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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. [ABSTRACT FROM AUTHOR]

The declining trend in vehicle emissions has underscored the growing significance of volatile organic compound (VOC) emissions from volatile chemical products (VCPs). However, accurately representing VOC chemistry in simplified chemical mechanisms remains challenging due to its chemical complexity including speciation and reactivity. Previous studies have predominantly focused on VOCs from fossil fuel sources, leading to an underrepresentation of VOC chemistry from VCP sources. We developed an integrated chemical mechanism, RACM2B-VCP, that is compatible with WRF-Chem and is aimed at enhancing the representation of VOC chemistry, particularly from VCP sources, within the present urban environment. Evaluation against the Air Quality System (AQS) network data demonstrates that our model configured with RACM2B-VCP reproduces both the magnitude and spatial variability of O3 and PM 2.5 in Los Angeles. Furthermore, evaluation against comprehensive measurements of O3 and PM 2.5 precursors from the Reevaluating the Chemistry of Air Pollutants in California (RECAP-CA) airborne campaign and the Southwest Urban NO x and VOC Experiment (SUNVEx) ground site and mobile laboratory campaign confirm the model's accuracy in representing NO x and many VOCs and highlight remaining biases. Although there exists an underprediction in the total VOC reactivity of observed VOC species, our model with RACM2B-VCP exhibits good agreement for VOC markers emitted from different sectors, including biogenic, fossil fuel, and VCP sources. Through sensitivity analyses, we probe the contributions of VCP and fossil fuel emissions to total VOC reactivity and O3. Our results reveal that 52 % of the VOC reactivity and 35 % of the local enhancement of MDA8 O3 arise from anthropogenic VOC emissions in Los Angeles. Significantly, over 50 % of this anthropogenic fraction of either VOC reactivity or O3 is attributed to VCP emissions. The RACM2B-VCP mechanism created, described, and evaluated in this work is ideally suited for accurately representing ozone for the right reasons in the present urban environment where mobile, biogenic, and VCP VOCs are all important contributors to ozone formation. [ABSTRACT FROM AUTHOR]

Proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) is a technique commonly used to measure ambient volatile organic compounds (VOCs) in urban, rural, and remote environments. PTR-ToF-MS is known to produce artifacts from ion fragmentation, which complicates the interpretation and quantification of key atmospheric VOCs. This study evaluates the extent to which fragmentation and other ionization processes impact urban measurements of the PTR-ToF-MS ions typically assigned to isoprene (m/z 69, C 5 H 8 H +), acetaldehyde (m/z 45, CH 3 CHO +), and benzene (m/z 79, C 6 H 6 H +). Interferences from fragmentation are identified using gas chromatography (GC) pre-separation, and the impact of these interferences is quantified using ground-based and airborne measurements in a number of US cities, including Las Vegas, Los Angeles, New York City, and Detroit. In urban regions with low biogenic isoprene emissions (e.g., Las Vegas), fragmentation from higher-carbon aldehydes and cycloalkanes emitted from anthropogenic sources may contribute to m/z 69 by as much as 50 % during the day, while the majority of the signal at m/z 69 is attributed to fragmentation during the night. Interferences are a higher fraction of m/z 69 during airborne studies, which likely results from differences in the reactivity between isoprene and the interfering species along with the subsequent changes to the VOC mixture at higher altitudes. For other PTR masses, including m/z 45 and m/z 79, interferences are observed due to fragmentation and O 2+ ionization of VOCs typically used in solvents, which are becoming a more important source of anthropogenic VOCs in urban areas. We present methods to correct these interferences, which provide better agreement with GC measurements of isomer-specific molecules. These observations show the utility of deploying GC pre-separation for the interpretation PTR-ToF-MS spectra. [ABSTRACT FROM AUTHOR]

