Transpacific Transport of Asian Peroxyacetyl Nitrate (PAN) Observed from Satellite: Implications for Ozone.

Peroxyacetyl nitrate (PAN) is produced in the atmosphere by photochemical oxidation of non-methane volatile organic compounds in the presence of nitrogen oxides (NOx), and it can be transported over long distances at cold temperatures before decomposing thermally to release NOx in the remote troposphere. It is both a tracer and a precursor for transpacific ozone pollution transported from East Asia to North America. Here, we directly demonstrate this transport with PAN satellite observations from the infrared atmospheric sounding interferometer (IASI). We reprocess the IASI PAN retrievals by replacing the constant prior vertical profile with vertical shape factors from the GEOS-Chem model that capture the contrasting shapes observed from aircraft over South Korea (KORUS-AQ) and the North Pacific (ATom). The reprocessed IASI PAN observations show maximum transpacific transport of East Asian pollution in spring, with events over the Northeast Pacific offshore from the Western US associated in GEOS-Chem with elevated ozone in the lower free troposphere. However, these events increase surface ozone in the US by less than 1 ppbv because the East Asian pollution mainly remains offshore as it circulates the Pacific High.

Key results from the salt lake regional smoke, ozone, and aerosol study (SAMOZA).

The Northern Wasatch Front area is one of ~ 50 metropolitan regions in the U.S. that do not meet the 2015 O3 standard. To better understand the causes of high O3 days in this region we conducted the Salt Lake regional Smoke, Ozone and Aerosol Study (SAMOZA) in the summer of 2022. The primary goals of SAMOZA were: Measure a suite of VOCs, by Proton Transfer Reaction Mass Spectrometry (PTR-MS) and the 2,4-dinitrophenylhydrazine (DNPH) cartridge method.Evaluate whether the standard UV O3 measurements made in SLC show a positive bias during smoke events, as has been suggested in some recent studies.Use the observations to conduct photochemical modeling and statistical/machine learning analyses to understand photochemistry on both smoke-influenced and non-smoke days.Implications: The Northern Wasatch Front area is one of ~50 metropolitan regions in the U.S. that do not meet the 2015 O3 standard. To better understand the causes of high O3 days in this region we conducted the Salt Lake regional Smoke, Ozone and Aerosol Study (SAMOZA) in the summer of 2022. A number of policy relevant findings are identified in the manuscript including role of smoke and NOx vs VOC sensitivity.

We found no significant difference in the O₃ measurements using a "scrubber-less" UV instrument compared to the standard O₃ measurements at PM_2.5 concentrations up to 60 µg m⁻³.On days with smoke, we found that PM_2.5, CO, O₃ and nearly all VOCs were significantly enhanced. On average, NO_x was also enhanced on days with smoke, but this was complicated by day of week effects.Photochemical modeling of O₃ production rates at the Utah Tech Center demonstrates a strong sensitivity to VOC concentrations and less sensitivity to NOx. For non-smoke days, achieving the current O₃ standard would require regional reductions in VOCs of ~40% or reductions in NO_x ~ 60%.The photochemical modeling shows that formaldehyde and other OVOCs, along with alkenes, were the most important O₃ precursors.Generalized Additive Modeling (GAM) gave similar MDA8 O₃ enhancements on smoky days as the photochemical modeling. Analysis of the GAM results show that 23% of the smoke days have GAM residuals that exceed the U.S. EPA's criteria for inclusion as exceptional event documentation.

Impact of wildfire smoke on ozone concentrations using a Generalized Additive model in Salt Lake City, Utah, USA, 2006-2022.

