Wildfires Increase Concentrations of Hazardous Air Pollutants in Downwind Communities.

Due in part to climate change, wildfire activity is increasing, with the potential for greater public health impact from smoke in downwind communities. Studies examining the health effects of wildfire smoke have focused primarily on fine particulate matter (PM2.5), but there is a need to better characterize other constituents, such as hazardous air pollutants (HAPs). HAPs are chemicals known or suspected to cause cancer or other serious health effects that are regulated by the United States (US) Environmental Protection Agency. Here, we analyzed concentrations of 21 HAPs in wildfire smoke from 2006 to 2020 at 309 monitors across the western US. Additionally, we examined HAP concentrations measured in a major population center (San Jose, CA) affected by multiple fires from 2017 to 2020. We found that concentrations of select HAPs, namely acetaldehyde, acrolein, chloroform, formaldehyde, manganese, and tetrachloroethylene, were all significantly elevated on smoke-impacted versus nonsmoke days (P < 0.05). The largest median increase on smoke-impacted days was observed for formaldehyde, 1.3 µg/m3 (43%) higher than that on nonsmoke days. Acetaldehyde increased 0.73 µg/m3 (36%), and acrolein increased 0.14 µg/m3 (34%). By better characterizing these chemicals in wildfire smoke, we anticipate that this research will aid efforts to reduce exposures in downwind communities.

Beyond Particulate Matter Mass: Heightened Levels of Lead and Other Pollutants Associated with Destructive Fire Events in California.

As the climate warms, wildfire activity is increasing, posing a risk to human health. Studies have reported on particulate matter (PM) in wildfire smoke, yet the chemicals associated with PM have received considerably less attention. Here, we analyzed 13 years (2006-2018) of PM2.5 chemical composition data from monitors in California on smoke-impacted days. Select chemicals (e.g., aluminum and sulfate) were statistically elevated on smoke-impacted days in over half of the years studied. Other chemicals, mostly trace metals harmful to human health (e.g., copper and lead), were elevated during particular fires only. For instance, in 2018, lead was more than 40 times higher on smoke days on average at the Point Reyes monitoring station, due mostly to the Camp Fire, burning approximately 200 km away. There was an association between these metals and the combustion of anthropogenic material (e.g., the burning of houses and vehicles). Although still currently rare, these infrastructure fires are likely becoming more common and can mobilize trace metals in smoke far downwind, at levels generally unseen except in the most polluted areas of the country. We hope a better understanding of the chemicals in wildfire smoke will assist in the communication and reduction of public health risks.

Impact of do-it-yourself air cleaner design on the reduction of simulated wildfire smoke in a controlled chamber environment.

During wildfire smoke events public health agencies release advisories to stay indoors, close doors and windows, and operate a portable air cleaner (PAC). The do-it-yourself (DIY) air cleaner consisting of a box fan and a furnace filter is a widely used low-cost alternative to commercial PACs because of its increased accessibility. In this study, we evaluate the clean air delivery rate (CADR) of different DIY air cleaner designs for reducing simulated wildfire smoke and identify operating parameters that may impact their performance and use. The simplest formulation of a DIY air cleaner (box fan with taped on minimum effectiveness reporting value - [MERV] 13 furnace filter) had a CADR of 111.2 ± 1.3 ft3 /min (CFM). Increasing the fan flow by changing the fan type, increasing the fan setting, or reducing the pressure drop across the filtering surface increased the CADR. Large increases in CADR could be obtained by using a shroud (40%), using a 4″ thick filter (123%) using two filters in a wedge shape (137%), or using four filters in a Corsi-Rosenthal (CR) box design (261%). The CADR was greatly reduced with filters heavily loaded with smoke, pointing to the need for frequent filter changes during smoke events.

Correction and Accuracy of PurpleAir PM2.5 Measurements for Extreme Wildfire Smoke.