The declining trend in vehicle emissions has underscored the growing significance of Volatile Organic Compound (VOC) emissions from Volatile Chemical Products (VCP). However, accurately representing VOC chemistry in simplified chemical mechanisms remains challenging due to its chemical complexity including speciation and reactivity. Previous studies have predominantly focused on VOCs from fossil fuel sources, leading to an underrepresentation of VOC chemistry from VCP sources. We developed an integrated chemical mechanism, RACM2B-VCP, that is compatible with WRF-Chem and is aimed to enhance the representation of VOC chemistry, particularly from VCP sources, within the present urban environment. Evaluation against the Air Quality System (AQS) network data demonstrates that our model configured with RACM2B-VCP reproduces both the magnitude and spatial variability of O3 as well as PM2.5 in Los Angeles. Furthermore, evaluation against comprehensive measurements of O3 and PM2.5 precursors from the Reevaluating the Chemistry of Air Pollutants in California (RECAP-CA) airborne campaign and the Southwest Urban NOx and VOC Experiment (SUNVEx) ground site and mobile laboratory campaign, confirm the model's accuracy in representing NOx and many VOCs and highlight remaining biases. Although there exists an underprediction in the total VOC reactivity of observed VOC species, our model with RACM2B-VCP exhibits good agreement for VOC markers emitted from different sectors, including biogenic, fossil fuel, and VCP sources. Through sensitivity analyses, we probe the contributions of VCP and fossil fuel emissions to total VOC reactivity and O3. Our results reveal that 52% of the VOC reactivity and 35% of the local enhancement of MDA8 O3 arise from anthropogenic VOC emissions in Los Angeles. Significantly, over 50% of this anthropogenic fraction of either VOC reactivity or O3 is attributed to VCP emissions. The RACM2B-VCP mechanism created, described, and evaluated in this work is ideally suited for accurately representing ozone for the right reasons in the present urban environment where mobile, biogenic, and VCP VOCs are all important contributors to ozone formation. [ABSTRACT FROM AUTHOR]

The declining trend in vehicle emissions has underscored the growing significance of Volatile Organic Compound (VOC) emissions from Volatile Chemical Products (VCP). However, accurately representing VOC chemistry in simplified chemical mechanisms remains challenging due to its chemical complexity including speciation and reactivity. Previous studies have predominantly focused on VOCs from fossil fuel sources, leading to an underrepresentation of VOC chemistry from VCP sources. We developed an integrated chemical mechanism, RACM2B-VCP, that is compatible with WRF-Chem and is aimed to enhance the representation of VOC chemistry, particularly from VCP sources, within the present urban environment. Evaluation against the Air Quality System (AQS) network data demonstrates that our model configured with RACM2B-VCP reproduces both the magnitude and spatial variability of O3 as well as PM2.5 in Los Angeles. Furthermore, evaluation against comprehensive measurements of O3 and PM2.5 precursors from the Reevaluating the Chemistry of Air Pollutants in California (RECAP-CA) airborne campaign and the Southwest Urban NOx and VOC Experiment (SUNVEx) ground site and mobile laboratory campaign, confirm the model's accuracy in representing NOx and many VOCs and highlight remaining biases. Although there exists an underprediction in the total VOC reactivity of observed VOC species, our model with RACM2B-VCP exhibits good agreement for VOC markers emitted from different sectors, including biogenic, fossil fuel, and VCP sources. Through sensitivity analyses, we probe the contributions of VCP and fossil fuel emissions to total VOC reactivity and O3. Our results reveal that 52 % of the VOC reactivity and 35 % of the local enhancement of MDA8 O3 arise from anthropogenic VOC emissions in Los Angeles. Significantly, over 50 % of this anthropogenic fraction of either VOC reactivity or O3 is attributed to VCP emissions. The RACM2B-VCP mechanism created, described, and evaluated in this work is ideally suited for accurately representing ozone for the right reasons in the present urban environment where mobile, biogenic, and VCP VOCs are all important contributors to ozone formation. [ABSTRACT FROM AUTHOR]

Nitrogen oxides (NOx≡NO+NO2) are involved in most atmospheric photochemistry, including the formation of tropospheric ozone (O 3). While various methods exist to accurately measure NOx concentrations, it is still a challenge to quantify the source and flux of NOx emissions. We present airborne measurements of NOx and winds used to infer the emission of NOx across Los Angeles. The measurements were obtained during the research aircraft campaign RECAP-CA (Re-Evaluating the Chemistry of Air Pollutants in CAlifornia) in June 2021. Geographic allocations of the fluxes are compared to the NOx emission inventory from the California Air Resources Board (CARB). We find that the NOx fluxes have a pronounced weekend effect and are highest in the eastern part of the San Bernardino Valley. The comparison of the RECAP-CA and the modeled CARB NOx fluxes suggests that the modeled emissions are higher than expected near the coast and in Downtown Los Angeles and lower than expected further inland in the eastern part of the San Bernardino Valley. [ABSTRACT FROM AUTHOR]

