aspects of water quality, including
design and conduct studies that explicitly couple spatial the effects of wildfires on water quality and environmental
variability of wildfire behavior and fuel combustion with photochemistry.

■
chemical changes in soil and water to evaluate laboratory and
field-based observations across a range of conditions. In
ACKNOWLEDGMENTS
addition to characterizing wildfires, these approaches have
utility for evaluating the biogeochemical consequences and The authors acknowledge the contributions of Ariel Retuta and
Yun Yu to the research described herein.

■
effectiveness of postfire watershed rehabilitation treatments,
prescribed fire, and forest fuel removal activities aimed at
reducing threats to water supplies from severe wildfire. There REFERENCES
is also the need to account for the added capital, operational, (1) Westerling, A. L. Increasing Western US Forest Wildfire Activity:
and monitoring costs of treating water from burned water- Sensitivity to Changes in the Timing of Spring. Philos. Trans. R. Soc., B
2016, 371, 20150178.
sheds, and to evaluate how adjustments and investments in
(2) Sommerfeld, A.; Senf, C.; Buma, B.; D’Amato, A. W.; Després,
treatment processes may help communities adapt to higher T.; Díaz-Hormazábal, I.; Fraver, S.; Frelich, L. E.; Gutiérrez, Á . G.;
frequency of severe wildfires. The short- and long-term risks Hart, S. J.; Harvey, B. J.; He, H. S.; Hlásny, T.; Holz, A.; Kitzberger,
water providers may experience, and the probability of such T.; Kulakowski, D.; Lindenmayer, D.; Mori, A. S.; Müller, J.; Paritsis,
occurrences need to be understood to strengthen the resiliency J.; Perry, G. L. W.; Stephens, S. L.; Svoboda, M.; Turner, M. G.;
of potable water supplies. Communities in fire-prone Veblen, T. T.; Seidl, R. Patterns and Drivers of Recent Disturbances
ecosystems confront the significant challenge of how to Across the Temperate Forest Biome. Nat. Commun. 2018, 9, 2833.
(3) Dennison, P. E.; Brewer, S. C.; Arnold, J. D.; Moritz, M. A. Large
develop and operate efficient drinking water systems to treat Wildfire Trends in the Western United States, 1984−2011. Geophys.
higher sediment, nutrients, and DOM exported from burned Res. Lett. 2014, 41, 2928−2933.
watersheds, as well as unknown risks from changing fire (4) Raffa, K. F.; Aukema, B. H.; Bentz, B. J.; Carroll, A. L.; Hicke, J.
behavior. A.; Turner, M. G.; Romme, W. H. Cross-Scale Drivers of Natural