We investigated the impact of wildfires on maximum daily 8-hr average ozone concentrations (MDA8 O3) at four sites in Salt Lake City (SLC), Utah for May to September for 2006-2022. Smoke days, which were identified by a combination of overhead satellite smoke detection and surface PM2.5 data and accounted for approximately 9% of the total number of days, exhibited O3 levels 6.8 to 8.9 ppb higher than no-smoke days and were predominantly characterized by high daily maximum temperatures and low relative humidity. A Generalized Additive Model (GAM) was developed to quantify the impact of wildfire contributions to O3. The GAM, which provides smooth functions that make the interpretation of relationships more intuitive, employed 17 predictors and demonstrated reliable performance in various evaluation metrics. The mean of the residuals for all sites was approximately zero for the training and cross-validation data and 5.1 ppb for smoke days. We developed three approaches to estimate the contribution of smoke to O3 from the model residuals. These generate a minimum and maximum contribution for each smoke day. The average of the minimum and maximum wildfire contributions to O3 for the SLC sites was 5.1 and 8.5 ppb, respectively. Between 2006 and 2022, an increasing trend in the wildfire contributions to O3 was observed in SLC. Moreover, trends of the fourth-highest MDA8 O3 before and after removing the wildfire contributions to O3 at the SLC Hawthorne site in 2006-2022 were quite different. Whereas the unadjusted data do not meet the current O3 standard, after removing the contributions from wildfires the SLC region is close to achieving levels that are consistent with meeting the O3 standard. We also found that the wildfire contribution during smoke days was particularly high under conditions of high temperature, high PM2.5 concentration, and low cloud fraction.Implications: In this study, we quantified the impact of wildfires on maximum daily 8-hr average ozone concentrations (MDA8 O3) in Salt Lake City, Utah, using a Generalized Additive Model (GAM). The GAM results demonstrate the importance of wildfires as contributors to O3 air pollution. Our results suggest that states could use the GAM approach to assist in quantifying the wildfire contribution to MDA8 O3 under the U.S. EPA exceptional events rule. These findings also highlight the need for strategies to manage wildfires and their subsequent impacts on air quality in an era of climate warming.

Investigation of Ozone Formation Chemistry during the Salt Lake Regional Smoke, Ozone, and Aerosol Study (SAMOZA).

Salt Lake City (SLC), UT, is an urban area where ozone (O3) concentrations frequently exceed health standards. This study uses an observationally constrained photochemical box model to investigate the drivers of O3 production during the Salt Lake Regional Smoke, Ozone, and Aerosol Study (SAMOZA), which took place from August to September 2022 in SLC. During SAMOZA, a suite of volatile organic compounds (VOCs), oxides of nitrogen (NOx), and other parameters were measured at the Utah Technical Center, a high-NOx site in the urban core. We examined four high-O3 cases: 4 August and 3, 11, and 12 September, which were classified as a nonsmoky weekday, a weekend day with minimal smoke influence, a smoky weekend day, and a smoky weekday, respectively. The modeled O3 production on 4 August and 3 September was highly sensitive to VOCs and insensitive to NOx reductions of ≤50%. Box model results suggest that the directly emitted formaldehyde contributed to the rapid increase in morning O3 concentrations on 3 September. Model sensitivity tests for September 11-12 indicated that smoke-emitted VOCs, especially aldehydes, had a much larger impact on O3 production than NOx and/or anthropogenic VOCs. On 11 and 12 September, smoke-emitted VOCs enhanced model-predicted maximum daily 8 h average O3 concentrations by 21 and 13 parts per billion (ppb), respectively. Overall, our results suggest that regionwide VOC reductions of at least 30-50% or NOx reductions of at least 60% are needed to bring SLC into compliance with the national O3 standard of 70 ppb.

Omega-3 Index improves after increased intake of foods with omega-3 polyunsaturated fatty acids among US service academy cadets.