PurpleAir particulate matter (PM) sensors are increasingly used in the United States and other countries for real-time air quality information, particularly during wildfire smoke episodes. Uncorrected PurpleAir data can be biased and may exhibit a nonlinear response at extreme smoke concentrations (>300 µg/m3). This bias and nonlinearity result in a disagreement with the traditional ambient monitoring network, leading to the public's confusion during smoke episodes. These sensors must be evaluated during smoke-impacted times and then corrected for bias, to ensure that accurate data are reported. The nearby public PurpleAir sensor and monitor pairs were identified during the summer of 2020 and were used to supplement the data from collocated pairs to develop an extended U.S.-wide correction for high concentrations. We evaluated several correction schemes to identify an optimal correction, using the previously developed U.S.-wide correction, up to 300 µg/m3, transitioning to a quadradic fit above 400 µg/m3. The correction reduces the bias at each air quality index (AQI) breakpoint; most ambient collocations that were studied met the Environmental Protection Agency's (EPA) performance targets (twelve of the thirteen ambient sensors met the EPA's targets) and some smoke-impacted sites (5 out of 15 met the EPA's performance targets in terms of the 1-h averages). This correction can also be used to improve the comparability of PurpleAir sensor data with regulatory-grade monitors when they are collectively analyzed or shown together on public information websites; the methods developed in this paper can also be used to correct future air-sensor types. The PurpleAir network is already filling in spatial and temporal gaps in the regulatory monitoring network and providing valuable air-quality information during smoke episodes.

Monoterpenes are the largest source of summertime organic aerosol in the southeastern United States.

The chemical complexity of atmospheric organic aerosol (OA) has caused substantial uncertainties in understanding its origins and environmental impacts. Here, we provide constraints on OA origins through compositional characterization with molecular-level details. Our results suggest that secondary OA (SOA) from monoterpene oxidation accounts for approximately half of summertime fine OA in Centreville, AL, a forested area in the southeastern United States influenced by anthropogenic pollution. We find that different chemical processes involving nitrogen oxides, during days and nights, play a central role in determining the mass of monoterpene SOA produced. These findings elucidate the strong anthropogenic-biogenic interaction affecting ambient aerosol in the southeastern United States and point out the importance of reducing anthropogenic emissions, especially under a changing climate, where biogenic emissions will likely keep increasing.

Field Evaluation of Low-Cost Particulate Matter Sensors for Measuring Wildfire Smoke.

Until recently, air quality impacts from wildfires were predominantly determined based on data from permanent stationary regulatory air pollution monitors. However, low-cost particulate matter (PM) sensors are now widely used by the public as a source of air quality information during wildfires, although their performance during smoke impacted conditions has not been thoroughly evaluated. We collocated three types of low-cost fine PM (PM2.5) sensors with reference instruments near multiple fires in the western and eastern United States (maximum hourly PM2.5 = 295 µg/m3). Sensors were moderately to strongly correlated with reference instruments (hourly averaged r2 = 0.52-0.95), but overpredicted PM2.5 concentrations (normalized root mean square errors, NRMSE = 80-167%). We developed a correction equation for wildfire smoke that reduced the NRMSE to less than 27%. Correction equations were specific to each sensor package, demonstrating the impact of the physical configuration and the algorithm used to translate the size and count information into PM2.5 concentrations. These results suggest the low-cost sensors can fill in the large spatial gaps in monitoring networks near wildfires with mean absolute errors of less than 10 µg/m3 in the hourly PM2.5 concentrations when using a sensor-specific smoke correction equation.

Assessing PM2.5 Model Performance for the Conterminous U.S. with Comparison to Model Performance Statistics from 2007-2015.

Previous studies have proposed that model performance statistics from earlier photochemical grid model (PGM) applications can be used to benchmark performance in new PGM applications. A challenge in implementing this approach is that limited information is available on consistently calculated model performance statistics that vary spatially and temporally over the U.S. Here, a consistent set of model performance statistics are calculated by year, season, region, and monitoring network for PM2.5 and its major components using simulations from versions 4.7.1-5.2.1 of the Community Multiscale Air Quality (CMAQ) model for years 2007-2015. The multi-year set of statistics is then used to provide quantitative context for model performance results from the 2015 simulation. Model performance for PM2.5 organic carbon in the 2015 simulation ranked high (i.e., favorable performance) in the multi-year dataset, due to factors including recent improvements in biogenic secondary organic aerosol and atmospheric mixing parameterizations in CMAQ. Model performance statistics for the Northwest region in 2015 ranked low (i.e., unfavorable performance) for many species in comparison to the 2007-2015 dataset. This finding motivated additional investigation that suggests a need for improved speciation of wildfire PM2.5emissions and modeling of boundary layer dynamics near water bodies. Several limitations were identified in the approach of benchmarking new model performance results with previous results. Since performance statistics vary widely by region and season, a simple set of national performance benchmarks (e.g., one or two targets per species and statistic) as proposed previously are inadequate to assess model performance throughout the U.S. Also, trends in model performance statistics for sulfate over the 2007 to 2015 period suggest that model performance for earlier years may not be a useful reference for assessing model performance for recent years in some cases. Comparisons of results from the 2015 base case with results from five sensitivity simulations demonstrated the importance of parameterizations of NH3 surface exchange, organic aerosol volatility and production, and emissions of crustal cations for predicting PM2.5 species concentrations.

