Why do models overestimate surface ozone in the Southeast United States

Ozone pollution in the Southeast US involves complex chemistry driven by emissions of anthropogenic nitrogen oxide radicals (NOx  ≡  NO + NO2) and biogenic isoprene. Model estimates of surface ozone concentrations tend to be biased high in the region and this is of concern for designing effective emission control strategies to meet air quality standards. We use detailed chemical observations from the SEAC4RS aircraft campaign in August and September 2013, interpreted with the GEOS-Chem chemical transport model at 0.25°  ×  0.3125° horizontal resolution, to better understand the factors controlling surface ozone in the Southeast US. We find that the National Emission Inventory (NEI) for NOx from the US Environmental Protection Agency (EPA) is too high. This finding is based on SEAC4RS observations of NOx and its oxidation products, surface network observations of nitrate wet deposition fluxes, and OMI satellite observations of tropospheric NO2 columns. Our results indicate that NEI NOx emissions from mobile and industrial sources must be reduced by 30–60 %, dependent on the assumption of the contribution by soil NOx emissions. Upper-tropospheric NO2 from lightning makes a large contribution to satellite observations of tropospheric NO2 that must be accounted for when using these data to estimate surface NOx emissions. We find that only half of isoprene oxidation proceeds by the high-NOx pathway to produce ozone; this fraction is only moderately sensitive to changes in NOx emissions because isoprene and NOx emissions are spatially segregated. GEOS-Chem with reduced NOx emissions provides an unbiased simulation of ozone observations from the aircraft and reproduces the observed ozone production efficiency in the boundary layer as derived from a regression of ozone and NOx oxidation products. However, the model is still biased high by 6 ± 14 ppb relative to observed surface ozone in the Southeast US. Ozonesondes launched during midday hours show a 7 ppb ozone decrease from 1.5 km to the surface that GEOS-Chem does not capture. This bias may reflect a combination of excessive vertical mixing and net ozone production in the model boundary layer

Observation-based modeling of ozone chemistry in the Seoul metropolitan area during the Korea-United States Air Quality Study (KORUS-AQ)

The Seoul Metropolitan Area (SMA) has a population of 24 million and frequently experiences unhealthy levels of ozone (O3). In this work, measurements taken during the Korea-United States Air Quality Study (KORUS-AQ, 2016) are used to explore regional gradients in O3 and its chemical precursors, and an observationally-constrained 0-D photochemical box model is used to quantify key aspects of O3 production including its sensitivity to precursor gases. Box model performance was evaluated by comparing modeled concentrations of select secondary species to airborne measurements. These comparisons indicate that the steady state assumption used in 0-D box models cannot describe select intermediate species, highlighting the importance of having a broad suite of trace gases as model constraints. When fully constrained, aggregated statistics of modeled O3 production rates agreed with observed changes in O3, indicating that the box model was able to represent the majority of O3 chemistry. Comparison of airborne observations between urban Seoul and a downwind receptor site reveal a positive gradient in O3 coinciding with a negative gradient in NOx, no gradient in CH2O, and a slight positive gradient in modeled rates of O3 production. Together, these observations indicate a radical-limited (VOC-limited) O3 production environment in the SMA. Zero-out simulations identified C7+ aromatics as the dominant VOC contributors to O3 production, with isoprene and anthropogenic alkenes making smaller but appreciable contributions. Simulations of model sensitivity to decreases in NOx produced results that were not spatially uniform, with large increases in O3 production predicted for urban Seoul and decreases in O3 production predicted for far-outlying areas. The policy implications of this work are clear: Effective O3 mitigation strategies in the SMA must focus on reducing local emissions of C7+ aromatics, while reductions in NOx emissions may increase O3 in some areas but generally decrease the regional extent of O3 exposure

Observed NO/NO2 Ratios in the Upper Troposphere Imply Errors in NO-NO2-O3 Cycling Kinetics or an Unaccounted NOx Reservoir