The inclusion of omega-3 fatty acids in our dietary intake is important for performance and recovery and may reduce the risk of various health issues. Studies have shown the omega-3 fatty acid status of US service members is low. The purpose of this study was to evaluate whether offering fish and omega-3-enhanced foods would increase the Omega-3 Index (O3I). We hypothesize cadets will increase O3I with enhanced omega-3 options more than fish alone. Food service venues at 3 US service academies offered fish and other omega-3 foods to cadets for 12 weeks. Questionnaires were used to collect information on the dietary habits and omega-3 food intake of participants. The O3I of each participant was measured at baseline, mid- (6 weeks), and after data collection (12 weeks) time points. Following the 12 weeks, we found a significant increase in O3I. More specifically, the intake of other omega-3 foods, smoothies (3 per week) and toppings (3 per week), increased O3I in cadets. This study identified a strategy encouraging omega-3 food intake and improving O3I among cadets. These results help us understand how we can more effectively impact military service member nutrition for optimal health and performance.

Using the Black Carbon Particle Mixing State to Characterize the Lifecycle of Biomass Burning Aerosols.

The lifecycle of black carbon (BC)-containing particles from biomass burns is examined using aircraft and surface observations of the BC mixing state for plume ages from ∼15 min to 10 days. Because BC is nonvolatile and chemically inert, changes in the mixing state of BC-containing particles are driven solely by changes in particle coating, which is mainly secondary organic aerosol (SOA). The coating mass initially increases rapidly (kgrowth = 0.84 h-1), then remains relatively constant for 1-2 days as plume dilution no longer supports further growth, and then decreases slowly until only ∼30% of the maximum coating mass remains after 10 days (kloss = 0.011 h-1). The mass ratio of coating-to-core for a BC-containing particle with a 100 nm mass-equivalent diameter BC core reaches a maximum of ∼20 after a few hours and drops to ∼5 after 10 days of aging. The initial increase in coating mass can be used to determine SOA formation rates. The slow loss of coating material, not captured in global models, comprises the dominant fraction of the lifecycle of these particles. Coating-to-core mass ratios of BC particles in the stratosphere are much greater than those in the free troposphere indicating a different lifecycle.

NOx and O3 Trends at U.S. Non-Attainment Areas for 1995-2020: Influence of COVID-19 Reductions and Wildland Fires on Policy-Relevant Concentrations.

We analyzed NO2 and O3 data from 32 U.S. non-attainment areas (NAAs) for 1995-2020. Since 1995, all regions have shown steady reductions in NO2 and the weekend-weekday pattern indicates that the O3 production regime in most NAAs has transitioned to a NOx-limited regime, while a few NAAs remain NOx-saturated. In the eastern U.S., all NAAs have made steady progress toward meeting the current (70 ppb) O3 standard, but this is less true in midwestern and western NAAs, with most showing little improvement in peak O3 concentrations since about 2010. Due to COVID-19 restrictions, NO2 concentrations were substantially reduced in 2020. In the eastern NAAs, we see significant reductions in both NO2 and peak O3 concentrations. In the midwestern U.S., results were more variable, with both higher and lower O3 values in 2020. In the western U.S. (WUS), we see variable reductions in NO2 but substantial increases in O3 at most sites, due to the influence from huge wildland fires. The recent pattern over the past decade shows that the large amount of wildland fires has a strong influence on the policy-relevant O3 metric in the WUS, and this is making it more difficult for these regions to meet the O3 standard.

Persistent Influence of Wildfire Emissions in the Western United States and Characteristics of Aged Biomass Burning Organic Aerosols under Clean Air Conditions.