Light Absorption of Secondary Organic Aerosol: Composition and Contribution of Nitroaromatic Compounds.

Secondary organic aerosol (SOA) can affect the atmospheric radiation balance through absorbing light at shorter visible and UV wavelengths. However, the composition and optical properties of light-absorbing SOA is poorly understood. In this work, SOA filter samples were collected during individual chamber experiments conducted with three biogenic and eight aromatic volatile organic compound (VOC) precursors in the presence of NOX and H2O2. Compared with the SOA generated using the aromatic precursors, biogenic SOA generally exhibits negligible light absorption above 350 nm; the aromatic SOA generated in the presence of NOX shows stronger light absorption than that generated with H2O2. Fifteen nitroaromatic compound (NAC) chemical formulas were identified and quantified in SOA samples. Their contributions to the light absorption of sample extracts were also estimated. On average, the m-cresol/NOX SOA sample has the highest mass contribution from NACs (10.4 ± 6.74%, w/w), followed by naphthalene/NOX (6.41 ± 2.08%) and benzene/NOX (5.81 ± 3.82%) SOA. The average contributions of NACs to total light absorption were at least two times greater than their average mass contributions at 365 and 400 nm, revealing the potential use of chromophoric NACs as brown carbon (BrC) tracers in source apportionment and air quality modeling studies.

Effects of Aftermarket Control Technologies on Gas and Particle Phase Oxidative Potential from Diesel Engine Emissions.

Particulate matter (PM) originating from diesel combustion is a public health concern due to its association with adverse effects on respiratory and cardiovascular diseases and lung cancer. This study investigated emissions from three stationary diesel engines (gensets) and varying power output (230 kW, 400 kW, and 600 kW) at 50% and 90% load to determine concentrations of gaseous (GROS) and PM reactive oxygen species (PMROS). In addition, the influence of three modern emission control technologies on ROS emissions was evaluated: active and passive diesel particulate filters (A-DPF and P-DPF) and a diesel oxidation catalyst (DOC). PMROS made up 30-50% of the total ROS measured without aftermarket controls. All applied controls removed PMROS by more than 75% on average. However, the oxidative potential of PM downstream of these devices was not diminished at the same rate and particles surviving the A-PDF had an even higher oxidative potential on a per PM mass basis compared to the particles emitted by uncontrolled gensets. Further, the GROS as compared to PMROS emissions were not reduced with the same efficiency (<36%). GROS concentrations were highest with the DOC in use, indicating continued formation of GROS with this control. Correlation analyses showed that PMROS and to a lesser extent GROS have a good correlation with semivolatile organic carbon (OC1) subfraction. In addition, results suggest that chemical composition, rather than PM size, is responsible for differences in the PM oxidative potential.

Gas and particle emissions from rifle and pistol firing.