Observations from the SEAC4RS aircraft campaign over the southeast United States in August-September 2013 show NO/NO2 concentration ratios in the upper troposphere that are approximately half of photochemical equilibrium values computed from Jet Propulsion Laboratory (JPL) kinetic data. One possible explanation is the presence of labile NOx reservoir species, presumably organic, decomposing thermally to NO2 in the instrument. The NO2 instrument corrects for this artifact from known labile HNO4 and CH3O2NO2 NOx reservoirs. To bridge the gap between measured and simulated NO2, additional unaccounted labile NOx reservoir species would have to be present at a mean concentration of ~40 ppt for the SEAC4RS conditions (compared with 197 ppt for NOx). An alternative explanation is error in the low-temperature rate constant for the NO + O3 reaction (30% 1-σ uncertainty in JPL at 240 K) and/or in the spectroscopic data for NO2 photolysis (20% 1-σ uncertainty). Resolving this discrepancy is important for understanding global budgets of tropospheric oxidants and for interpreting satellite observations of tropospheric NO2 columns

Quantitative detection of iodine in the stratosphere

Oceanic emissions of iodine destroy ozone, modify oxidative capacity, and can form new particles in the troposphere. However, the impact of iodine in the stratosphere is highly uncertain due to the lack of previous quantitative measurements. Here, we report quantitative measurements of iodine monoxide radicals and particulate iodine (Iy,part) from aircraft in the stratosphere. These measurements support that 0.77 ± 0.10 parts per trillion by volume (pptv) total inorganic iodine (Iy) is injected to the stratosphere. These high Iy amounts are indicative of active iodine recycling on ice in the upper troposphere (UT), support the upper end of recent Iy estimates (0 to 0.8 pptv) by the World Meteorological Organization, and are incompatible with zero stratospheric iodine injection. Gasphase iodine (Iy,gas) in the UT (0.67 ± 0.09 pptv) converts to Iy,part sharply near the tropopause. In the stratosphere, IO radicals remain detectable (0.06 ± 0.03 pptv), indicating persistent Iy,part recycling back to Iy,gas as a result of active multiphase chemistry. At the observed levels, iodine is responsible for 32% of the halogen-induced ozone loss (bromine 40%, chlorine 28%), due primarily to previously unconsidered heterogeneous chemistry. Anthropogenic (pollution) ozone has increased iodine emissions since preindustrial times (ca. factor of 3 since 1950) and could be partly responsible for the continued decrease of ozone in the lower stratosphere. Increasing iodine emissions have implications for ozone radiative forcing and possibly new particle formation near the tropopause.Fil: Koenig, Theodore K.. State University of Colorado at Boulder; Estados UnidosFil: Baidar, Sunil. State University of Colorado at Boulder; Estados UnidosFil: Campuzano Jost, Pedro. State University of Colorado at Boulder; Estados UnidosFil: Cuevas, Carlos Alberto. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Dix, Barbara. State University of Colorado at Boulder; Estados UnidosFil: Fernandez, Rafael Pedro. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; España. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Interdisciplinario de Ciencias Básicas. - Universidad Nacional de Cuyo. Instituto Interdisciplinario de Ciencias Básicas; ArgentinaFil: Guo, Hongyu. State University of Colorado at Boulder; Estados UnidosFil: Hall, Samuel R.. National Center for Atmospheric Research; Estados UnidosFil: Kinnison, Douglas. National Center for Atmospheric Research; Estados UnidosFil: Nault, Benjamin A.. State University of Colorado at Boulder; Estados UnidosFil: Ullmann, Kirk. National Center for Atmospheric Research; Estados UnidosFil: Jimenez, Jose L.. State University of Colorado at Boulder; Estados UnidosFil: Saiz López, Alfonso. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Volkamer, Rainer. State University of Colorado at Boulder; Estados Unido

Corporate Social Responsibility in Tourism Small and Medium Enterprises. Evidence from Europe and Latin America

