scholarly journals Model uncertainties affecting satellite-based inverse modeling of nitrogen oxides emissions and implications for surface ozone simulation

2012 ◽  
Vol 12 (6) ◽  
pp. 14269-14327 ◽  
Author(s):  
J.-T. Lin ◽  
Z. Liu ◽  
Q. Zhang ◽  
H. Liu ◽  
J. Mao ◽  
...  

Abstract. Errors in chemical transport models (CTMs) interpreting the relation between space-retrieved tropospheric column densities of nitrogen dioxide (NO2) and emissions of nitrogen oxides (NOx) have important consequences on the inverse modeling. They are however difficult to quantify due to lack of adequate in situ measurements, particularly over China and other developing countries. This study proposes an alternate approach for model evaluation over East China, by analyzing the sensitivity of modeled NO2 columns to errors in meteorological and chemical parameters/processes important to the nitrogen abundance. As a demonstration, it evaluates the nested version of GEOS-Chem driven by the GEOS-5 meteorology and the INTEX-B anthropogenic emissions and used with retrievals from the Ozone Monitoring Instrument (OMI) to constrain emissions of NOx. The CTM has been used extensively for such applications. Errors are examined for a comprehensive set of meteorological and chemical parameters using measurements and/or uncertainty analysis based on current knowledge. Results are exploited then for sensitivity simulations perturbing the respective parameters, as the basis of the following post-model linearized and localized first-order modification. It is found that the model meteorology likely contains errors of various magnitudes in cloud optical depth, air temperature, water vapor, boundary layer height and many other parameters. Model errors also exist in gaseous and heterogeneous reactions, aerosol optical properties and emissions of non-nitrogen species affecting the nitrogen chemistry. Modifications accounting for quantified errors in 10 selected parameters increase the NO2 columns in most areas with an average positive impact of 22% in July and 10% in January. This suggests a possible systematic model bias such that the top-down emissions will be overestimated by the same magnitudes if the model is used for emission inversion without corrections. The modifications however cannot account for the large model underestimates in cities and other extremely polluted areas (particularly in the north) as compared to satellite retrievals, likely pointing to underestimates of the a priori emission inventory in these places with important implications for understanding of atmospheric chemistry and air quality. Post-model modifications also have large impacts on surface ozone concentrations with the peak values in July over North China decreasing by about 15 ppb. Individually, modification for the uptake of the hydroperoxyl radical on aerosols has the largest impact for both NO2 and ozone, followed by various other parameters important for some species in some seasons. Note that these modifications are simplified and should be used with caution for error apportionment.

2012 ◽  
Vol 12 (24) ◽  
pp. 12255-12275 ◽  
Author(s):  
J.-T. Lin ◽  
Z. Liu ◽  
Q. Zhang ◽  
H. Liu ◽  
J. Mao ◽  
...  

Abstract. Errors in chemical transport models (CTMs) interpreting the relation between space-retrieved tropospheric column densities of nitrogen dioxide (NO2) and emissions of nitrogen oxides (NOx) have important consequences on the inverse modeling. They are however difficult to quantify due to lack of adequate in situ measurements, particularly over China and other developing countries. This study proposes an alternate approach for model evaluation over East China, by analyzing the sensitivity of modeled NO2 columns to errors in meteorological and chemical parameters/processes important to the nitrogen abundance. As a demonstration, it evaluates the nested version of GEOS-Chem driven by the GEOS-5 meteorology and the INTEX-B anthropogenic emissions and used with retrievals from the Ozone Monitoring Instrument (OMI) to constrain emissions of NOx. The CTM has been used extensively for such applications. Errors are examined for a comprehensive set of meteorological and chemical parameters using measurements and/or uncertainty analysis based on current knowledge. Results are exploited then for sensitivity simulations perturbing the respective parameters, as the basis of the following post-model linearized and localized first-order modification. It is found that the model meteorology likely contains errors of various magnitudes in cloud optical depth, air temperature, water vapor, boundary layer height and many other parameters. Model errors also exist in gaseous and heterogeneous reactions, aerosol optical properties and emissions of non-nitrogen species affecting the nitrogen chemistry. Modifications accounting for quantified errors in 10 selected parameters increase the NO2 columns in most areas with an average positive impact of 18% in July and 8% in January, the most important factor being modified uptake of the hydroperoxyl radical (HO2) on aerosols. This suggests a possible systematic model bias such that the top-down emissions will be overestimated by the same magnitude if the model is used for emission inversion without corrections. The modifications however cannot eliminate the large model underestimates in cities and other extremely polluted areas (particularly in the north) as compared to satellite retrievals, likely pointing to underestimates of the a priori emission inventory in these places with important implications for understanding of atmospheric chemistry and air quality. Note that these modifications are simplified and should be interpreted with caution for error apportionment.