Wildfire-influenced air masses under regional background conditions were characterized at the Mt. Bachelor Observatory (∼2800 m a.s.l.) in summer 2019 to provide a better understanding of the aging of biomass burning organic aerosols (BBOAs) and their impacts on the remote troposphere in the western United States. Submicron aerosol (PM1) concentrations were low (average ± 1σ = 2.2 ± 1.9 µg sm-3), but oxidized BBOAs (average O/C = 0.84) were constantly detected throughout the study. The BBOA correlated well with black carbon, furfural, and acetonitrile and comprised above 50% of PM1 during plume events when the peak PM1 concentration reached 18.0 µg sm-3. Wildfire plumes with estimated transport times varying from ∼10 h to >10 days were identified. The plumes showed ΔOA/ΔCO values ranging from 0.038 to 0.122 ppb ppb-1 with a significant negative relation to plume age, indicating BBOA loss relative to CO during long-range transport. Additionally, increases of average O/C and aerosol sizes were seen in more aged plumes. The mass-based size mode was approximately 700 nm (Dva) in the most oxidized plume that likely originated in Siberia, suggesting aqueous-phase processing during transport. This work highlights the widespread impacts that wildfire emissions have on aerosol concentration and properties, and thus climate, in the western United States.

Contrasting Controls on the Diel Isotopic Variation of Hg0 at Two High Elevation Sites in the Western United States.

The atmosphere is a significant global reservoir for mercury (Hg) and its isotopic characterization is important to understand sources, distribution, and deposition of Hg to the Earth's surface. To better understand Hg isotope variability in the remote background atmosphere, we collected continuous 12-h Hg0 samples for 1 week from two high elevation sites, Camp Davis, Wyoming (valley), and Mount Bachelor, Oregon (mountaintop). The samples collected at Camp Davis displayed strong diel variation in δ202Hg values of Hg0, but not in Δ199Hg or Δ200Hg values. We attribute this pattern to nightly atmospheric inversions trapping Hg in the valley and the subsequent nighttime uptake of Hg by vegetation, which depletes Hg from the atmosphere. At Mount Bachelor, the samples displayed diel variation in both δ202Hg and Δ199Hg, but not Δ200Hg. We attribute this pattern to differences in the vertical distribution of Hg in the atmosphere as Mount Bachelor received free tropospheric air masses on certain nights during the sampling period. Near the end of the sampling period at Mount Bachelor, the observed diel pattern dissipated due to the influence of a nearby forest fire. The processes governing the Hg isotopic fractionation differ across sites depending on mixing, topography, and vegetation cover.

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.

Relationships between Particulate Matter, Ozone, and Nitrogen Oxides during Urban Smoke Events in the Western US.

Urban ozone (O3) pollution is influenced by the transport of wildfire smoke but observed impacts are highly variable. We investigate O3 impacts from smoke in 18 western US cities during July-September, 2013-2017, with ground-based monitoring data from air quality system sites, using satellite-based hazard mapping system (HMS) fire and smoke product to identify overhead smoke. We present four key findings. First, O3 and PM2.5 (particulate matter <2.5 µm in diameter) are elevated at nearly all sites on days influenced by smoke, with the greatest mean enhancement occurring during multiday smoke events; nitrogen oxides (NOx) are not consistently elevated across all sites. Second, PM2.5 and O3 exhibit a nonlinear relationship such that O3 increases with PM2.5 at low to moderate 24 h PM2.5, peaks around 30-50 µg m-3, and declines at higher PM2.5. Third, the rate of increase of morning O3 is higher and NO/NO2 ratios are lower on smoke-influenced days, which could result from additional atmospheric oxidants in smoke. Fourth, while the HMS product is a useful tool for identifying smoke, O3 and PM2.5 are elevated on days before and after HMS-identified smoke events implying that a significant fraction of smoke events is not detected.

US particulate matter air quality improves except in wildfire-prone areas.