1242 DOI: 10.1021/[Link].8b00670

Acc. Chem. Res. 2019, 52, 1234−1244
Accounts of Chemical Research Article

Disturbances Prone to Anthropogenic Amplification: the Dynamics of Downstream Legacy Effects After Wildfire in Large River Systems.
Bark Beetle Eruptions. BioScience 2008, 58, 501−517. Global Change Biology 2016, 22, 1168−1184.
(5) Radeloff, V. C.; Helmers, D. P.; Kramer, H. A.; Mockrin, M. H.; (25) Rust, A. J.; Hogue, T. S.; Saxe, S.; McCray, J. Post-Fire Water-
Alexandre, P. M.; Bar-Massada, A.; Butsic, V.; Hawbaker, T. J.; Quality Response in the Western United States. Int. J. Wildland Fire
Martinuzzi, S.; Syphard, A. D.; Stewart, S. I. Rapid Growth of the US 2018, 27, 203.
Wildland-Urban Interface Raises Wildfire Risk. Proc. Natl. Acad. Sci. (26) Smith, H. G.; Sheridan, G. J.; Lane, P. N. J.; Nyman, P.;
U. S. A. 2018, 115, 3314−3319. Haydon, S. Wildfire Effects on Water Quality in Forest Catchments: a
(6) Liu, Y.; Stanturf, J.; Goodrick, S. Trends in Global Wildfire Review with Implications for Water Supply. J. Hydrol. 2011, 396,
Potential in a Changing Climate. For. Ecol. Manage. 2010, 259, 685− 170−192.
697. (27) United States Environmental Protection Agency. Office of
(7) Hurteau, M. D.; Westerling, A. L.; Wiedinmyer, C.; Bryant, B. P. Water. Comprehensive Disinfectants and Disinfection Byproducts Rules
Projected Effects of Climate and Development on California Wildfire (Stage 1 and Stage 2: Quick Reference Guide); 2010; EPA 816-F-10-
Emissions Through 2100. Environ. Sci. Technol. 2014, 48, 2298−2304. 080; pp 1−2; [Link]
(8) Jolly, W. M.; Cochrane, M. A.; Freeborn, P. H.; Holden, Z. A.; (28) Keeley, J. E. Fire Intensity, Fire Severity and Burn Severity: a
Brown, T. J.; Williamson, G. J.; Bowman, D. M. J. S. Climate-Induced Brief Review and Suggested Usage. Int. J. Wildland Fire 2009, 18, 116.
Variations in Global Wildfire Danger From 1979 to 2013. Nat. (29) Spencer, C. N.; Hauer, F. R. Phosphorus and Nitrogen
Commun. 2015, 6, 7537. Dynamics in Streams During a Wildfire. Journal of the North American
(9) BBC. Portugal Wildfires: Why Are They So Deadly? [Link]. Benthological Society 1991, 10 (1), 24−30.
com; June 1, 2017. (30) Robichaud, P. R.; MacDonald, L. H.; Freeouf, J.; Neary, D.;
(10) Jergler, D. Official Figure on Insured Losses for 2018 California Martin, D.; Ashmun, L. E. Postfire Rehabilitation of the Hayman Fire;
Wildfires Reaches $9B; [Link]. USDA Forest Service Rocky Mountain Research Station General
(11) Blanchi, R.; Lucas, C.; Leonard, J.; Finkele, K. Meteorological Technical Report, 14,; 2003; pp 1−22.
Conditions and Wildfire-Related Houseloss in Australia. Int. J. (31) Blake, W. H.; Theocharopoulos, S. P.; Skoulikidis, N.; Clark, P.;
Wildland Fire 2010, 19, 914. Tountas, P.; Hartley, R.; Amaxidis, Y. Wildfire Impacts on Hillslope
(12) Schoennagel, T.; Balch, J. K.; Brenkert-Smith, H.; Dennison, P. Sediment and Phosphorus Yields. J. Soils Sediments 2010, 10, 671−
E.; Harvey, B. J.; Krawchuk, M. A.; Mietkiewicz, N.; Morgan, P.; 682.
Moritz, M. A.; Rasker, R.; Turner, M. G.; Whitlock, C. Adapt to More (32) Pannkuk, C. D.; Robichaud, P. R. Effectiveness of Needle Cast
Wildfire in Western North American Forests as Climate Changes. at Reducing Erosion After Forest Fires. Water Resour. Res. 2003, 39,
Proc. Natl. Acad. Sci. U. S. A. 2017, 114, 4582−4590. 1515.
(13) Higuera, P. E. Taking Time to Consider the Causes and (33) Cerdà, A.; Doerr, S. H. The Effect of Ash and Needle Cover on
Consequences of Large Wildfires. Proc. Natl. Acad. Sci. U. S. A. 2015, Surface Runoff and Erosion in the Immediate Post-Fire Period.
112, 13137−13138. Catena 2008, 74, 256−263.
(14) Bladon, K. D.; Emelko, M. B.; Silins, U.; Stone, M. Wildfire and (34) Wagenbrenner, J. W.; MacDonald, L. H.; Rough, D.
the Future of Water Supply. Environ. Sci. Technol. 2014, 48, 8936− Effectiveness of Three Post-Fire Rehabilitation Treatments in the