The San Joaquin Valley is an agricultural region in California that suffers from poor air quality. Since traffic emissions are decreasing, other sources of volatile organic compounds (VOCs) are gaining importance in the formation of secondary air pollutants. Using airborne eddy covariance, we conducted direct, spatially resolved flux observations of a wide range of VOCs in the San Joaquin Valley during June 2021 at 23–36 ∘ C. Through land-cover-informed footprint disaggregation, we were able to attribute emissions to sources and identify tracers for distinct source types. VOC mass fluxes were dominated by alcohols, mainly from dairy farms, while oak isoprene and citrus monoterpenes were important sources of reactivity. Comparisons with two commonly used inventories showed that isoprene emissions in the croplands were overestimated, while dairy and highway VOC emissions were generally underestimated in the inventories, and important citrus and biofuel VOC point sources were missing from the inventories. This study thus presents unprecedented insights into the VOC sources in an intensive agricultural region and provides much needed information for the improvement of inventories, air quality predictions, and regulations. [ABSTRACT FROM AUTHOR]

Nitrogen oxides (NOx) are principle components of air pollution and serve as important ozone precursors. As the San Joaquin Valley (SJV) experiences some of the worst air quality in the United States, reducing NOx emissions is a pressing need, yet quantifying current emissions is complicated due to a mixture of mobile and agriculture sources. We performed airborne eddy covariance flux measurements during the Re-Evaluating the Chemistry of Air Pollutants in California (RECAP-CA) field campaign in June 2021. Combining footprint calculations and land cover statistics, we disaggregate the observed fluxes into component fluxes characterized by three different land cover types. On average, we find emissions of 0.95 mg N m -2 h -1 over highways, 0.43 mg N m -2 h -1 over urban areas, and 0.30 mg N m -2 h -1 over croplands. The calculated NOx emissions using flux observations are utilized to evaluate anthropogenic emissions inventories and soil NOx emissions schemes. We show that two anthropogenic inventories for mobile sources, EMFAC (EMission FACtors) and FIVE (Fuel-based Inventory for Vehicle Emissions), yield strong agreement with emissions derived from measured fluxes over urban regions. Three soil NOx schemes, including the MEGAN v3 (Model of Emissions of Gases and Aerosols from Nature), BEIS v3.14 (Biogenic Emission Inventory System), and BDISNP (Berkeley–Dalhousie–Iowa Soil NO Parameterization), show substantial underestimates over the study domain. Compared to the cultivated soil NOx emissions derived from measured fluxes, MEGAN and BEIS are lower by more than 1 order of magnitude, and BDISNP is lower by a factor of 2.2. Despite the low bias, observed soil NOx emissions and BDISNP present a similar spatial pattern and temperature dependence. We conclude that soil NOx is a key feature of the NOx emissions in the SJV and that a biogeochemical-process-based model of these emissions is needed to simulate emissions for modeling air quality in the region. [ABSTRACT FROM AUTHOR]

Proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) is a technique commonly used to measure ambient volatile organic compounds (VOCs) in urban, rural, and remote environments. PTR-ToF-MS is known to produce artifacts from ion fragmentation, which complicates the interpretation and quantification of key atmospheric VOCs. This study evaluates the extent to which fragmentation and other ionization processes impacts urban measurements of the PTR-ToF-MS ions typically assigned to isoprene (m/z 69, C5H8H+), acetaldehyde (m/z 45, CH3CHO+), and benzene (m/z 79, C6H6H+). Interferences from fragmentation are identified using gas-chromatography (GC) pre-separation and the impact of these interferences are quantified using ground-based and airborne measurements in a number of US cities, including Las Vegas, Los Angeles, New York City, and Detroit. In urban regions with low biogenic isoprene emissions (e.g., Las Vegas), fragmentation from higher carbon aldehydes and cycloalkanes emitted from anthropogenic sources may contribute to m/z 69 by as much as 50 % during the day, while the majority of the signal at m/z 69 is attributed to fragmentation during the night. Interferences are a higher fraction of m/z 69 during airborne studies, which likely results from differences in the reactivity between isoprene and the interfering species along with the subsequent changes to the VOC mixture at higher altitudes. For other PTR masses, including m/z 45 and m/z 79, interferences are observed due to the fragmentation and secondary ionization of VOCs typically used in solvents, which are becoming a more important source of anthropogenic VOCs in urban areas. We present methods to correct these interferences, which provide better agreement with GC measurements of isomer specific molecules. These observations show the utility of deploying GC pre-separation for the interpretation PTR-ToF-MS spectra. [ABSTRACT FROM AUTHOR]

