Estimate of OH trends over one decade in North American cities.

The hydroxyl radical (OH) is the most important oxidant on global and local scales in the troposphere. Urban OH controls the removal rate of primary pollutants and triggers the production of ozone. Interannual trends of OH in urban areas are not well documented or understood due to the short lifetime and high spatial heterogeneity of OH. We utilize machine learning with observational inputs emphasizing satellite remote sensing observations to predict surface OH in 49 North American cities from 2005 to 2014. We observe changes in the summertime OH over one decade, with wide variation among different cities. In 2014, compared to the summertime OH in 2005, 3 cities show a significant increase of OH, whereas, in 27 cities, OH decreases in 2014. The year-to-year variation of OH is mapped to the decline of the NO2 column. We conclude that these cities in this analysis are either in the NOx-limited regime or at the transition from a NOx suppressed regime to a NOx-limited regime. The result emphasizes that, in the future, controlling NOx emissions will be most effective in regulating the ozone pollution in these cities.

Comparison between Spatially Resolved Airborne Flux Measurements and Emission Inventories of Volatile Organic Compounds in Los Angeles.

Los Angeles is a major hotspot for ozone and particulate matter air pollution in the United States. Ozone and PM2.5 in this region have not improved substantially for the past decade, despite a reduction in vehicular emissions of their precursors, NOx and volatile organic compounds (VOCs). This reduction in "traditional" sources has made the current emission mixture of air pollutant precursors more uncertain. To map and quantify emissions of a wide range of VOCs in this urban area, we performed airborne eddy covariance measurements with wavelet analysis. VOC fluxes measured include tracers for source categories, such as traffic, vegetation, and volatile chemical products (VCPs). Mass fluxes were dominated by oxygenated VOCs, with ethanol contributing ∼29% of the total. In terms of OH reactivity and aerosol formation potential, terpenoids contributed more than half. Observed fluxes were compared with two commonly used emission inventories: the California Air Resources Board inventory and the combination of the Biogenic Emission Inventory System with the Fuel-based Inventory of Vehicle Emissions combined with Volatile Chemical Products (FIVE-VCP). The comparison shows mismatches regarding the amount, spatial distribution, and weekend effects of observed VOC emissions with the inventories. The agreement was best for typical transportation related VOCs, while discrepancies were larger for biogenic and VCP-related VOCs.

Methane Emissions from Dairy Operations in California's San Joaquin Valley Evaluated Using Airborne Flux Measurements.

State inventories indicate that dairy operations account for nearly half of California's methane budget. Recent analyses suggest, however, that these emissions may be underestimated, complicating efforts to develop emission reduction strategies. Here, we report estimates of dairy methane emissions in the southern San Joaquin Valley (SJV) of California in June 2021 using airborne flux measurements. We find average dairy methane fluxes of 512 ± 178 mg m-2 h-1 from a region of 300+ dairies near Visalia, CA using a combination of eddy covariance and mass balance-based techniques, corresponding to 118 ± 41 kg dairy-1 h-1. These values estimated during our June campaign are 39 ± 48% larger than annual average estimates from the recently developed VISTA-CA inventory. We observed notable increases in emissions with temperature. Our estimates align well with inventory predictions when parametrizations for the temperature dependence of emissions are applied. Our measurements further demonstrate that the VISTA-CA emission inventory is considerably more accurate than the EPA GHG-I inventory in this region. Source apportionment analyses confirm that dairy operations produce the majority of methane emissions in the southern SJV (∼65%). Fugitive oil and gas (O&G) sources account for the remaining ∼35%. Our results support the accuracy of the process-based models used to develop dairy emission inventories and highlight the need for additional investigation of the meteorological dependence of these emissions.

Improved Spatial Resolution in Modeling of Nitrogen Oxide Concentrations in the Los Angeles Basin.

The extent to which emission control technologies and policies have reduced anthropogenic NOx emissions from motor vehicles is large but uncertain. We evaluate a fuel-based emission inventory for southern California during the June 2021 period, coinciding with the Re-Evaluating the Chemistry of Air Pollutants in CAlifornia (RECAP-CA) field campaign. A modified version of the Fuel-based Inventory of Vehicle Emissions (FIVE) is presented, incorporating 1.3 km resolution gridding and a new light-/medium-duty diesel vehicle category. NOx concentrations and weekday-weekend differences were predicted using the WRF-Chem model and evaluated using satellite and aircraft observations. Model performance was similar on weekdays and weekends, indicating appropriate day-of-week scaling of NOx emissions and a reasonable distribution of emissions by sector. Large observed weekend decreases in NOx are mainly due to changes in on-road vehicle emissions. The inventory presented in this study suggests that on-road vehicles were responsible for 55-72% of the NOx emissions in the South Coast Air Basin, compared to the corresponding fraction (43%) in the planning inventory from the South Coast Air Quality Management District. This fuel-based inventory suggests on-road NOx emissions that are 1.5 ± 0.4, 2.8 ± 0.6, and 1.3 ± 0.7 times the reference EMFAC model estimates for on-road gasoline, light- and medium-duty diesel, and heavy-duty diesel, respectively.

Combining Machine Learning and Satellite Observations to Predict Spatial and Temporal Variation of near Surface OH in North American Cities.

