Search

A flexible treatment for gas- and aerosol-phase chemical processes has been developed for models of diverse scale, from box models up to global models. At the core of this novel framework is an “abstracted aerosol representation” that allows a given chemical mechanism to be solved in atmospheric models with different aerosol representations (e.g., sectional, modal, or particle-resolved). This is accomplished by treating aerosols as a collection of condensed phases that are implemented according to the aerosol representation of the host model. The framework also allows multiple chemical processes (e.g., gas- and aerosol-phase chemical reactions, emissions, deposition, photolysis, and mass transfer) to be solved simultaneously as a single system. The flexibility of the model is achieved by (1) using an object-oriented design that facilitates extensibility to new types of chemical processes and to new ways of representing aerosol systems, (2) runtime model configuration using JSON input files that permits making changes to any part of the chemical mechanism without recompiling the model (this widely used, human-readable format allows entire gas- and aerosol-phase chemical mechanisms to be described with as much complexity as necessary), and (3) automated comprehensive testing that ensures stability of the code as new functionality is introduced. Together, these design choices enable users to build a customized multiphase mechanism without having to handle preprocessors, solvers, or compilers. Removing these hurdles makes this type of modeling accessible to a much wider community, including modelers, experimentalists, and educators. This new treatment compiles as a stand-alone library and has been deployed in the particle-resolved PartMC model and in the Multiscale Online AtmospheRe CHemistry (MONARCH) chemical weather prediction system for use at regional and global scales. Results from the initial deployment to box models of different complexity and MONARCH will be di, Matthew L. Dawson has received funding from the European Union's Horizon 2020 research and innovation program under Marie Skłodowska-Curie grant agreement no. 747048. Matthew L. Dawson, Oriol Jorba, and Christian Guzman have been supported by the Ministerio de Ciencia, Innovación y Universidades (grant no. RTI2018-099894-BI00). Christian Guzman acknowledges funding from the AXA Research Fund. Nicole Riemer, Matthew West, and Jeffrey H. Curtis acknowledge funding from the National Science Foundation (grant no. AGS 19-41110). This material is based upon work supported by the National Center for Atmospheric Research, which is a major facility sponsored by the National Science Foundation under cooperative agreement no. 1852977., Peer Reviewed, Postprint (published version)

A flexible treatment for gas- and aerosol-phase chemical processes has been developed for models of diverse scale, from box models up to global models. At the core of this novel framework is an "abstracted aerosol representation" that allows a given chemical mechanism to be solved in atmospheric models with different aerosol representations (e.g., sectional, modal, or particle-resolved). This is accomplished by treating aerosols as a collection of condensed phases that are implemented according to the aerosol representation of the host model. The framework also allows multiple chemical processes (e.g., gas- and aerosol-phase chemical reactions, emissions, deposition, photolysis, and mass-transfer) to be solved simultaneously as a single system. The flexibility of the model is achieved by (1) using an object-oriented design that facilitates extensibility to new types of chemical processes and to new ways of representing aerosol systems; (2) runtime model configuration using JSON input files that permits making changes to any part of the chemical mechanism without recompiling the model; this widely used, human-readable format allows entire gas- and aerosol-phase chemical mechanisms to be described with as much complexity as necessary; and (3) automated comprehensive testing that ensures stability of the code as new functionality is introduced. Together, these design choices enable users to build a customized multiphase mechanism, without having to handle pre-processors, solvers or compilers. This new treatment compiles as a stand-alone library and has been deployed in the particle-resolved PartMC model and in the MONARCH chemical weather prediction system for use at regional and global scales. Results from the initial deployment will be discussed, along with future extension to more complex gas-aerosol systems, and the integration of GPU-based solvers.