Emissions were sampled from firing an M4 carbine rifle and a M9 (military issue of Beretta 75 FS 9 mm pistol) to develop sampling methods and assess potential exposures and range contamination issues. Breech and muzzle emissions were sampled from the rifle when firing M855A1 ammunition (lead (Pb)-free slugs) in single- and triple-shot burst mode and from single pistol shots when firing 9 mm XM1152 ammunition (not Pb-free). Emissions were sampled for carbon monoxide (CO), carbon dioxide (CO2), methane, hydrogen cyanide, ammonia, particulate matter by size, polycylic aromatic hydrocarbons, and volatile organics. Analyses on the particles included elemental composition, size distribution, carbon composition (black, total, organic, and elemental carbon), and particle composition and morphology. Emission concentrations from both the rifle and pistol were characterized by CO/CO2 ratios between, approximately, 1/1 and 2/1, respectfully, indicating incomplete carbon oxidation. The initial particle size distribution was dominated in number by particles smaller than 40 nm but the high particle concentrations led to rapid agglomeration. The abundance of CO and metals of inhalable particle size are noteworthy and indicate that further assessment of exposure would determine potential inhalation health hazards, particularly in indoor firing ranges.

Emissions of polycyclic aromatic hydrocarbons, polychlorinated dibenzo-p-dioxins, and dibenzofurans from incineration of nanomaterials.

Disposal of some nanomaterial-laden waste through incineration is inevitable, and nanomaterials' influence on combustion byproduct formation under high-temperature, oxidative conditions is not well understood. This work reports the formation of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated-dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from incineration of paper and plastic waste containing various nanomaterials, including titania, nickel oxide, silver, ceria, iron oxide, quantum dots, and C60-fullerene, in a laboratory-scale furnace. The presence of nanomaterials in the waste stream resulted in higher emissions of some PAH species and lower emissions of others, depending on the type of waste. The major PAH species formed were phenanthrene and anthracene, and emissions were sensitive to the amount of nanomaterials in the waste. Generally, there were no significant differences in emission factors for the larger PAH species when nanomaterials were added to the waste. The total PAH emission factors were on average ~6 times higher for waste spiked with nanomaterials v. their bulk counterparts. Emissions of chlorinated dioxins from poly(vinyl chloride) (PVC) waste were not detected; however, chlorinated furans were formed at elevated concentrations with wastes containing silver and titania nanomaterials, and toxicity was attributable mainly to 2,3,4,7,8-pentachlorodibenzofuran. The combination of high specific surface area and catalytic, including electrocatalytic, properties of nanomaterials might be responsible for affecting the formation of toxic pollutants during incineration.

Particulate Pb emission factors from wildland fires in the United States.

Wildland fires, which includes both wild and prescribed fires, and agricultural fires in sum are one of the largest sources of fine particulate matter (PM2.5) emissions to the atmosphere in the United States (US). Although wildland fire PM2.5 emissions are primarily composed of carbonaceous material, many other elements including trace metals are emitted at very low levels. Lead (Pb) is a US Environmental Protection Agency (EPA) criteria pollutant that is ubiquitous in the environment at very low concentrations including in biomass that can burn and emit Pb into the atmosphere. Although fires may emit Pb at very low concentrations, they can be a source of sizeable Pb emissions to the atmosphere because of the large quantity of PM2.5 emitted from fires. In this work, we measure Pb concentrations in unburned biomass, ash/residues, and particulate matter <2.5 µm (PM2.5) emitted from wildland fires using in-field measurements near prescribed fires and in laboratory simulations. Emission factors were calculated for multiple biomass types, representative of different regions of the US including grasslands in Oregon and Kansas; forest litter from Oregon, Montana, Minnesota, and North Carolina; and peat cores from Minnesota. Most of the biomass Pb remains in the ash/residues. The small percentage (<10%) that is emitted in PM2.5 is dependent on the biomass Pb concentration. The emissions factors measured here are several orders of magnitude lower than some reported in the literature, but the studies exhibited a wide range of values, which may be due to large uncertainties in the measurement method rather than differences in Pb emissions. Wildland fires are expected to increase in size and frequency in future years and these new emission factors can be used to improve the accuracy of Pb emissions estimates and better constrain our understanding of Pb emissions to the atmosphere.

Hazardous air pollutant emissions estimates from wildfires in the wildland urban interface.