2011 ◽  
Vol 11 (15) ◽  
pp. 8075-8085 ◽  
Author(s):  
J.-B. Wu ◽  
Z. F. Wang ◽  
W. Zhang ◽  
H. B. Dong ◽  
X. L. Pan ◽  
...  

Abstract. This study investigates the effects of the total solar eclipse of 22 July 2009 on surface ozone and other photo-oxidants over China. A box model was used to study the sensitivity of ozone to the limb darkening effect during an eclipse event, and to show that the impact on ozone is small (less than 0.5 %). In addition, the regional model WRF-Chem was applied to study the effects of the eclipse on meteorological and chemical parameters, focusing on different regions in China. Chemical and meteorological observations were used to validate the model and to show that it can capture the effects of the total solar eclipse well. Model calculations show distinct differences in the spatial distributions of meteorological and chemical parameters with and without the eclipse. The maximum impacts of the eclipse occur over the area of totality, where there is a decrease in surface temperature of 1.5 °C and decrease in wind speed of 1 m s−1. The maximum impacts on atmospheric pollutants occur over parts of north and east China where emissions are greater, with an increase of 5 ppbv in NO2 and 25 ppbv in CO and a decrease of 10 ppbv in O3 and 4 ppbv in NO. This study also demonstrates the effects of the solar eclipse on surface photo-oxidants in different parts of China. Although the sun was obscured to a smaller extent in polluted areas than in clean areas, the impacts of the eclipse in polluted areas are greater and last longer than they do in clean areas. In contrast, the change in radical concentrations (OH, HO2 and NO3) in clean areas is much larger than in polluted areas mainly because of the limited source of radicals in these areas. The change in radical concentrations during the eclipse reveals that nighttime chemistry dominates in both clean and polluted areas. As solar eclipses provide a natural opportunity to test more thoroughly our understanding of atmospheric chemistry, especially that governed by photolysis, a comprehensive experimental campaign during a future solar eclipse is highly desirable.


2021 ◽  
Author(s):  
Tamara Emmerichs ◽  
Bruno Franco ◽  
Catherine Wespes ◽  
Vinod Kumar ◽  
Andrea Pozzer ◽  
...  

Abstract. Near-surface ozone is an harmful air pollutant, which is determined to a considerable extent by weather-controlled processes, and may be significantly impacted by water vapour forming complexes with peroxy radicals. The role of water in the reaction of HO2 radical with nitrogen oxides is known from the literature, and in current models the water complex is considered by assuming a linear dependence on water concentrations. In fact, recent experimental evidence has been published, showing the significant role of water on the kinetics of one of the most important reaction for ozone chemistry, namely NO2 + OH. Here, the available kinetic data for the HOx + NOx reactions have been included in the atmospheric chemistry model ECHAM5/MESSy (EMAC) to test its global significance. Among the modified kinetics, the newly added HNO3 channel from HO2 + NO, dominates, significantly reducing NO2. A major removal process of near-surface ozone is dry deposition accounting for 20 % of the total tropospheric ozone loss mostly occurring over vegetation. However, parameterizations for modelling dry deposition represent a major source of uncertainty for tropospheric ozone simulations. This potentially belongs to the reasons why global models, such as EMAC used here, overestimate ozone with respect to observations. In fact, the employed parameterization is hardly sensitive to local meteorological conditions (e.g., humidity) and lacks non-stomatal deposition. In this study, a dry deposition scheme including these features have been used in EMAC, affecting not only the deposition of ozone but of its precursors, resulting in lower chemical production of ozone. Additionally, we improved the emissions of isoprene and nitrous acid (HONO). Namely, for isoprene emissions we have accounted for the impact of drought stress which confers a higher model sensitivity to meteorology leading to reduced annual emissions down to 32 %. For HONO, we have implemented soil emissions, which depend on soil moisture and thus on precipitation. We estimate for the first time a global source strength of 7 Tg(N) a−1. Furthermore, the usage of a parameterization for the production of lightning NOx that depends on cloud top height contributes to a more realistic representation of NO2 columns over remote oceans with respect to the satellite measurements of the Ozone Monitoring Instrument (OMI). The combination of all the model modifications reduces the simulated global ozone burden by ≈ 20 % to 337 Tg, which is in better agreement with recent estimates. By comparing simulation results with measurements from the Infrared Atmospheric Sounding Interferometer (IASI) and the Tropospheric Ozone Assessment Report (TOAR) databases (of 2009) we demonstrate an overall reduction of the ozone bias by a factor of 2.