This paper presents a comprehensive description and benchmark evaluation of the tropospheric gas-phase chemistry component of the Multiscale Online Nonhydrostatic AtmospheRe CHemistry model (NMMB-MONARCH), formerly known as NMMB/BSC-CTM, that can be run on both regional and global domains. Here, we provide an extensive evaluation of a global annual cycle simulation using a variety of background surface stations (EMEP, WDCGG and CASTNET), ozonesondes (WOUDC, CMD and SHADOZ), aircraft data (MOZAIC and several campaigns), and satellite observations (SCIAMACHY and MOPITT). We also include an extensive discussion of our results in comparison to other state-of-the-art models. We note that in this study, we omitted aerosol processes and some natural emissions (lightning and volcano emissions). The model shows a realistic oxidative capacity across the globe. The seasonal cycle for CO is fairly well represented at different locations (correlations around 0.3–0.7 in surface concentrations), although concentrations are underestimated in spring and winter in the Northern Hemisphere, and are overestimated throughout the year at 800 and 500 hPa in the Southern Hemisphere. Nitrogen species are well represented in almost all locations, particularly NO2 in Europe (root mean square error – RMSE – below 5 ppb). The modeled vertical distributions of NOx and HNO3 are in excellent agreement with the observed values and the spatial and seasonal trends of tropospheric NO2 columns correspond well to observations from SCIAMACHY, capturing the highly polluted areas and the biomass burning cycle throughout the year. Over Asia, the model underestimates NOx from March to August, probably due to an underestimation of NOx emissions in the region. Overall, the comparison of the modeled CO and NO2 with MOPITT and SCIAMACHY observations emphasizes the need for more accurate emission rates from anthropogenic and biomass burning sources (i.e., specification of temporal variability). The resulting ozone, The authors wish to thank WOUDC, GAW, EMEP, WDCGG, CASTNET-EPA, NADP and EANET for the provision of measurement stations. The authors acknowledge for the strong support of the European Commission, Airbus, and the Airlines (Lufthansa, Austrian, Air France) who carry free of charge the MOZAIC equipment and perform the maintenance since 1994. MOZAIC is presently funded by INSU-CNRS (France), Meteo-France, and Forschungszentrum (FZJ, Julich, Germany). The MOZAIC database is supported by ETHER (CNES and INSU-CNRS). Also, thanks go to the free use of the MOPITTCO data obtained from the NASA Langley Research Center Atmospheric Science Data Center. SCIAMACHY radiances have been provided by ESA. We also thank Beatriz Monge-Sanz for providing the COPCAT coefficients. This work is funded by grants CGL2013-46736-R, Supercomputación and e-ciencia Project (CSD2007-0050) from the Consolider-Ingenio 2010 program of the Spanish Ministry of Economy and Competitiveness. Further support was provided by the SEV-2011-00067 grant of the Severo Ochoa Program, awarded by the Spanish Government. Andreas Hilboll received funding from the Earth System Science Research School (ESSReS), an initiative of the Helmholtz Association of German research centres (HGF) at the Alfred Wegener Institute for Polar and Marine Research. Carlos Pérez García-Pando acknowledges long-term support from the AXA Research Fund. The authors thankfully acknowledge the computer resources at MareNostrum and the technical support provided by Barcelona Supercomputing Center (RES-AECT-2015-1-0007). Comments from two anonymous reviewers are gratefully acknowledge., Peer Reviewed, Postprint (published version)

The authors wish to thank WOUDC, GAW, EMEP, WDCGG, CASTNET-EPA, NADP and EANET for the provision of measurement stations. Also, thanks go to the free use of the MOPITT CO data obtained from the NASA Langley Research Center Atmospheric Science Data Center. SCIAMACHY radiances have been provided by ESA. This work is funded by grants CGL2013-46736-R, Supercomputación and e-ciencia Project (CSD2007-0050) from the Consolider-Ingenio 2010 program of the Spanish Ministry of Economy and Competitiveness. Further support was provided by the SEV-2011-00067 grant of the Severo Ochoa Program, awarded by the Spanish Government. A.H. received funding from the Earth System Science Research School (ESSReS), an initiative of the Helmholtz Association of German research centres (HGF) at the AlfredWegener Institute for Polar and Marine Research. All the numerical simulations were performed with the MareNostrum Supercomputer hosted by the Barcelona Supercomputing Center. We also thank Beatriz Monge-Sanz for providing the COPCAT coefficients., Peer Reviewed, Postprint (author's final draft)

The use of massively parallel computers provides an avenue to overcome the computational requirements in the study of atmospheric chemical dynamics. General considerations on parallel implementation of air quality models are outlined including domain decomposition strategies, algorithm evaluation and design, portability, modularity, and buffering techniques used in I/O operations. Results are given for the implementation of the CIT urban air pollution model on distributed memory multiple instruction / multiple data (MIMD) machines ranging from a cluster of workstations to a 512 node Intel Paragon. The central challenge in developing a parallel air pollution model is the implementation of the chemistry and transport operators used in the solution of the atmospheric reaction-diffusion equation. The chemistry operator is generally the most computationally intensive step in atmospheric air quality models. A new method based on Richardson extrapolation to solve the chemical kinetics is presented. The transport operator is the most challenging to solve numerically. Because of its hyperbolic nature non-physical oscillations and/or negative concentrations appear near steep gradient regions of the solution. Six algorithms for solving the advection equation are compared to determine their suitability for use in parallel photochemical air quality models. Four algorithms for filtering the numerical noise produced when solving the advection equation are also compared. A speed-up factor of 94.9 has been measured when the I/O, transport, and chemistry portions of the model are performed in parallel. This work provides the computational infrastructure required to incorporate new physico-chemical phenomena in the next generation of urban- or regional-scale air quality models. Finally, the SARMAP model is used to model the San Joaquin Valley of California. SARMAP is the updated version of RADM. It can be considered a state-of-the- art regional air pollution model. Like the CIT model

The use of massively parallel computers provides an avenue to overcome the computational requirements in the study of atmospheric chemical dynamics. General considerations on parallel implementation of air quality models are outlined including domain decomposition strategies, algorithm evaluation and design, portability, modularity, and buffering techniques used in I/O operations. Results are given for the implementation of the CIT urban air pollution model on distributed memory multiple instruction / multiple data (MIMD) machines ranging from a cluster of workstations to a 512 node Intel Paragon. The central challenge in developing a parallel air pollution model is the implementation of the chemistry and transport operators used in the solution of the atmospheric reaction-diffusion equation. The chemistry operator is generally the most computationally intensive step in atmospheric air quality models. A new method based on Richardson extrapolation to solve the chemical kinetics is presented. The transport operator is the most challenging to solve numerically. Because of its hyperbolic nature non-physical oscillations and/or negative concentrations appear near steep gradient regions of the solution. Six algorithms for solving the advection equation are compared to determine their suitability for use in parallel photochemical air quality models. Four algorithms for filtering the numerical noise produced when solving the advection equation are also compared. A speed-up factor of 94.9 has been measured when the I/O, transport, and chemistry portions of the model are performed in parallel. This work provides the computational infrastructure required to incorporate new physico-chemical phenomena in the next generation of urban- or regional-scale air quality models. Finally, the SARMAP model is used to model the San Joaquin Valley of California. SARMAP is the updated version of RADM. It can be considered a state-of-the- art regional air pollution model. Like the CIT model