8943. Colorado Front Range. Hydrol. Processes 2006, 20, 2989−3006.
(15) Bormann, B. T.; Homann, P. S.; Darbyshire, R. L.; Morrissette, (35) DeBano, L. F. The Role of Fire and Soil Heating on Water
B. A. Intense Forest Wildfire Sharply Reduces Mineral Soil C and N: Repellency in Wildland Environments: a Review. J. Hydrol. 2000, 231,
the First Direct Evidence. Can. J. For. Res. 2008, 38, 2771−2783. 195−206.
(16) Homann, P. S.; Bormann, B. T.; Darbyshire, R. L.; Morrissette, (36) DeBano, L. F. Water Repellency in Soils: a Historical Overview.
B. A. Forest Soil Carbon and Nitrogen Losses Associated with J. Hydrol. 2000, 231, 4−32.
Wildfire and Prescribed Fire. Soil Science Society of America Journal (37) Neary, D. G.; Ice, G. G.; Jackson, C. R. Linkages Between
2011, 75, 1926. Forest Soils and Water Quality and Quantity. For. Ecol. Manage. 2009,
(17) Larsen, I. J.; MacDonald, L. H.; Brown, E.; Rough, D.; Welsh, 258, 2269−2281.
M. J.; Pietraszek, J. H.; Libohova, Z.; de Dios Benavides-Solorio, J.; (38) Knicker, H.; González-Vila, F. J.; Polvillo, O.; Gonzalez, J.;
Schaffrath, K. Causes of Post-Fire Runoff and Erosion: Water Almendros, G. Fire-Induced Transformation of C- and N- Forms in
Repellency, Cover, or Soil Sealing? Soil Sci. Soc. Am. J. 2009, 73, 1393. Different Organic Soil Fractions From a Dystric Cambisol Under a
(18) Pierson, D. N.; Robichaud, P. R.; Rhoades, C. C.; Brown, R. E. Mediterranean Pine Forest (). Soil Biol. Biochem. 2005, 37, 701−718.
Carbon and Nitrogen Eroded From Burned Forests in the Western (39) Bodí, M. B.; Martin, D. A.; Balfour, V. N.; Santín, C.; Doerr, S.
U.S. Int. J. Wildland Fire 2019, DOI: 10.1071/WF18193. H.; Pereira, P.; Cerdà, A.; Mataix-Solera, J. Wildland Fire Ash:
(19) Wan, S. Q.; Hui, D. F.; Luo, Y. Q. Fire Effects on Nitrogen Production, Composition and Eco-Hydro-Geomorphic Effects. Earth-
Pools and Dynamics in Terrestrial Ecosystems: a Meta-Analysis. Sci. Rev. 2014, 130, 103−127.
Ecological Applications 2001, 11, 1349−1365. (40) Retuta, A. M. Effect of Heating Temperature on Dissolvable
(20) Certini, G. Effects of Fire on Properties of Forest Soils: a Constituents From Soil and Litter Material in the Colorado Front
Review. Oecologia 2005, 143, 1−10. Range. Masters Thesis, University of Colorado at Boulder, 2018; pp
(21) Turner, M. G.; Smithwick, E. A. H.; Metzger, K. L.; Tinker, D. 1−111.
B.; Romme, W. H. Inorganic Nitrogen Availability After Severe Stand- (41) Wang, J.-J.; Dahlgren, R. A.; Chow, A. T. Controlled Burning of
Replacing Fire in the Greater Yellowstone Ecosystem. Proc. Natl. Forest Detritus Altering Spectroscopic Characteristics and Chlorine
Acad. Sci. U. S. A. 2007, 104, 4782−4789. Reactivity of Dissolved Organic Matter: Effects of Temperature and
(22) Emelko, M. B.; Silins, U.; Bladon, K. D.; Stone, M. Implications Oxygen Availability. Environ. Sci. Technol. 2015, 49, 14019−14027.
of Land Disturbance on Drinking Water Treatability in a Changing (42) Cawley, K. M.; Hohner, A. K.; Podgorski, D. C.; Cooper, W.
Climate: Demonstrating the Need for “Source Water Supply and T.; Korak, J. A.; Rosario-Ortiz, F. L. Molecular and Spectroscopic
Protection” Strategies. Water Res. 2011, 45, 461−472. Characterization of Water Extractable Organic Matter From
(23) Hohner, A. K.; Cawley, K.; Oropeza, J.; Summers, R. S.; Thermally Altered Soils Reveal Insight Into Disinfection Byproduct
Rosario-Ortiz, F. L. Drinking Water Treatment Response Following a Precursors. Environ. Sci. Technol. 2017, 51, 771−779.
Colorado Wildfire. Water Res. 2016, 105, 187−198. (43) Santos, F.; Russell, D.; Berhe, A. A. Thermal Alteration of
(24) Emelko, M. B.; Stone, M.; Silins, U.; Allin, D.; Collins, A. L.; Water Extractable Organic Matter in Climosequence Soils From the
Williams, C. H. S.; Martens, A. M.; Bladon, K. D. Sediment- Sierra Nevada, California. J. Geophys. Res.: Biogeosci. 2016, 121, 2877−
Phosphorus Dynamics Can Shift Aquatic Ecology and Cause 2885.