Using data from rural monitoring sites across the contiguous United States, we evaluated fine particulate matter (PM2.5) trends for 1988-2016. We calculate trends in the policy-relevant 98th quantile of PM2.5 using Quantile Regression. We use Kriging and Gaussian Geostatistical Simulations to interpolate trends between observed data points. Overall, we found positive trends in 98th quantile PM2.5 at sites within the Northwest United States (average 0.21 ± 0.12 µg·m-3·y-1; ±95% confidence interval). This was in contrast with sites throughout the rest of country, which showed a negative trend in 98th quantile PM2.5, likely due to reductions in anthropogenic emissions (average -0.66 ± 0.10 µg·m-3·y-1). The positive trend in 98th quantile PM2.5 is due to wildfire activity and was supported by positive trends in total carbon and no trend in sulfate across the Northwest. We also evaluated daily moderate resolution imaging spectroradiometer (MODIS) aerosol optical depth (AOD) for 2002-2017 throughout the United States to compare with ground-based trends. For both Interagency Monitoring of Protected Visual Environments (IMPROVE) PM2.5 and MODIS AOD datasets, we found positive 98th quantile trends in the Northwest (1.77 ± 0.68% and 2.12 ± 0.81% per year, respectively) through 2016. The trend in Northwest AOD is even greater if data for the high-fire year of 2017 are included. These results indicate a decrease in PM2.5 over most of the country but a positive trend in the 98th quantile PM2.5 across the Northwest due to wildfires.

Quantifying O3 Impacts in Urban Areas Due to Wildfires Using a Generalized Additive Model.

Wildfires emit O3 precursors but there are large variations in emissions, plume heights, and photochemical processing. These factors make it challenging to model O3 production from wildfires using Eulerian models. Here we describe a statistical approach to characterize the maximum daily 8-h average O3 (MDA8) for 8 cities in the U.S. for typical, nonfire, conditions. The statistical model represents between 35% and 81% of the variance in MDA8 for each city. We then examine the residual from the model under conditions with elevated particulate matter (PM) and satellite observed smoke ("smoke days"). For these days, the residuals are elevated by an average of 3-8 ppb (MDA8) compared to nonsmoke days. We found that while smoke days are only 4.1% of all days (May-Sept) they are 19% of days with an MDA8 greater than 75 ppb. We also show that a published method that does not account for transport patterns gives rise to large overestimates in the amount of O3 from fires, particularly for coastal cities. Finally, we apply this method to a case study from August 2015, and show that the method gives results that are directly applicable to the EPA guidance on excluding data due to an uncontrollable source.

Biomass Burning Smoke Climatology of the United States: Implications for Particulate Matter Air Quality.

We utilize the NOAA Hazard Mapping System smoke product for the period of 2005 to 2016 to develop climatology of smoke occurrence over the Continental United States (CONUS) region and to study the impact of wildland fires on particulate matter air quality at the surface. Our results indicate that smoke is most frequently found over the Great Plains and western states during the summer months. Other hotspots of smoke occurrence are found over state and national parks in the southeast during winter and spring, in the Gulf of Mexico southwards of the Texas and Louisiana coastline during spring season and along the Mississippi River Delta during the fall season. A substantial portion (20%) of the 24 h federal standard for particulate pollution exceedance events in the CONUS region occur when smoke is present. If the U.S. Environmental Protection Agency regulations continue to reduce anthropogenic emissions, wildland fire emissions will become the major contributor to particulate pollution and exceedance events. In this context, we show that HMS smoke product is a valuable tool for analysis of exceptional events caused by wildland fires and our results indicate that these tools can be valuable for policy and decision makers.

Regional Influence of Aerosol Emissions from Wildfires Driven by Combustion Efficiency: Insights from the BBOP Campaign.

Wildfires are important contributors to atmospheric aerosols and a large source of emissions that impact regional air quality and global climate. In this study, the regional and nearfield influences of wildfire emissions on ambient aerosol concentration and chemical properties in the Pacific Northwest region of the United States were studied using real-time measurements from a fixed ground site located in Central Oregon at the Mt. Bachelor Observatory (∼2700 m a.s.l.) as well as near their sources using an aircraft. The regional characteristics of biomass burning aerosols were found to depend strongly on the modified combustion efficiency (MCE), an index of the combustion processes of a fire. Organic aerosol emissions had negative correlations with MCE, whereas the oxidation state of organic aerosol increased with MCE and plume aging. The relationships between the aerosol properties and MCE were consistent between fresh emissions (∼1 h old) and emissions sampled after atmospheric transport (6-45 h), suggesting that biomass burning organic aerosol concentration and chemical properties were strongly influenced by combustion processes at the source and conserved to a significant extent during regional transport. These results suggest that MCE can be a useful metric for describing aerosol properties of wildfire emissions and their impacts on regional air quality and global climate.