The use of massively parallel computers provides an avenue to overcome the computational requirements in the study of atmospheric chemical dynamics. General considerations on parallel implementation of air quality models are outlined including domain decomposition strategies, algorithm evaluation and design, portability, modularity, and buffering techniques used in I/O operations. Results are given for the implementation of the CIT urban air pollution model on distributed memory multiple instruction / multiple data (MIMD) machines ranging from a cluster of workstations to a 512 node Intel Paragon. The central challenge in developing a parallel air pollution model is the implementation of the chemistry and transport operators used in the solution of the atmospheric reaction-diffusion equation. The chemistry operator is generally the most computationally intensive step in atmospheric air quality models. A new method based on Richardson extrapolation to solve the chemical kinetics is presented. The transport operator is the most challenging to solve numerically. Because of its hyperbolic nature non-physical oscillations and/or negative concentrations appear near steep gradient regions of the solution. Six algorithms for solving the advection equation are compared to determine their suitability for use in parallel photochemical air quality models. Four algorithms for filtering the numerical noise produced when solving the advection equation are also compared. A speed-up factor of 94.9 has been measured when the I/O, transport, and chemistry portions of the model are performed in parallel. This work provides the computational infrastructure required to incorporate new physico-chemical phenomena in the next generation of urban- or regional-scale air quality models. Finally, the SARMAP model is used to model the San Joaquin Valley of California. SARMAP is the updated version of RADM. It can be considered a state-of-the- art regional air pollution model. Like the CIT model

Sulfuric acid (H2SO4), formed from oxidation of sulfur dioxide (SO2) emitted during fossil fuel combustion, is a major precursor of new airborne particles, which have well-documented detrimental effects on health, air quality, and climate. Another precursor is methanesulfonic acid (MSA), produced simultaneously with SO2 during the atmospheric oxidation of organosulfur compounds (OSCs), such as dimethyl sulfide. In the present work, a multidisciplinary approach is used to examine how contributions of H2SO4 and MSA to particle formation will change in a large coastal urban area as anthropogenic fossil fuel emissions of SO2 decline. The 3-dimensional University of California Irvine-California Institute of Technology airshed model is used to compare atmospheric concentrations of gas phase MSA, H2SO4, and SO2 under current emissions of fossil fuel-associated SO2 and a best-case futuristic scenario with zero fossil fuel sulfur emissions. Model additions include results from (i) quantum chemical calculations that clarify the previously uncertain gas phase mechanism of formation of MSA and (ii) a combination of published and experimental estimates of OSC emissions, such as those from marine, agricultural, and urban processes, which include pet waste and human breath. Results show that in the zero anthropogenic SO2 emissions case, particle formation potential from H2SO4 will drop by about two orders of magnitude compared with the current situation. However, particles will continue to be generated from the oxidation of natural and anthropogenic sources of OSCs, with contributions from MSA and H2SO4 of a similar order of magnitude. This could be particularly important in agricultural areas where there are significant sources of OSCs.

Sulfuric acid (H2SO4), formed from oxidation of sulfur dioxide (SO2) emitted during fossil fuel combustion, is a major precursor of new airborne particles, which have well-documented detrimental effects on health, air quality, and climate. Another precursor is methanesulfonic acid (MSA), produced simultaneously with SO2 during the atmospheric oxidation of organosulfur compounds (OSCs), such as dimethyl sulfide. In the present work, a multidisciplinary approach is used to examine how contributions of H2SO4 and MSA to particle formation will change in a large coastal urban area as anthropogenic fossil fuel emissions of SO2 decline. The 3-dimensional University of California Irvine-California Institute of Technology airshed model is used to compare atmospheric concentrations of gas phase MSA, H2SO4, and SO2 under current emissions of fossil fuel-associated SO2 and a best-case futuristic scenario with zero fossil fuel sulfur emissions. Model additions include results from (i) quantum chemical calculations that clarify the previously uncertain gas phase mechanism of formation of MSA and (ii) a combination of published and experimental estimates of OSC emissions, such as those from marine, agricultural, and urban processes, which include pet waste and human breath. Results show that in the zero anthropogenic SO2 emissions case, particle formation potential from H2SO4 will drop by about two orders of magnitude compared with the current situation. However, particles will continue to be generated from the oxidation of natural and anthropogenic sources of OSCs, with contributions from MSA and H2SO4 of a similar order of magnitude. This could be particularly important in agricultural areas where there are significant sources of OSCs.