1243 DOI: 10.1021/[Link].8b00670

Acc. Chem. Res. 2019, 52, 1234−1244
Accounts of Chemical Research Article

(44) Jian, M.; Berli, M.; Ghezzehei, T. A. Soil Structural Degradation (63) Quang, V. L.; Choi, I.; Hur, J. Tracking the Behavior of
During Low-Severity Burns. Geophys. Res. Lett. 2018, 45, 5553−5561. Different Size Fractions of Dissolved Organic Matter in a Full-Scale
(45) Preston, C. M.; Schmidt, M. W. I. Black (Pyrogenic) Carbon: a Advanced Drinking Water Treatment Plant. Environ. Sci. Pollut. Res.
Synthesis of Current Knowledge and Uncertainties with Special 2015, 22, 18176−18184.
Consideration of Boreal Regions. Biogeosciences 2006, 3, 397−420. (64) Archer, A. D.; Singer, P. C. An Evaluation of the Relationship
(46) Wagner, S.; Cawley, K. M.; Rosario-Ortiz, F. L.; Jaffé, R. In- Between SUVA and NOM Coagulation Using the ICR Database. J. -
Stream Sources and Links Between Particulate and Dissolved Black Am. Water Works Assoc. 2006, 98, 110−123.
Carbon Following a Wildfire. Biogeochemistry 2015, 124, 145−161. (65) White, M. C.; Thompson, J. D.; Harrington, G. W.; Singer, P.
(47) Almendros, G.; Knicker, H.; González-Vila, F. J. Rearrangement C. Evaluating Criteria for Enhanced Coagulation Compliance. J. - Am.
of Carbon and Nitrogen Forms in Peat After Progressive Thermal Water Works Assoc. 1997, 89 (5), 64−77.
Oxidation as Determined by Solid-State 13C- and 15N-NMR (66) Liang, L.; Singer, P. C. Factors Influencing the Formation and
Spectroscopy. Org. Geochem. 2003, 34, 1559−1568. Relative Distribution of Haloacetic Acids and Trihalomethanes in
(48) Knicker, H. Black Nitrogen” − an Important Fraction in Drinking Water. Environ. Sci. Technol. 2003, 37, 2920−2928.
Determining the Recalcitrance of Charcoal. Org. Geochem. 2010, 41, (67) Hohner, A. K.; Webster, J.; Cawley, K.; Rosario-Ortiz, F. L.;
947−950. Becker, W. C. Wildfire Impacts on Drinking Water Treatment Process
(49) Riggan, P. J.; Lockwood, R. N.; Jacks, P. M.; Colver, C. G.; Performance: Development of Evaluation Protocols and Management
Weirich, F.; DeBano, L. F.; Brass, J. A. Effects of Fire Severity on Practices; Water Research Foundation, Ed.; Water Research
Nitrate Mobilization in Watersheds Subject to Chronic Atmospheric Foundation: Denver, CO, 2018; pp 1−122.
Deposition. Environ. Sci. Technol. 1994, 28, 369−375. (68) Fernández, I.; Cabaneiro, A.; Carballas, T. Organic Matter
(50) Rhoades, C. C.; Entwistle, D.; Butler, D. The Influence of Changes Immediately After a Wildfire in an Atlantic Forest Soil and
Comparison with Laboratory Soil Heating. Soil Biol. Biochem. 1997,
Wildfire Extent and Severity on Streamwater Chemistry, Sediment
29, 1−11.
and Temperature Following the Hayman Fire, Colorado. Int. J.
(69) Helms, J. R.; Stubbins, A.; Ritchie, J. D.; et al. Absorption
Wildland Fire 2011, 20, 430.
Spectral Slopes and Slope Ratios as Indicators of Molecular Weight,
(51) Rhoades, C. C.; Chow, A. T.; Covino, T. P.; Fegel, T. S.;
Source, and Photobleaching of Chromophoric Dissolved Organic
Pierson, D. N.; Rhea, A. E. The Legacy of a Severe Wildfire on Stream Matter. Limnol. Oceanogr. 2008, 53, 955−969.
Nitrogen and Carbon in Headwater Catchments. Ecosystems 2018, 1− (70) Peuravuori, J.; Pihlaja, K. Molecular Size Distribution and
15. Spectroscopic Properties of Aquatic Humic Substances. Anal. Chim.
