Multi-scale modeling study of the source contributions to near-surface ozone and sulfur oxides levels over California during the ARCTAS-CARB period

Chronic high surface ozone (O3) levels and the increasing sulfur oxides (SOx = SO2+SO4) ambient concentrations over South Coast (SC) and other areas of California (CA) are affected by both local emissions and long-range transport. In this paper, multi-scale tracer, full-chemistry and adjoint simulations using the STEM atmospheric chemistry model are conducted to assess the contribution of local emission sourcesto SC O3 and to evaluate the impacts of transported sulfur and local emissions on the SC sulfur budgetduring the ARCTAS-CARB experiment period in 2008. Sensitivity simulations quantify contributions of biogenic and fire emissions to SC O3 levels. California biogenic and fire emissions contribute 3–4 ppb to near-surface O3 over SC, with larger contributions to other regions in CA. During a long-range transport event from Asia starting from 22 June, high SOx levels (up to ~0.7 ppb of SO2 and ~1.3 ppb of SO4) is observed above ~6 km, but they did not affect CA surface air quality. The elevated SOx observed at 1–4 km is estimated to enhance surface SOx over SC by ~0.25 ppb (upper limit) on ~24 June. The near-surface SOx levels over SC during the flight week are attributed mostly to local emissions. Two anthropogenic SOx emission inventories (EIs) from the California Air Resources Board (CARB) and the US Environmental Protection Agency (EPA) are compared and applied in 60 km and 12 km chemical transport simulations, and the results are compared withobservations. The CARB EI shows improvements over the National Emission Inventory (NEI) by EPA, but generally underestimates surface SC SOx by about a factor of two. Adjoint sensitivity analysis indicated that SO2 levels at 00:00 UTC (17:00 local time) at six SC surface sites were influenced by previous day maritime emissions over the ocean, the terrestrial emissions over nearby urban areas, and by transported SO2 from the north through both terrestrial and maritime areas. Overall maritime emissions contribute 10–70% of SO2 and 20–60% fine SO4 on-shore and over the most terrestrial areas, with contributions decreasing with in-land distance from the coast. Maritime emissions also modify the photochemical environment, shifting O3 production over coastal SC to more VOC-limited conditions. These suggest an important role for shipping emission controls in reducing fine particle and O3concentrations in SC

Simulating reactive nitrogen, carbon monoxide, and ozone in California during ARCTAS-CARB 2008 with high wildfire activity

Predictions of O_3, CO, total NO_y and individual NO_y species (NO, NO_2, HNO_3, PAN, alkyl nitrates and aerosol nitrate) from a fine resolution regional air quality modeling system for the South Coast Air Basin (SoCAB) and San Joaquin Valley Air Basin (SJVAB) of California are presented and evaluated for the 2008 ARCTAS-CARB campaign. The measurements of the chemical compounds from the fire plumes during the field campaign allow for the evaluation of the model's ability to simulate fire-influenced air masses as well. In general, the model successfully simulated the broad spatial distribution of chemical compounds in both air basins as well as the variation within the basins. Using inventories that reflect 2008 emissions levels, the model performed well in simulating NO_x (NO + NO_2) in SoCAB. Therefore, the under prediction of O_3 over these areas is more likely caused by uncertainties with the VOC emissions, chemistry, or discrepancies in the meteorology. The model did not capture the relatively high levels of O_3, and some reactive nitrogen species that were measured off shore of the SoCAB, indicating potential missing sources or the transport from on shore to off shore was not successfully captured. In SJVAB, the model had good performance in simulating different chemical compounds in the Fresno and Arvin areas. However, enhanced concentrations of O_3, NO_x, HNO_3 and PAN near dairy farms were significantly underestimated in the model. Negative biases also exist for O_3 and HNO_3 near oil fields, suggesting larger uncertainties associated with these emission sources. While the model simulated the total NO_y mixing ratios reasonably well, the prediction for partitioning between individual compounds showed larger uncertainties in the model simulation. Although the fire emissions inventory was updated to include the latest emissions estimates and speciation profiles, our model shows limited improvement in simulating the enhancement of O_3, CO, and PAN under fire impact as compared to a previous version of the modeling system. Further improvements in simulating fire emissions, especially the timing and the plume injection heights, are desired in order to better simulate the impact of fires