Postprint (published version)

Distributed power generation-electricity generation that is produced by many small stationary power generators distributed throughout an urban air basin-has the potential to supply a significant portion of electricity in future years. As a result, distributed generation may lead to increased pollutant emissions within an urban air basin, which could adversely affect air quality. However, the use of combined heating and power with distributed generation may reduce the energy consumption for space heating and air conditioning, resulting in a net decrease of pollutant and greenhouse gas emissions. This work used a systematic approach based on land-use geographical information system data to determine the spatial and temporal distribution of distributed generation emissions in the San Joaquin Valley Air Basin of California and simulated the potential air quality impacts using state-of-the-art three-dimensional computer models. The evaluation of the potential market penetration of distributed generation focuses on the year 2023. In general, the air quality impacts of distributed generation were found to be small due to the restrictive 2007 California Air Resources Board air emission standards applied to all distributed generation units and due to the use of combined heating and power. Results suggest that if distributed generation units were allowed to emit at the current Best Available Control Technology standards (which are less restrictive than the 2007 California Air Resources Board standards), air quality impacts of distributed generation could compromise compliance with the federal 8-hr average ozone standard in the region.

The combined sea port of Los Angeles and Long Beach in California constitutes the second busiest port in the United States by shipping volume. Communities near the ports face environmental justice concerns from a variety of sources including roadway and port related activities. This study examines the transport and diffusion of PM2.5 and NOX in port communities using the high-resolution plume model AERMOD, incorporating surface and aloft observed meteorology and local topography. Pollution impacts of roadway related emissions, direct port activity of cargo handling equipment and commercial shipping vessels are modeled for representative cold and hot months in 2005. Predictions from roadway emissions are compared with the same episode modeled with CALINE4 line dispersion model. Results show high spatial variability as well as increased transport during cold months. In addition, research also shows that while the port activity significantly impacts in-port air pollution, the effects of port activity is limited to within 2-6 km of the ports. Port adjacent communities are most sensitive to roadway related emissions. AERMOD PM2.5 and NOX predictions show a peak correlation coefficient of 43% and 50% compared with observations, respectively. (c) Author(s) 2011. This work is distributed under the Creative Commons Attribution 3.0 License.

The combined sea port of Los Angeles and Long Beach in California constitutes the second busiest port in the United States by shipping volume. Communities near the ports face environmental justice concerns from a variety of sources including roadway and port related activities. This study examines the transport and diffusion of PM2.5 and NOX in port communities using the high-resolution plume model AERMOD, incorporating surface and aloft observed meteorology and local topography. Pollution impacts of roadway related emissions, direct port activity of cargo handling equipment and commercial shipping vessels are modeled for representative cold and hot months in 2005. Predictions from roadway emissions are compared with the same episode modeled with CALINE4 line dispersion model. Results show high spatial variability as well as increased transport during cold months. In addition, research also shows that while the port activity significantly impacts in-port air pollution, the effects of port activity is limited to within 2-6 km of the ports. Port adjacent communities are most sensitive to roadway related emissions. AERMOD PM2.5 and NOX predictions show a peak correlation coefficient of 43% and 50% compared with observations, respectively. (c) Author(s) 2011. This work is distributed under the Creative Commons Attribution 3.0 License.

Distributed power generation-electricity generation that is produced by many small stationary power generators distributed throughout an urban air basin-has the potential to supply a significant portion of electricity in future years. As a result, distributed generation may lead to increased pollutant emissions within an urban air basin, which could adversely affect air quality. However, the use of combined heating and power with distributed generation may reduce the energy consumption for space heating and air conditioning, resulting in a net decrease of pollutant and greenhouse gas emissions. This work used a systematic approach based on land-use geographical information system data to determine the spatial and temporal distribution of distributed generation emissions in the San Joaquin Valley Air Basin of California and simulated the potential air quality impacts using state-of-the-art three-dimensional computer models. The evaluation of the potential market penetration of distributed generation focuses on the year 2023. In general, the air quality impacts of distributed generation were found to be small due to the restrictive 2007 California Air Resources Board air emission standards applied to all distributed generation units and due to the use of combined heating and power. Results suggest that if distributed generation units were allowed to emit at the current Best Available Control Technology standards (which are less restrictive than the 2007 California Air Resources Board standards), air quality impacts of distributed generation could compromise compliance with the federal 8-hr average ozone standard in the region.

The model NMMB/BSC-CTM is a new fully on-line chemical weather prediction system under development at the Earth Sciences Department of the Barcelona Supercomputing Center in collaboration with several research institutions. The basis of the development is the NCEP new global/regional Nonhydrostatic Multiscale Model on the B grid (NMMB). Its unified nonhydrostatic dynamical core allows regional and global simulations and forecasts. A mineral dust module has been coupled within the NMMB. The new system, NMMB/BSCDUST, simulates the atmospheric life cycle of the eroded desert dust. The main characteristics are its on-line coupling of the dust scheme with the meteorological driver, the wide range of applications from meso to global scales, and the dust shortwave and longwave radiative feedbacks on meteorology. In order to complement such development, the BSC works also in the implementation of a fully on-line gas-phase chemical mechanism. Chemical species are advected and mixed at the corresponding time steps of the meteorological tracers using the same numerical scheme of the NMMB. Advection is Eulerian, positive definite and monotone. The final objective of the work is to develop a fully chemical weather prediction system, namely NMMB/BSC-CTM, able to resolve gas-aerosol-meteorology interactions from global to local scales. Future efforts will be oriented to incorporate a multi-component aerosol module within the system with the aim to solve the life-cycle of relevant aerosols at global scale (dust, sea salt, sulfate, black carbon and organic carbon). In the present contribution we describe the status of development of the system and first evaluation results of the gas-phase chemistry., Postprint (published version)