(52) United States Environmental Protection Agency. Nutrient Acta 1997, 337, 133−149.
Criteria Technical Guidance Manual Rivers and Streams; Washington, (71) González-Pérez, J. A.; González-Vila, F. J.; Almendros, G.;
DC, 2000; pp 1−253. Knicker, H. The Effect of Fire on Soil Organic Mattera Review.
(53) Mast, M. A.; Murphy, S. F.; Clow, D. W.; Penn, C. A.; Sexstone, Environ. Int. 2004, 30, 855−870.
G. A. Water-Quality Response to a High-Elevation Wildfire in the (72) Westerhoff, P.; Mash, H. Dissolved Organic Nitrogen in
Colorado Front Range. Hydrol. Process. 2016, 30, 1811−1823. Drinking Water Supplies: a Review. Aqua 2002, 51, 415−448.
(54) Murphy, S. F.; Writer, J. H.; McCleskey, R. B.; Martin, D. A. (73) Hu, J.; Song, H.; Addison, J. W.; Karanfil, T. Halonitromethane
The Role of Precipitation Type, Intensity, and Spatial Distribution in Formation Potentials in Drinking Waters. Water Res. 2010, 44, 105−
Source Water Quality After Wildfire. Environ. Res. Lett. 2015, 10, 1− 114.
13. (74) Plewa, M. J.; Wagner, E. D.; Jazwierska, P.; Richardson, S. D.;
(55) Becker, W. C.; Hohner, A.; Rosario-Ortiz, F.; DeWolfe, J. Chen, P. H.; McKague, A. B. Halonitromethane Drinking Water
Preparing for Wildfires and Extreme Weather: Plant Design and Disinfection Byproducts: Chemical Characterization and Mammalian
Operation Recommendations. J. - Am. Water Works Assoc. 2018, 110, Cell Cytotoxicity and Genotoxicity. Environ. Sci. Technol. 2004, 38,
32−40. 62−68.
(56) Wang, J.-J.; Dahlgren, R. A.; Erşan, M. S.; Karanfil, T.; Chow, A. (75) Muellner, M. G.; Wagner, E. D.; McCalla, K.; Richardson, S.
T. Wildfire Altering Terrestrial Precursors of Disinfection Byproducts D.; Woo, Y.-T.; Plewa, M. J. Haloacetonitriles vs. Regulated
in Forest Detritus. Environ. Sci. Technol. 2015, 49, 5921−5929. Haloacetic Acids: Are Nitrogen-Containing DBPs More Toxic?
(57) Hohner, A. K.; Terry, L. G.; Townsend, E. B.; Summers, R. S.; Environ. Sci. Technol. 2007, 41, 645−651.
Rosario-Ortiz, F. L. Water Treatment Process Evaluation of Wildfire-
Affected Sediment Leachates. Environmental Science: Water Research
& Technology 2017, 3, 352−365.
(58) Writer, J. H.; Hohner, A.; Oropeza, J.; Schmidt, A.; Cawley, K.;
Rosario-Ortiz, F. L. Water Treatment Implications After the High
Park Wildfire, Colorado. J. - Am. Water Works Assoc. 2014, 106,
E189−E199.
(59) Weishaar, J. L.; Aiken, G. R.; Bergamaschi, B. A.; Fram, M. S.;
Fujii, R.; Mopper, K. Evaluation of Specific Ultraviolet Absorbance as
an Indicator of the Chemical Composition and Reactivity of
Dissolved Organic Carbon. Environ. Sci. Technol. 2003, 37, 4702−
4708.
(60) Chow, C.; van Leeuwen, J. A.; Drikas, M.; Fabris, R.; Spark, K.
M.; Page, D. W. The Impact of the Character of Natural Organic
Matter in Conventional Treatment with Alum. Water Sci. Technol.
1999, 40, 97−104.
(61) Leenheer, J. A.; Croué, J.-P. Peer Reviewed: Characterizing
Aquatic Dissolved Organic Matter. Environ. Sci. Technol. 2003, 37,
18A−26A.
(62) Romera-Castillo, C.; Chen, M.; Yamashita, Y.; Jaffé, R.
Fluorescence Characteristics of Size-Fractionated Dissolved Organic
Matter: Implications for a Molecular Assembly Based Structure?
Water Res. 2014, 55, 40−51.

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Acc. Chem. Res. 2019, 52, 1234−1244