The San Joaquin Valley is an agricultural region in California that suffers from poor air quality. Since traffic emissions are decreasing, other sources of volatile organic compounds (VOCs) are gaining importance in the formation of secondary air pollutants. Using airborne eddy covariance, we conducted direct, spatially resolved flux observations of a wide range of VOCs in the San Joaquin Valley during June 2021 at 23–36 °C. Through landcover-informed footprint disaggregation, we were able to attribute emissions to sources and identify tracers for distinct source types. VOC mass fluxes were dominated by alcohols, mainly from dairy farms, while oak isoprene and citrus monoterpenes were important sources of reactivity. Comparisons with two commonly used inventories showed that isoprene emissions in the croplands were overestimated, while dairy and highway VOC emissions were generally underestimated in the inventories, and important citrus and biofuel VOC point sources were missing from the inventories. This study thus presents unprecedented insights into the VOC sources in an intensive agricultural region and provides much needed information for the improvement of inventories, air quality predictions and regulations. [ABSTRACT FROM AUTHOR]

Nitrogen oxides (NO x ≡ NO + NO2) are involved in most atmospheric photochemistry, including the formation of tropospheric ozone (O3). While various methods exist to accurately measure NO x concentrations, it is still a challenge to quantify the source and flux of NO x emissions. We present airborne measurements of NO x and winds used to infer the emission of NO x across Los Angeles. The measurements were obtained during the research aircraft campaign RECAP-CA (Re-Evaluating the Chemistry of Air Pollutants in CAlifornia) in June 2021. Geographic allocations of the fluxes are compared to the NO x emission inventory from the California Air Resources Board (CARB). We find that the NO x fluxes have a pronounced weekend effect and are highest in the Eastern part of the San Bernardino valley. The comparison of the RECAP-CA and the modeled CARB NO x fluxes suggest the modeled emissions are too high near the coast and in downtown Los Angeles and too low further inland in the Eastern part of the San Bernardino valley. [ABSTRACT FROM AUTHOR]

Nitrogen oxides (NOx) are principle components of air pollution and serve as important ozone precursors. As the San Joaquin Valley (SJV) experiences some of the worst air quality in the United States, reducing NOx emissions is a pressing need, yet quantifying current emissions is complicated due to a mixture of mobile and agriculture sources. We performed airborne eddy covariance flux measurements during the Re-Evaluating the Chemistry of Air Pollutants in CAlifornia (RECAPCA) field campaign in June 2021. Combining footprint calculations and land cover statistics, we disaggregate the observed fluxes into component fluxes characterized by three different land cover types. On average we find emissions of 2.95 mg m−2 h −1 over highways, 1.24 mg m−2 h −1 over urban areas and 0.79 mg m−2 h −1 over croplands. The calculated NOx emissions using flux observations are utilized to evaluate anthropogenic emission inventories and soil NOx emission schemes. We show that two anthropogenic inventories for mobile sources, EMFAC (EMssion FACtor) and FIVE (Fuel-based Inventory for Vehicle Emissions), yield similar agreement with emissions derived from measured fluxes over urban regions with 24% and 22% low bias, respectively. Three soil NOx schemes, including MEGAN v3 (Model of Emissions of Gases and Aerosols from Nature), BEIS v3.14 (Biogenic Emission Inventory System) and BDISNP (Berkeley Dalhousie Iowa Soil NO Parameterization), show substantial underestimates over the study domain. Compared to the cultivated soil NOx emissions derived from measured fluxes, MEGAN and BEIS are lower by more than one order of magnitude and BDISNP is lower by a factor of 2.7. Despite the low bias, observed soil NOx emissions and BDISNP present a similar spatial pattern as well as temperature dependence. We conclude that soil NOx is a key feature of the NOx emissions in the SJV and that a state-of-the-science model of these emissions is needed to simulate emissions for modeling air quality in the region. [ABSTRACT FROM AUTHOR]