The hydroxyl radical (OH) is the primary cleansing agent in the atmosphere. The abundance of OH in cities initiates the removal of local pollutants; therefore, it serves as the key species describing the urban chemical environment. We propose a machine learning (ML) approach as an efficient alternative to OH simulation using a computationally expensive chemical transport model. The ML model is trained on the parameters simulated from the WRF-Chem model, and it suggests that six predictive parameters are capable of explaining 76% of the OH variability. The parameters are the tropospheric NO2 column, the tropospheric HCHO column, J(O1D), H2O, temperature, and pressure. We then use observations of the tropospheric NO2 column and HCHO column from OMI as input to the ML model to enable measurement-based prediction of daily near surface OH at 1:30 pm local time across 49 North American cities over the course of 10 years between 2005 and 2014. The result is validated by comparing the OH predictions to measurements of isoprene, which has a source that is uncorrelated with OH and is removed rapidly and almost exclusively by OH in the daytime. We demonstrate that the predicted OH is, as expected, anticorrelated with isoprene. We also show that this ML model is consistent with our understanding of OH chemistry given the solely data-driven nature.

Elucidating Contributions of Anthropogenic Volatile Organic Compounds and Particulate Matter to Ozone Trends over China.

In China, emissions of ozone (O3)-producing pollutants have been targeted for mitigation to reduce O3 pollution. However, the observed O3 decrease is slower than/opposite to expectations affecting the health of millions of people. For a better understanding of this failure and its connection with anthropogenic emissions, we quantify the summer O3 trends that would have occurred had the weather stayed constant by applying a numerical tool that "de-weathers" observations across 31 urban regions (123 cities and 392 sites) over 8 years. O3 trends are significant (p < 0.05) over 234 sites after de-weathering, contrary to the directly observed trends (only 39 significant due to high meteorology-induced variability). The de-weathered data allow categorizing cities in China into four different groups regarding O3 mitigation, with group 1 exhibiting steady O3 reductions, while group 4 showing significant (p < 0.05) O3 increases. Analysis of the relationships between de-weathered odd oxygen and nitrogen oxides illustrates how the changes in NOx, in anthropogenic volatile organic compounds (VOCs), and reductions in fine particulate matter (PM2.5) affect the O3 trends differently in these groups. While this analysis suggests that VOC reductions are the main driver of O3 decreases in group 1, groups 3 and 4 are primarily affected by decreasing PM2.5, which results in enhanced O3 formation. Our analysis demonstrates both the importance of and possibility for isolating emission-driven changes from climate and weather for interpreting short-term air quality observations.

The effects of facemasks on airway inflammation and endothelial dysfunction in healthy young adults: a double-blind, randomized, controlled crossover study.

BACKGROUND: Facemasks are increasingly worn during air pollution episodes in China, but their protective effects are poorly understood. We aimed to evaluate the filtration efficiencies of N95 facemasks and the cardiopulmonary benefits associated with wearing facemasks during episodes of pollution. RESULTS: We measured the filtration efficiencies of particles in ambient air of six types of N95 facemasks with a manikin headform. The most effective one was used in a double-blind, randomized, controlled crossover study, involving 15 healthy young adults, conducted during 2 days of severe pollution in Beijing, China. Subjects were asked to walk along a busy-traffic road for 2 h wearing authentic or sham N95 facemasks. Clinical tests were performed four times to determine changes in the levels of biomarkers of airway inflammation, endothelial dysfunction, and oxidative stress within 24 h after exposure. The facemasks removed 48-75% of number concentrations of ambient air particles between 5.6 and 560 nm in diameter. After adjustments for multiple comparison, the exhaled nitric oxide level and the levels of interleukin-1α, interleukin-1ß, and interleukin-6 in exhaled breath condensate increased significantly in all subjects; however, the increases in those wearing authentic facemasks were statistically significantly lower than in the sham group. No significant between-group difference was evident in the urinary creatinine-corrected malondialdehyde level. In arterial stiffness indicators, the ejection duration of subjects wearing authentic facemasks was higher after exposure compared to the sham group; no significant between-group difference was found in augmentation pressure or the augmentation index. CONCLUSIONS: In young healthy adults, N95 facemasks partially reduced acute particle-associated airway inflammation, but neither systemic oxidative stress nor endothelial dysfunction improved significantly. The clinical significance of these findings long-term remains to be determined. TRIAL REGISTRATION: The trial registration number (TRN) for this study is ChiCTR1800016099 , which was retrospectively registered on May 11, 2018.

Temperature-dependent emissions dominate aerosol and ozone formation in Los Angeles.

Despite declines in transportation emissions, urban North America and Europe still face unhealthy air pollution levels. This has challenged conventional understanding of the sources of their volatile organic compound (VOC) precursors. Using airborne flux measurements to map emissions of a wide range of VOCs, we demonstrate that biogenic terpenoid emissions contribute ~60% of emitted VOC OH reactivity, ozone, and secondary organic aerosol formation potential in summertime Los Angeles and that this contribution strongly increases with temperature. This implies that control of nitrogen oxides is key to reducing ozone formation in Los Angeles. We also show some anthropogenic VOC emissions increase with temperature, which is an effect not represented in current inventories. Air pollution mitigation efforts must consider that climate warming will strongly change emission amounts and composition.