Application of a novel multiple-scattering approach to photoelectron diffraction and auger electron diffraction

Thesis (Ph. D.)--University of Hawaii at Manoa, 1991.Includes bibliographical references.Microfiche.xxv, 301 leaves, bound ill. 29 c

An extended approach to calculate the ozone relative response factors used in the attainment demonstration for the National Ambient Air Quality Standards

<div><p>With the promulgation of the National Ambient Air Quality Standards (NAAQS or standard) for 8-hr ozone (O₃), the U.S. Environmental Protection Agency (EPA) issued modeling guidance that advocated the use of results from photochemical air quality models in a relative sense. In doing so, the EPA provided guidance on how to calculate relative response factors (RRFs) that can project current design value (DV) mixing ratios into the future for the purpose of determining the attainment status with respect to the O₃ standard. The RRFs recommended by the EPA represent the average response of the photochemical model over a broad range of O₃ mixing ratios above a specified cutoff threshold. However, it is known that O₃ response to emission reductions of limiting precursors (i.e., NO_x and/or VOC) is greater on days with higher O₃ mixing ratios compared to days with lower mixing ratios. In this study, we present a segmented RRF concept termed band-RRF, which takes into account the different model responses at different O₃ mixing ratios. The new band-RRF concept is demonstrated in the San Joaquin Valley (SJV) region of California for the 1-hr and 8-hr O₃ standards. The 1-hr O₃ analysis is relevant to work done in support of the SJV O₃ State Implementation Plan (SIP) submitted to the EPA in 2013. The 8-hr example for the future year of 2019 is presented for illustrative purposes only. Further work will be conducted with attainment deadline of 2032 as part of upcoming SIPs for the 0.075 parts per million (ppm) 8-hr O₃ standard. The applicability of the band-RRF concept to the particulate matter (PM_2.5) standards is also discussed. </p><p></p><p>Implications:</p><p>Results of photochemical models are used in regulatory applications in a relative sense using relative response factors (RRFs), which represent the impacts of emissions reductions over a wide range of ozone (O₃) values. It is possible to extend the concept of RRFs to account for the fact that higher O₃ mixing ratios (both 1-hr and 8-hr) respond more to emissions controls of limiting precursors than do lower O₃ mixing ratios. We demonstrate this extended concept, termed band-RRF, for the 1-hr and 8-hr O₃ National Ambient Air Quality Standard (NAAQS or standard) in the San Joaquin Valley of California. This extension can also be made applicable to the 24-hr PM_2.5 and annual PM_2.5 standards.</p><p></p><p></p></div

Simulating reactive nitrogen, carbon monoxide, and ozone in California during ARCTAS-CARB 2008 with high wildfire activity

Predictions of O3, CO, total NOy and individual NOy species (NO, NO2, HNO3, PAN, alkyl nitrates and aerosol nitrate) from a fine resolution regional air quality modeling system for the South Coast Air Basin (SoCAB) and San Joaquin Valley Air Basin (SJVAB) of California are presented and evaluated for the 2008 ARCTAS-CARB campaign. The measurements of the chemical compounds from the fire plumes during the field campaign allow for the evaluation of the model\u27s ability to simulate fire-influenced air masses as well. In general, the model successfully simulated the broad spatial distribution of chemical compounds in both air basins as well as the variation within the basins. Using inventories that reflect 2008 emissions levels, the model performed well in simulating NOx (NO + NO2) in SoCAB. Therefore, the under prediction of O3 over these areas is more likely caused by uncertainties with the VOC emissions, chemistry, or discrepancies in the meteorology. The model did not capture the relatively high levels of O3, and some reactive nitrogen species that were measured off shore of the SoCAB, indicating potential missing sources or the transport from on shore to off shore was not successfully captured. In SJVAB, the model had good performance in simulating different chemical compounds in the Fresno and Arvin areas. However, enhanced concentrations of O3, NOx, HNO3 and PAN near dairy farms were significantly underestimated in the model. Negative biases also exist for O3 and HNO3 near oil fields, suggesting larger uncertainties associated with these emission sources. While the model simulated the total NOy mixing ratios reasonably well, the prediction for partitioning between individual compounds showed larger uncertainties in the model simulation. Although the fire emissions inventory was updated to include the latest emissions estimates and speciation profiles, our model shows limited improvement in simulating the enhancement of O3, CO, and PAN under fire impact as compared to a previous version of the modeling system. Further improvements in simulating fire emissions, especially the timing and the plume injection heights, are desired in order to better simulate the impact of fires