Hydroxyl radical (OH) is a primary oxidant in the atmosphere and affects both gasphase pollutants and particulate matter levels. Nitrous acid (HONO) acts as an important source of OH in the urban atmosphere. Therefore it is important to account accu- 5 rately for HONO sources within air quality models in order to predict air pollution dynamics. HONO observations in urban areas are characterized by high concentrations at night and low concentrations around midday. Existing gas-phase chemical mechanisms do not reproduce the observed HONO levels, suggesting a lack of sources, such as direct emissions or heterogeneous reactions. Specific HONO emission rates, het10 erogeneous chemical mechanisms leading to its formation and related kinetics are still unclear. Therefore, most air quality models consider exclusively gas-phase chemistry related to HONO. This work applies the WRF-ARW/HERMES/CMAQ modeling system to quantify the effect of the addition of HONO sources in the predictability of HONO profiles, and its subsequent effect on secondary pollutants formation (mainly O3 and 15 PM2.5)., Peer Reviewed, Postprint (published version)

Adoption of hydrogen infrastructure and hydrogen fuel cell vehicles (HFCVs) to replace gasoline internal combustion engine (ICE) vehicles has been proposed as a strategy to reduce criteria pollutant and greenhouse gas (GHG) emissions from the transportation sector and transition to fuel independence. However, it is uncertain (1) to what degree the reduction in criteria pollutants will impact urban air quality, and (2) how the reductions in pollutant emissions and concomitant urban air quality impacts compare to ultralow emission gasoline-powered vehicles projected for a future year (e.g., 2060). To address these questions, the present study introduces a "spatially and temporally resolved energy and environment tool" (STREET) to characterize the pollutant and GHG emissions associated with a comprehensive hydrogen supply infrastructure and HFCVs at a high level of geographic and temporal resolution. To demonstrate the utility of STREET, two spatially and temporally resolved scenarios for hydrogen infrastructure are evaluated in a prototypical urban airshed (the South Coast Air Basin of California) using geographic information systems (GIS) data. The well-to-wheels (WTW) GHG emissions are quantified and the air quality is established using a detailed atmospheric chemistry and transport model followed by a comparison to a future gasoline scenario comprised of advanced ICE vehicles. One hydrogen scenario includes more renewable primary energy sources for hydrogen generation and the other includes more fossil fuel sources. The two scenarios encompass a variety of hydrogen generation, distribution, and fueling strategies. GHG emissions reductions range from 61 to 68% for both hydrogen scenarios in parallel with substantial improvements in urban air quality (e.g., reductions of 10 ppb in peak 8-h-averaged ozone and 6 mug/m(3) in 24-h-averaged particulate matter concentrations, particularly in regions of the airshed where concentrations are highest for the gasoline scenario)

Gaseous HCl generated from a variety of sources is ubiquitous in both outdoor and indoor air. Oxides of nitrogen (NO(y)) are also globally distributed, because NO formed in combustion processes is oxidized to NO(2), HNO(3), N(2)O(5) and a variety of other nitrogen oxides during transport. Deposition of HCl and NO(y) onto surfaces is commonly regarded as providing permanent removal mechanisms. However, we show here a new surface-mediated coupling of nitrogen oxide and halogen activation cycles in which uptake of gaseous NO(2) or N(2)O(5) on solid substrates generates adsorbed intermediates that react with HCl to generate gaseous nitrosyl chloride (ClNO) and nitryl chloride (ClNO(2)), respectively. These are potentially harmful gases that photolyze to form highly reactive chlorine atoms. The reactions are shown both experimentally and theoretically to be enhanced by water, a surprising result given the availability of competing hydrolysis reaction pathways. Airshed modeling incorporating HCl generated from sea salt shows that in coastal urban regions, this heterogeneous chemistry increases surface-level ozone, a criteria air pollutant, greenhouse gas and source of atmospheric oxidants. In addition, it may contribute to recently measured high levels of ClNO(2) in the polluted coastal marine boundary layer. This work also suggests the potential for chlorine atom chemistry to occur indoors where significant concentrations of oxides of nitrogen and HCl coexist.

Gaseous HCl generated from a variety of sources is ubiquitous in both outdoor and indoor air. Oxides of nitrogen (NO(y)) are also globally distributed, because NO formed in combustion processes is oxidized to NO(2), HNO(3), N(2)O(5) and a variety of other nitrogen oxides during transport. Deposition of HCl and NO(y) onto surfaces is commonly regarded as providing permanent removal mechanisms. However, we show here a new surface-mediated coupling of nitrogen oxide and halogen activation cycles in which uptake of gaseous NO(2) or N(2)O(5) on solid substrates generates adsorbed intermediates that react with HCl to generate gaseous nitrosyl chloride (ClNO) and nitryl chloride (ClNO(2)), respectively. These are potentially harmful gases that photolyze to form highly reactive chlorine atoms. The reactions are shown both experimentally and theoretically to be enhanced by water, a surprising result given the availability of competing hydrolysis reaction pathways. Airshed modeling incorporating HCl generated from sea salt shows that in coastal urban regions, this heterogeneous chemistry increases surface-level ozone, a criteria air pollutant, greenhouse gas and source of atmospheric oxidants. In addition, it may contribute to recently measured high levels of ClNO(2) in the polluted coastal marine boundary layer. This work also suggests the potential for chlorine atom chemistry to occur indoors where significant concentrations of oxides of nitrogen and HCl coexist.

