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.

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.

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.

Atmospheric biogenic volatile organic compounds in the Alaskan Arctic tundra: constraints from measurements at Toolik Field Station.

The Arctic is a climatically sensitive region that has experienced warming at almost 3 times the global average rate in recent decades, leading to an increase in Arctic greenness and a greater abundance of plants that emit biogenic volatile organic compounds (BVOCs). These changes in atmospheric emissions are expected to significantly modify the overall oxidative chemistry of the region and lead to changes in VOC composition and abundance, with implications for atmospheric processes. Nonetheless, observations needed to constrain our current understanding of these issues in this critical environment are sparse. This work presents novel atmospheric in situ proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) measurements of VOCs at Toolik Field Station (TFS; 68°38' N, 149°36' W), in the Alaskan Arctic tundra during May-June 2019. We employ a custom nested grid version of the GEOS-Chem chemical transport model (CTM), driven with MEGANv2.1 (Model of Emissions of Gases and Aerosols from Nature version 2.1) biogenic emissions for Alaska at 0.25° × 0.3125° resolution, to interpret the observations in terms of their constraints on BVOC emissions, total reactive organic carbon (ROC) composition, and calculated OH reactivity (OHr) in this environment. We find total ambient mole fraction of 78 identified VOCs to be 6.3 ± 0.4 ppbv (10.8 ± 0.5 ppbC), with overwhelming (> 80 %) contributions are from short-chain oxygenated VOCs (OVOCs) including methanol, acetone and formaldehyde. Isoprene was the most abundant terpene identified. GEOS-Chem captures the observed isoprene (and its oxidation products), acetone and acetaldehyde abundances within the combined model and observation uncertainties (±25 %), but underestimates other OVOCs including methanol, formaldehyde, formic acid and acetic acid by a factor of 3 to 12. The negative model bias for methanol is attributed to underestimated biogenic methanol emissions for the Alaskan tundra in MEGANv2.1. Observed formaldehyde mole fractions increase exponentially with air temperature, likely reflecting its biogenic precursors and pointing to a systematic model underprediction of its secondary production. The median campaign-calculated OHr from VOCs measured at TFS was 0.7 s-1, roughly 5 % of the values typically reported in lower-latitude forested ecosystems. Ten species account for over 80 % of the calculated VOC OHr, with formaldehyde, isoprene and acetaldehyde together accounting for nearly half of the total. Simulated OHr based on median-modeled VOCs included in GEOS-Chem averages 0.5 s-1 and is dominated by isoprene (30 %) and monoterpenes (17 %). The data presented here serve as a critical evaluation of our knowledge of BVOCs and ROC budgets in high-latitude environments and represent a foundation for investigating and interpreting future warming-driven changes in VOC emissions in the Alaskan Arctic tundra.

Observations of volatile organic and sulfur compounds in ambient air and health risk assessment near a paper mill in rural Idaho, U. S. A.

The Lewis-Clark Valley is a rural area that includes the cities of Lewiston, Idaho and Clarkston, Washington and the surrounding areas. The largest industry in the Lewis-Clark Valley is a pulp paper mill located in Lewiston which emits particulate matter and odorous sulfur air pollutants. This study analyzed the Lewis-Clark Valley air composition and seasonal, temporal and spatial variations of volatile organic compounds (VOCs) from 2017 to 2018 to determine potential health risks of the paper mill emissions to the surrounding community. Both active and passive air sampling via sorbent tubes were analyzed by thermal desorption - gas chromatography-mass spectrometry (TD-GC-MS). Fifty VOCs including benzene, toluene, chloroform, dimethyl sulfide and dimethyl disulfide were measured in the ambient air of the Lewis-Clark Valley at ten different sites, totaling over 800 samples. In addition, passive sorbent tubes were deployed in 2018 to obtain monthly averages in Lewis-Clark Valley and three urban locations in Idaho and Washington for comparison. United States Environmental Protection Agency (2001) methodology was used to assess cancer risks in the community based on the upper confidence levels of five carcinogens and nine air toxics. The Lewis-Clark Valley had similar levels of benzene to urban areas but had a strong signature of chloroform and sulfides from the paper mill. The cumulative cancer risk was 2 x 10-6 - 11 × 10-6 mainly due to the compounds chloroform, benzene and carbon tetrachloride. The hazard index of other air toxics was less than one. Overall, these air pollutants were considered low risk to the local population.

Biogenic volatile organic compound ambient mixing ratios and emission rates in the Alaskan Arctic tundra.

Rapid Arctic warming, a lengthening growing season, and the increasing abundance of biogenic volatile-organic-compound-emitting shrubs are all anticipated to increase atmospheric biogenic volatile organic compounds (BVOCs) in the Arctic atmosphere, with implications for atmospheric oxidation processes and climate feedbacks. Quantifying these changes requires an accurate understanding of the underlying processes driving BVOC emissions in the Arctic. While boreal ecosystems have been widely studied, little attention has been paid to Arctic tundra environments. Here, we report terpenoid (isoprene, monoterpenes, and sesquiterpenes) ambient mixing ratios and emission rates from key dominant vegetation species at Toolik Field Station (TFS; 68°38' N, 149°36' W) in northern Alaska during two back-to-back field campaigns (summers of 2018 and 2019) covering the entire growing season. Isoprene ambient mixing ratios observed at TFS fell within the range of values reported in the Eurasian taiga (0-500 parts per trillion by volume - pptv), while monoterpene and sesquiterpene ambient mixing ratios were respectively close to and below the instrumental quantification limit (~ 2 pptv). Isoprene surface emission rates ranged from 0.2 to 2250 µgC m-2 h-1 (mean of 85 µgC m-2 h-1) and monoterpene emission rates remained, on average, below 1 µgC m-2 h-1 over the course of the study. We further quantified the temperature dependence of isoprene emissions from local vegetation, including Salix spp. (a known isoprene emitter), and compared the results to predictions from the Model of Emissions of Gases and Aerosols from Nature version 2.1 (MEGAN2.1). Our observations suggest a 180 %-215 % emission increase in response to a 3-4°C warming, and the MEGAN2.1 temperature algorithm exhibits a close fit with observations for enclosure temperatures in the 0-30°C range. The data presented here provide a baseline for investigating future changes in the BVOC emission potential of the under-studied Arctic tundra environment.