Simulating the Weekly Cycle of NO x

United States Environmental Protection Agency guidance on the use of photochemical models for assessing the efficacy of an emissions control strategy for ozone requires that modeling be used in a relative sense. Consequently, testing a modeling system's ability to predict changes in ozone resulting from emission changes is critical. We evaluate model simulations for precursor species (NO$_x$, CO, and volatile organic compounds [VOCs]), radicals (OH and HO$_2$), a secondary pollutant (O$_3$), and the model response of these compounds to weekend/weekday emission changes during California Nexus study in 2010. The modeling system correctly simulated the broad spatial and temporal variation of NO$_x$ and O$_3$ in California South Coast. Although the model generally underpredicted the daytime mixing ratios of NO$_2$ at the surface and overpredicted the NO$_2$ column, the simulated weekend to weekday ratios are consistent with each other and match the observed ratios well. The modeling system exhibited reasonable performance in simulating the VOC compounds with fossil fuel origins but has larger bias in simulating certain species associated with noncombustion sources. The modeling system successfully captured the weekend changes of the enhancement ratios for various VOC species to CO and the relative changes of HO$_x$, which are indicators of faster chemical processing on weekends. This work demonstrates satisfactory model performances for O$_3$ and most relevant chemical compounds with more robust performance in simulating weekend versus weekday changes. Improved planetary boundary layer height simulations, a better understanding of OH‐HO$_2$ cycling, continued improvement of emissions, especially urban biogenic emissions and emissions of oxygenated VOCs, are important for future model improvement

Simulating the Weekly Cycle of NOx_x-VOC-HOx_x-O3_3 Photochemical System in the South Coast of California During CalNex-2010 Campaign

United States Environmental Protection Agency guidance on the use of photochemical models for assessing the efficacy of an emissions control strategy for ozone requires that modeling be used in a relative sense. Consequently, testing a modeling system's ability to predict changes in ozone resulting from emission changes is critical. We evaluate model simulations for precursor species (NO$_x$, CO, and volatile organic compounds [VOCs]), radicals (OH and HO$_2$), a secondary pollutant (O$_3$), and the model response of these compounds to weekend/weekday emission changes during California Nexus study in 2010. The modeling system correctly simulated the broad spatial and temporal variation of NO$_x$ and O$_3$ in California South Coast. Although the model generally underpredicted the daytime mixing ratios of NO$_2$ at the surface and overpredicted the NO$_2$ column, the simulated weekend to weekday ratios are consistent with each other and match the observed ratios well. The modeling system exhibited reasonable performance in simulating the VOC compounds with fossil fuel origins but has larger bias in simulating certain species associated with noncombustion sources. The modeling system successfully captured the weekend changes of the enhancement ratios for various VOC species to CO and the relative changes of HO$_x$, which are indicators of faster chemical processing on weekends. This work demonstrates satisfactory model performances for O$_3$ and most relevant chemical compounds with more robust performance in simulating weekend versus weekday changes. Improved planetary boundary layer height simulations, a better understanding of OH‐HO$_2$ cycling, continued improvement of emissions, especially urban biogenic emissions and emissions of oxygenated VOCs, are important for future model improvement