Adoption of hydrogen infrastructure and hydrogen fuel cell vehicles (HFCVs) to replace gasoline internal combustion engine (ICE) vehicles has been proposed as a strategy to reduce criteria pollutant and greenhouse gas (GHG) emissions from the transportation sector and transition to fuel independence. However, it is uncertain (1) to what degree the reduction in criteria pollutants will impact urban air quality, and (2) how the reductions in pollutant emissions and concomitant urban air quality impacts compare to ultralow emission gasoline-powered vehicles projected for a future year (e.g., 2060). To address these questions, the present study introduces a "spatially and temporally resolved energy and environment tool" (STREET) to characterize the pollutant and GHG emissions associated with a comprehensive hydrogen supply infrastructure and HFCVs at a high level of geographic and temporal resolution. To demonstrate the utility of STREET, two spatially and temporally resolved scenarios for hydrogen infrastructure are evaluated in a prototypical urban airshed (the South Coast Air Basin of California) using geographic information systems (GIS) data. The well-to-wheels (WTW) GHG emissions are quantified and the air quality is established using a detailed atmospheric chemistry and transport model followed by a comparison to a future gasoline scenario comprised of advanced ICE vehicles. One hydrogen scenario includes more renewable primary energy sources for hydrogen generation and the other includes more fossil fuel sources. The two scenarios encompass a variety of hydrogen generation, distribution, and fueling strategies. GHG emissions reductions range from 61 to 68% for both hydrogen scenarios in parallel with substantial improvements in urban air quality (e.g., reductions of 10 ppb in peak 8-h-averaged ozone and 6 mug/m(3) in 24-h-averaged particulate matter concentrations, particularly in regions of the airshed where concentrations are highest for the gasoline scenario)

Emissions from the potential installation of distributed energy resources (DER) in the place of current utility-scale power generators have been introduced into an emissions inventory of the northeastern United States. A methodology for predicting future market penetration of DER that considers economics and emission factors was used to estimate the most likely implementation of DER. The methodology results in spatially and temporally resolved emission profiles of criteria pollutants that are subsequently introduced into a detailed atmospheric chemistry and transport model of the region. The DER technology determined by the methodology includes 62% reciprocating engines, 34% gas turbines, and 4% fuel cells and other emerging technologies. The introduction of DER leads to retirement of 2625 MW of existing power plants for which emissions are removed from the inventory. The air quality model predicts maximum differences in air pollutant concentrations that are located downwind from the central power plants that were removed from the domain. Maximum decreases in hourly peak ozone concentrations due to DER use are 10 ppb and are located over the state of New Jersey. Maximum decreases in 24-hr average fine particulate matter (PM2.5) concentrations reach 3 microg/m3 and are located off the coast of New Jersey and New York. The main contribution to decreased PM2.5 is the reduction of sulfate levels due to significant reductions in direct emissions of sulfur oxides (SO(x)) from the DER compared with the central power plants removed. The scenario presented here represents an accelerated DER penetration case with aggressive emission reductions due to removal of highly emitting power plants. Such scenario provides an upper bound for air quality benefits of DER implementation scenarios.

Emissions from the potential installation of distributed energy resources (DER) in the place of current utility-scale power generators have been introduced into an emissions inventory of the northeastern United States. A methodology for predicting future market penetration of DER that considers economics and emission factors was used to estimate the most likely implementation of DER. The methodology results in spatially and temporally resolved emission profiles of criteria pollutants that are subsequently introduced into a detailed atmospheric chemistry and transport model of the region. The DER technology determined by the methodology includes 62% reciprocating engines, 34% gas turbines, and 4% fuel cells and other emerging technologies. The introduction of DER leads to retirement of 2625 MW of existing power plants for which emissions are removed from the inventory. The air quality model predicts maximum differences in air pollutant concentrations that are located downwind from the central power plants that were removed from the domain. Maximum decreases in hourly peak ozone concentrations due to DER use are 10 ppb and are located over the state of New Jersey. Maximum decreases in 24-hr average fine particulate matter (PM2.5) concentrations reach 3 microg/m3 and are located off the coast of New Jersey and New York. The main contribution to decreased PM2.5 is the reduction of sulfate levels due to significant reductions in direct emissions of sulfur oxides (SO(x)) from the DER compared with the central power plants removed. The scenario presented here represents an accelerated DER penetration case with aggressive emission reductions due to removal of highly emitting power plants. Such scenario provides an upper bound for air quality benefits of DER implementation scenarios.