Fires that occur in the wildland urban interface (WUI) often burn structures, vehicles, and their contents in addition to biomass in the natural landscape. Because these fires burn near population centers, their emissions may have a sizeable impact on public health, necessitating a better understanding of criteria and hazardous air pollutants emitted from these fires and how they differ from wildland fires. Previous studies on the toxicity of emissions from the combustion of building materials and vehicles have shown that urban fires may emit numerous toxic species such as hydrogen cyanide, hydrogen fluoride, hydrogen chloride, isocyanates, polycyclic aromatic hydrocarbons (PAHs), dioxins and furans, and a range of toxic organic compounds (e.g. benzene toluene, xylenes, styrene, and formaldehyde) and metals (e.g. lead, chromium, cadmium, and arsenic). We surveyed the literature to create a compendium of emission factors for species emitted from the combustion of building and vehicle materials and compared them with those from wildland fires. Emission factors for some toxic species like PAH and some organic compounds were several orders of magnitude greater than those from wildfires. We used this emission factor compendium to calculate a bounding estimate of the emissions from several notable WUI fires in the western United States to show that urban fuels may contribute a sizeable portion of the toxic emissions into the atmosphere. However, large gaps remain in our understanding of the fuel composition, fuel consumption, and combustion conditions in WUI fires that constrain our ability to estimate the impact of WUI fires.

Particle-induced artifacts in the MTT and LDH viability assays.

In vitro testing is a common first step in assessing combustion-generated and engineered nanoparticle-related health hazards. Commercially available viability assays are frequently used to compare the toxicity of different particle types and to generate dose-response data. Nanoparticles, well-known for having large surface areas and chemically active surfaces, may interfere with viability assays, producing a false assessment of toxicity and making it difficult to compare toxicity data. The objective of this study is to measure the extent of particle interference in two common viability assays, the MTT reduction and the lactate dehydrogenase (LDH) release assays. Diesel particles, activated carbon, flame soot, oxidized flame soot, and titanium dioxide particles are assessed for interactions with the MTT and LDH assay under cell-free conditions. Diesel particles, at concentrations as low as 0.05 µg/mL, reduce MTT. Other particle types reduce MTT only at a concentration of 50 µg/mL and higher. The activated carbon, soot, and oxidized soot particles bind LDH to varying extents, reducing the concentration measured in the LDH assay. The interfering effects of the particles explain in part the different toxicities measured in human bronchial epithelial cells (16HBE14o). We conclude that valid particle toxicity assessments can only be assured after first performing controls to verify that the particles under investigation do not interfere with a specific assay at the expected concentrations.

Chemistry and lung toxicity of particulate matter emitted from firearms.

Smoke emissions produced by firearms contain hazardous chemicals, but little is known if their properties change depending on firearm and ammunition type and whether such changes affect toxicity outcomes. Pulmonary toxicity was assessed in mice exposed by oropharyngeal aspiration to six different types of smoke-related particulate matter (PM) samples; (1) handgun PM, (2) rifle PM, (3) copper (Cu) particles (a surrogate for Cu in the rifle PM) with and without the Cu chelator penicillamine, (4) water-soluble components of the rifle PM, (5) soluble components with removal of metal ions, and (6) insoluble components of the rifle PM. Gun firing smoke PM was in the respirable size range but the chemical composition varied with high levels of Pb in the handgun and Cu in the rifle smoke. The handgun PM did not induce appreciable lung toxicity at 4 and 24 h post-exposure while the rifle PM significantly increased lung inflammation and reduced lung function. The same levels of pure Cu particles alone and the soluble components from the rifle fire PM increased neutrophil numbers but did not cause appreciable cellular damage or lung function changes when compared to the negative (saline) control. Penicillamine treated rifle PM or Cu, slightly reduced lung inflammation and injury but did not improve the lung function decrements. Chelation of the soluble metal ions from the rifle fire PM neutralized the lung toxicity while the insoluble components induced the lung toxicity to the same degree as the rifle PM. The results show that different firearm types can generate contrasting chemical spectra in their emissions and that the rifle PM effects were mostly driven by water-insoluble components containing high levels of Cu. These findings provide better knowledge of hazardous substances in gun firing smoke and their potential toxicological profile.

Creating Clean Air Spaces During Wildland Fire Smoke Episodes: Web Summit Summary.