While there is a growing literature related with corporate social responsibility (CSR) in hospitality and tourism large firms, much remains to be done in the case of CSR in tourism small and medium enterprises (SMEs). In this paper we provide three studies regarding this particular aspect through the evidence present in different destinations: Catalonia, European natural parks and Chile. Among the conclusions that can be highlighted is the prevalence of altruism in the reasons for being responsible, the introduction of increasingly advanced measures or their impact on different business variables, and the link to financial performance

Ozone depletion due to dust release of iodine in the free troposphere

Iodine is an atmospheric trace element emitted from oceans that efficiently destroys ozone (O3). Low O3 in airborne dust layers is frequently observed but poorly understood. We show that dust is a source of gas-phase iodine, indicated by aircraft observations of iodine monoxide (IO) radicals inside lofted dust layers from the Atacama and Sechura Deserts that are up to a factor of 10 enhanced over background. Gas-phase iodine photochemistry, commensurate with observed IO, is needed to explain the low O3 inside these dust layers (below 15 ppbv; up to 75% depleted). The added dust iodine can explain decreases in O3 of 8% regionally and affects surface air quality. Our data suggest that iodate reduction to form volatile iodine species is a missing process in the geochemical iodine cycle and presents an unrecognized aeolian source of iodine. Atmospheric iodine has tripled since 1950 and affects ozone layer recovery and particle formation.Fil: Koenig, Theodore K.. State University of Colorado at Boulder; Estados Unidos. Cooperative Institute for Research in Environmental Sciences; Estados UnidosFil: Volkamer, Rainer. State University of Colorado at Boulder; Estados Unidos. Cooperative Institute for Research in Environmental Sciences; Estados UnidosFil: Apel, Eric C.. National Center for Atmospheric Research; Estados UnidosFil: Bresch, James F.. National Center for Atmospheric Research; Estados UnidosFil: Cuevas, Carlos A.. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Dix, Barbara. State University of Colorado at Boulder; Estados Unidos. Cooperative Institute for Research in Environmental Sciences; Estados UnidosFil: Eloranta, Edwin W.. University of Wisconsin; Estados UnidosFil: Fernandez, Rafael Pedro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Interdisciplinario de Ciencias Básicas. - Universidad Nacional de Cuyo. Instituto Interdisciplinario de Ciencias Básicas; ArgentinaFil: Hall, Samuel R.. National Center for Atmospheric Research; Estados UnidosFil: Hornbrook, Rebecca S.. National Center for Atmospheric Research; Estados UnidosFil: Pierce, R. Bradley. National Environmental Satellite, Data, and Information Service; Estados UnidosFil: Reeves, J. Michael. National Center for Atmospheric Research; Estados UnidosFil: Saiz López, Alfonso. Consejo Superior de Investigaciones Científicas. Instituto de Química Física; EspañaFil: Ullmann, Kirk. National Center for Atmospheric Research; Estados Unido

Atmospheric Acetaldehyde: Importance of Air-Sea Exchange and a Missing Source in the Remote Troposphere.

We report airborne measurements of acetaldehyde (CH3CHO) during the first and second deployments of the National Aeronautics and Space Administration (NASA) Atmospheric Tomography Mission (ATom). The budget of CH3CHO is examined using the Community Atmospheric Model with chemistry (CAM-chem), with a newly-developed online air-sea exchange module. The upper limit of the global ocean net emission of CH3CHO is estimated to be 34 Tg a-1 (42 Tg a-1 if considering bubble-mediated transfer), and the ocean impacts on tropospheric CH3CHO are mostly confined to the marine boundary layer. Our analysis suggests that there is an unaccounted CH3CHO source in the remote troposphere and that organic aerosols can only provide a fraction of this missing source. We propose that peroxyacetic acid (PAA) is an ideal indicator of the rapid CH3CHO production in the remote troposphere. The higher-than-expected CH3CHO measurements represent a missing sink of hydroxyl radicals (and halogen radical) in current chemistry-climate models