This study evaluates air quality model sensitivity to input and to model components. Simulations are performed using the California Institute of Technology (CIT) airshed model. Results show the impacts on ozone (O3) concentration in the South Coast Air Basin (SCAB) of California because of changes in: (1) input data, including meteorological conditions (temperature, UV radiation, mixing height, and wind speed), boundary conditions, and initial conditions (ICs); and (2) model components, including advection solver and chemical mechanism. O3 concentrations are strongly affected by meteorological conditions and, in particular, by temperature. ICs also affect O3 concentrations, especially in the first 2 days of simulation. On the other hand, boundary conditions do not significantly affect the absolute peak O3 concentration, although they do affect concentrations near the inflow boundaries. Moreover, predicted O3 concentrations are impacted considerably by the chemical mechanism. In addition, dispersion of pollutants is affected by the advection routine used to calculate its transport. Comparison among CIT, California Photochemical Grid Model (CALGRID), and Urban Airshed Model air quality models suggests that differences in O3 predictions are mainly caused by the different chemical mechanisms used. Additionally, advection solvers contribute to the differences observed among model predictions. Uncertainty in predicted peak O3 concentration suggests that air quality evaluation should not be based solely on this single value but also on trends predicted by air quality models using a number of chemical mechanisms and with an advection solver that is mass conservative.

While there is increasing evidence for unique chemical reactions at interfaces, there are fewer data on photochemistry at liquid-vapor junctions. This paper reports a comparison of the photolysis of molybdenum hexacarbonyl, Mo(CO)(6), in 1-decene either as liquid droplets or in bulk-liquid solutions. Mo(CO)(6) photolysis is faster by at least three orders of magnitude in the aerosols than in bulk-liquids. Two possible sources of this enhancement are considered: (1) increased light intensity due to either Morphology-Dependent Resonances (MDRs) in the spherical aerosol particles and/or to increased pathlengths for light inside the droplet due to refraction, which are termed physical effects in this paper; and (2) interface effects such as an incomplete solvent-cage at the gas-liquid boundary and/or enhanced interfacial concentrations of Mo(CO)(6), which are termed chemical effects. Quantitative calculations of the first possibility were carried out in which the light intensity distribution in the droplets averaged over 215-360 nm was obtained for 1-decene droplets. Calculations show that the average increase in light intensity over the entire droplet is 106%, with an average increase of 51% at the interface. These increases are much smaller than the observed increase in the apparent photolysis rate of droplets compared to the bulk. Thus, chemical effects, i.e., a decreased solvent-cage effect at the interface and/or enhancement in the surface concentration of Mo(CO)(6), are most likely responsible for the dramatic increase in the photolysis rate. Similar calculations were also carried out for broadband (290-600 nm) solar irradiation of water droplets, relevant to atmospheric conditions. These calculations show that, in agreement with previous calculations by Mayer and Madronich [B. Mayer and S. Madronich, Atmos. Chem. Phys., 2004, 4, 2241] MDRs produce only a moderate average intensity enhancement relative to the corresponding bulk-liquid slabs when averaged over a ra

While there is increasing evidence for unique chemical reactions at interfaces, there are fewer data on photochemistry at liquid-vapor junctions. This paper reports a comparison of the photolysis of molybdenum hexacarbonyl, Mo(CO)(6), in 1-decene either as liquid droplets or in bulk-liquid solutions. Mo(CO)(6) photolysis is faster by at least three orders of magnitude in the aerosols than in bulk-liquids. Two possible sources of this enhancement are considered: (1) increased light intensity due to either Morphology-Dependent Resonances (MDRs) in the spherical aerosol particles and/or to increased pathlengths for light inside the droplet due to refraction, which are termed physical effects in this paper; and (2) interface effects such as an incomplete solvent-cage at the gas-liquid boundary and/or enhanced interfacial concentrations of Mo(CO)(6), which are termed chemical effects. Quantitative calculations of the first possibility were carried out in which the light intensity distribution in the droplets averaged over 215-360 nm was obtained for 1-decene droplets. Calculations show that the average increase in light intensity over the entire droplet is 106%, with an average increase of 51% at the interface. These increases are much smaller than the observed increase in the apparent photolysis rate of droplets compared to the bulk. Thus, chemical effects, i.e., a decreased solvent-cage effect at the interface and/or enhancement in the surface concentration of Mo(CO)(6), are most likely responsible for the dramatic increase in the photolysis rate. Similar calculations were also carried out for broadband (290-600 nm) solar irradiation of water droplets, relevant to atmospheric conditions. These calculations show that, in agreement with previous calculations by Mayer and Madronich [B. Mayer and S. Madronich, Atmos. Chem. Phys., 2004, 4, 2241] MDRs produce only a moderate average intensity enhancement relative to the corresponding bulk-liquid slabs when averaged over a ra

This study evaluates air quality model sensitivity to input and to model components. Simulations are performed using the California Institute of Technology (CIT) airshed model. Results show the impacts on ozone (O3) concentration in the South Coast Air Basin (SCAB) of California because of changes in: (1) input data, including meteorological conditions (temperature, UV radiation, mixing height, and wind speed), boundary conditions, and initial conditions (ICs); and (2) model components, including advection solver and chemical mechanism. O3 concentrations are strongly affected by meteorological conditions and, in particular, by temperature. ICs also affect O3 concentrations, especially in the first 2 days of simulation. On the other hand, boundary conditions do not significantly affect the absolute peak O3 concentration, although they do affect concentrations near the inflow boundaries. Moreover, predicted O3 concentrations are impacted considerably by the chemical mechanism. In addition, dispersion of pollutants is affected by the advection routine used to calculate its transport. Comparison among CIT, California Photochemical Grid Model (CALGRID), and Urban Airshed Model air quality models suggests that differences in O3 predictions are mainly caused by the different chemical mechanisms used. Additionally, advection solvers contribute to the differences observed among model predictions. Uncertainty in predicted peak O3 concentration suggests that air quality evaluation should not be based solely on this single value but also on trends predicted by air quality models using a number of chemical mechanisms and with an advection solver that is mass conservative.