Effective strategies to reduce indoor air pollutant concentrations during wildfire smoke events are critically needed. Worldwide, communities in areas prone to wildfires may suffer from annual smoke exposure events lasting from days to weeks. In addition, there are many areas of the world where high pollution events are common and where methods employed to reduce exposure to pollution may have relevance to wildfire smoke pollution episodes and vice versa. This article summarizes a recent virtual meeting held by the United States Environmental Protection Agency (EPA) to share research, experiences, and other information that can inform best practices for creating clean air spaces during wildland fire smoke events. The meeting included presentations on the public health impacts of wildland fire smoke; public health agencies' experiences and resilience efforts; and methods to improve indoor air quality, including the effectiveness of air filtration methods [e.g., building heating ventilation and air conditioning (HVAC) systems and portable, free-standing air filtration systems]. These presentations and related research indicate that filtration has been demonstrated to effectively improve indoor air quality during high ambient air pollution events; however, several research questions remain regarding the longevity and maintenance of filtration equipment during and after smoke events, effects on the pollution mixture, and degree to which adverse health effects are reduced.

Chemical composition, structures, and light absorption of N-containing aromatic compounds emitted from burning wood and charcoal in household cookstoves.

N-containing aromatic compounds (NACs) are an important group of light-absorbing molecules in the atmosphere. They are often observed in combustion emissions, but their chemical formulas and structural characteristics remain uncertain. In this study, red oak wood and charcoal fuels were burned in cookstoves using the standard water boiling test (WBT) procedure. Submicron aerosol particles in the cookstove emissions were collected using quartz (Q f ) and polytetrafluoroethylene (PTFE) filter membranes positioned in parallel. A back-up quartz filter (Q b ) was also installed downstream of the PTFE filter to evaluate the effect of sampling artifact on NACs measurements. Liquid chromatography-mass spectroscopy (LC-MS) techniques identified seventeen NAC chemical formulas in the cookstove emissions. The average concentrations of total NACs in Q b samples (0.37 ± 0.31 - 1.79 ± 0.77 µg m-3) were greater than 50% of those observed in the Q f samples (0.51 ± 0.43 - 3.91 ± 2.06 µg m-3), and the Q b to Q f mass ratios of individual NACs had a range of 0.02 - 2.71, indicating that the identified NACs might have substantial fractions remaining in the gas-phase. In comparison to other sources, cookstove emissions from red oak or charcoal fuels did not exhibit unique NAC structural features, but had distinct NACs composition. However, before identifying NACs sources by combining their structural and compositional information, the gas-particle partitioning behaviors of NACs should be further investigated. The average contributions of total NACs to the light absorption of organic matter at λ = 365 nm (1.10 - 2.57%) in Q f and Q b samples (10.7 - 21.0%) are up to 10 times larger than their mass contributions (Q f 0.31 - 1.01%, Q b 1.08 - 3.31%), so the identified NACs are mostly strong light absorbers. To explain more sample extracts absorption, future research is needed to understand the chemical and optical properties of high molecular weight (e.g., MW > 500 Da) entities in particulate matter.

Wildfire and prescribed burning impacts on air quality in the United States.

Air quality impacts from wildfires have been dramatic in recent years, with millions of people exposed to elevated and sometimes hazardous fine particulate matter (PM 2.5 ) concentrations for extended periods. Fires emit particulate matter (PM) and gaseous compounds that can negatively impact human health and reduce visibility. While the overall trend in U.S. air quality has been improving for decades, largely due to implementation of the Clean Air Act, seasonal wildfires threaten to undo this in some regions of the United States. Our understanding of the health effects of smoke is growing with regard to respiratory and cardiovascular consequences and mortality. The costs of these health outcomes can exceed the billions already spent on wildfire suppression. In this critical review, we examine each of the processes that influence wildland fires and the effects of fires, including the natural role of wildland fire, forest management, ignitions, emissions, transport, chemistry, and human health impacts. We highlight key data gaps and examine the complexity and scope and scale of fire occurrence, estimated emissions, and resulting effects on regional air quality across the United States. The goal is to clarify which areas are well understood and which need more study. We conclude with a set of recommendations for future research. IMPLICATIONS: In the recent decade the area of wildfires in the United States has increased dramatically and the resulting smoke has exposed millions of people to unhealthy air quality. In this critical review we examine the key factors and impacts from fires including natural role of wildland fire, forest management, ignitions, emissions, transport, chemistry and human health.