Molecular Evidence for Metabolically Active Bacteria in the Atmosphere.

Bacterial metabolisms are responsible for critical chemical transformations in nearly all environments, including oceans, freshwater, and soil. Despite the ubiquity of bacteria in the atmosphere, little is known about the metabolic functioning of atmospheric bacterial communities. To gain a better understanding of the metabolism of bacterial communities in the atmosphere, we used a combined empirical and model-based approach to investigate the structure and composition of potentially active bacterial communities in air sampled at a high elevation research station. We found that the composition of the putatively active bacterial community (assayed via rRNA) differed significantly from the total bacterial community (assayed via rDNA). Rare taxa in the total (rDNA) community were disproportionately active relative to abundant taxa, and members of the order Rhodospirillales had the highest potential for activity. We developed theory to explore the effects of random sampling from the rRNA and rDNA communities on observed differences between the communities. We found that random sampling, particularly in cases where active taxa are rare in the rDNA community, will give rise to observed differences in community composition including the occurrence of "phantom taxa", taxa which are detected in the rRNA community but not the rDNA community. We show that the use of comparative rRNA/rDNA techniques can reveal the structure and composition of the metabolically active portion of bacterial communities. Our observations suggest that metabolically active bacteria exist in the atmosphere and that these communities may be involved in the cycling of organic compounds in the atmosphere.

Global Atmospheric Transport and Source-Receptor Relationships for Arsenic.

Arsenic and many of its compounds are toxic pollutants in the global environment. They can be transported long distances in the atmosphere before depositing to the surface, but the global source-receptor relationships between various regions have not yet been assessed. We develop the first global model for atmospheric arsenic to better understand and quantify its intercontinental transport. Our model reproduces the observed arsenic concentrations in surface air over various sites around the world. Arsenic emissions from Asia and South America are found to be the dominant sources for atmospheric arsenic in the Northern and Southern Hemispheres, respectively. Asian emissions are found to contribute 39% and 38% of the total arsenic deposition over the Arctic and Northern America, respectively. Another 14% of the arsenic deposition to the Arctic region is attributed to European emissions. Our results indicate that the reduction of anthropogenic arsenic emissions in Asia and South America can significantly reduce arsenic pollution not only locally but also globally.

Interannual Variability in Baseline Ozone and Its Relationship to Surface Ozone in the Western U.S.

Baseline ozone refers to observed concentrations of tropospheric ozone at sites that have a negligible influence from local emissions. The Mount Bachelor Observatory (MBO) was established in 2004 to examine baseline air masses as they arrive to North America from the west. In May 2012, we observed an O3 increase of 2.0-8.5 ppbv in monthly average maximum daily 8-hour average O3 mixing ratio (MDA8 O3) at MBO and numerous other sites in the western U.S. compared to previous years. This shift in the O3 distribution had an impact on the number of exceedance days. We also observed a good correlation between daily MDA8 variations at MBO and at downwind sites. This suggests that under specific meteorological conditions, synoptic variation in O3 at MBO can be observed at other surface sites in the western U.S. At MBO, the elevated O3 concentrations in May 2012 are associated with low CO values and low water vapor values, consistent with transport from the upper troposphere/lower stratosphere (UT/LS). Furthermore, the Real-time Air Quality Modeling System (RAQMS) analyses indicate that a large flux of O3 from the UT/LS in May 2012 contributed to the observed enhanced O3 across the western U.S. Our results suggest that a network of mountaintop observations, LiDAR and satellite observations of O3 could provide key data on daily and interannual variations in baseline O3.