In the introduction to the Technical Note, “Instantaneous secondary organic aerosol yields and their comparison with overall aerosol yields for aromatic and biogenic hydrocarbons”, Jiang (2003) states that “[t]o model the formation of secondary organic aerosol, SOA, a concept called aerosol yield (or SOA yield), loosely defined as the SOA mass formed per unit mass of reactive organic gas (ROG) reacted, has been widely used.” He goes on to suggest an expanded concept called instantaneous aerosol yield (IAY), applied to the case of pre-existing organic aerosol. While this IAY method may at first seem reasonable, there is a major assumption in its derivation that limits its use for atmospheric models. Additionally, aerosol yield approaches in general are inappropriate for describing the reversible partitioning process that occurs in the atmosphere.

In the introduction to the Technical Note, “Instantaneous secondary organic aerosol yields and their comparison with overall aerosol yields for aromatic and biogenic hydrocarbons”, Jiang (2003) states that “[t]o model the formation of secondary organic aerosol, SOA, a concept called aerosol yield (or SOA yield), loosely defined as the SOA mass formed per unit mass of reactive organic gas (ROG) reacted, has been widely used.” He goes on to suggest an expanded concept called instantaneous aerosol yield (IAY), applied to the case of pre-existing organic aerosol. While this IAY method may at first seem reasonable, there is a major assumption in its derivation that limits its use for atmospheric models. Additionally, aerosol yield approaches in general are inappropriate for describing the reversible partitioning process that occurs in the atmosphere.

Regional modeling analysis for the Intercontinental Transport and Chemical Transformation 2002 (ITCT 2K2) experiment over the eastern Pacific and U.S. West Coast is performed using a multiscale modeling system, including the regional tracer model Chemical Weather Forecasting System (CFORS), the Sulfur Transport and Emissions Model 2003 (STEM-2K3) regional chemical transport model, and an off-line coupling with the Model of Ozone and Related Chemical Tracers (MOZART) global chemical transport model. CO regional tracers calculated online in the CFORS model are used to identify aircraft measurement periods with Asian influences. Asian-influenced air masses measured by the National Oceanic and Atmospheric Administration (NOAA) WP-3 aircraft in this experiment are found to have lower ΔAcetone/ΔCO, ΔMethanol /ΔCO, and ΔPropane/ ΔEthyne ratios than air masses influenced by U.S. emissions, reflecting differences in regional emission signals. The Asian air masses in the eastern Pacific are found to usually be well aged (>5 days), to be highly diffused, and to have low NOy levels. Chemical budget analysis is performed for two flights, and the O3 net chemical budgets are found to be negative (net destructive) in the places dominated by Asian influences or clear sites and positive in polluted American air masses. During the trans-Pacific transport, part of gaseous HNO3 was converted to nitrate particle, and this conversion was attributed to NOy decline. Without the aerosol consideration, the model tends to overestimate HNO3 background concentration along the coast region. At the measurement site of Trinidad Head, northern California, high- concentration pollutants are usually associated with calm wind scenarios, implying that the accumulation of local pollutants leads to the high concentration. Seasonal variations are also discussed from April to May for this site. A high-resolution nesting simulation with 12-km horizontal resolution is used to study the WP-3 flight over Los An

Regional modeling analysis for the Intercontinental Transport and Chemical Transformation 2002 (ITCT 2K2) experiment over the eastern Pacific and U.S. West Coast is performed using a multiscale modeling system, including the regional tracer model Chemical Weather Forecasting System (CFORS), the Sulfur Transport and Emissions Model 2003 (STEM-2K3) regional chemical transport model, and an off-line coupling with the Model of Ozone and Related Chemical Tracers (MOZART) global chemical transport model. CO regional tracers calculated online in the CFORS model are used to identify aircraft measurement periods with Asian influences. Asian-influenced air masses measured by the National Oceanic and Atmospheric Administration (NOAA) WP-3 aircraft in this experiment are found to have lower ΔAcetone/ΔCO, ΔMethanol /ΔCO, and ΔPropane/ ΔEthyne ratios than air masses influenced by U.S. emissions, reflecting differences in regional emission signals. The Asian air masses in the eastern Pacific are found to usually be well aged (>5 days), to be highly diffused, and to have low NOy levels. Chemical budget analysis is performed for two flights, and the O3 net chemical budgets are found to be negative (net destructive) in the places dominated by Asian influences or clear sites and positive in polluted American air masses. During the trans-Pacific transport, part of gaseous HNO3 was converted to nitrate particle, and this conversion was attributed to NOy decline. Without the aerosol consideration, the model tends to overestimate HNO3 background concentration along the coast region. At the measurement site of Trinidad Head, northern California, high- concentration pollutants are usually associated with calm wind scenarios, implying that the accumulation of local pollutants leads to the high concentration. Seasonal variations are also discussed from April to May for this site. A high-resolution nesting simulation with 12-km horizontal resolution is used to study the WP-3 flight over Los An