2020 ◽  
Vol 32 (S1) ◽  
pp. 121-121
Author(s):  
Catarina Pedro ◽  
Beatriz Jorge ◽  
Mariana Duarte

Introduction:Dementia has become a worldwide concern. According to the World Health Organization, there are 50 million individuals suffering from dementia across the world and approximately 20 million new cases are diagnosed each year. The efficacy of medications in controlling agitation and psychotic symptoms is modest and may cause serious adverse effects, outlining the urge for new treatment methods for patients with dementia. Music therapy (MT) is a nonpharmacologic strategy that is used in patients with early-to-late stages of dementia with promising results.Objectives:The aim of this presentation is to evaluate the benefits of music therapy in cognitive functioning and neuropsychiatric symptoms in patients diagnosed with dementia. We also summarize the current knowledge about this topic.Methods:A non-systematic review of the literature was performed on PubMed, PsycINFO and Web of science using selected keywords.Results:MT sustains its benefit because musical memory regions in the brain are relatively spared compared to cognitive function. “Musical memories” can, thus, be stored longer than non-musical memories, allowing to recall associated life events and emotions. Systematic reviews suggest that MT seem to have a positive effect on symptoms such as depression, anxiety and behavioral problems while the findings concerning agitation/aggression are inconsistent. No large differences were found between studies using live or recorded music although the latter reported more of a consistently positive impact on behavioral and psychological outcomes. The studies using live music, however, reported specific benefits to relationships and interactions.Conclusions:The majority of the studies have methodological limitations, making it difficult to offer firm conclusions. Despite this, there were positive results on aspects of quality of life, cognitive function, behavioral, psychological, physiological and communication outcomes.


2012 ◽  
Vol 12 (3) ◽  
pp. 1377-1395 ◽  
Author(s):  
K. He ◽  
Q. Zhao ◽  
Y. Ma ◽  
F. Duan ◽  
F. Yang ◽  
...  

Abstract. Aerosol acidity is one of the most important parameters influencing atmospheric chemistry and physics. Based on continuous field observations from January 2005 to May 2006 and thermodynamic modeling, we investigated the spatial and seasonal variations in PM2.5 acidity in two megacities in China, Beijing and Chongqing. Spatially, PM2.5 was generally more acidic in Chongqing than in Beijing, but a reverse spatial pattern was found within the two cities, with more acidic PM2.5 at the urban site in Beijing whereas the rural site in Chongqing. Ionic compositions of PM2.5 revealed that it was the higher concentrations of NO3− at the urban site in Beijing and the lower concentrations of Ca2+ within the rural site in Chongqing that made their PM2.5 more acidic. Temporally, PM2.5 was more acidic in summer and fall than in winter, while in the spring of 2006, the acidity of PM2.5 was higher in Beijing but lower in Chongqing than that in 2005. These were attributed to the more efficient formation of nitrate relative to sulfate as a result of the influence of Asian desert dust in 2006 in Beijing and the greater wet deposition of ammonium compared to sulfate and nitrate in 2005 in Chongqing. Furthermore, simultaneous increase of PM2.5 acidity was observed from spring to early summer of 2005 in both cities. This synoptic-scale evolution of PM2.5 acidity was accompanied by the changes in air masses origins, which were influenced by the movements of a subtropical high over the northwestern Pacific in early summer. Finally, the correlations between [NO3−]/[SO42−] and [NH4+]/[SO42−] suggests that under conditions of high aerosol acidity, heterogeneous reactions became one of the major pathways for the formation of nitrate at both cities. These findings provided new insights in our understanding of the spatial and temporal variations in aerosol acidity in Beijing and Chongqing, as well as those reported in other cities in China.


2021 ◽  
Vol ahead-of-print (ahead-of-print) ◽  
Author(s):  
Rafael P. Albuquerque ◽  
João J. Ferreira

Purpose This paper aims to verify co-creation behavior and understand a relationship between perception of service quality, loyalty and co-creation, from Starbucks customers' perspective. Design/methodology/approach A quantitative methodology was carried out, operationalized by applying a questionnaire to a sample of 385 respondents. Findings The results showed that service quality has a positive impact on loyalty and co-creation behavior in all its aspects; loyalty can be considered an important attribute in the intention of co-creation by customers. Originality/value This research extends the current knowledge on the subject and examines the associations between other attributes discussed. The implications of the study suggest strategic directions for using the clients' co-creation as a competitive alternative and generating value.


2017 ◽  
Author(s):  
Liang Feng ◽  
Paul I. Palmer ◽  
Robyn Butler ◽  
Stephen J. Andrews ◽  
Elliot L. Atlas ◽  
...  

Abstract. We infer surface fluxes of bromoform (CHBr3) and dibromoform (CH2Br2) from aircraft observations over the western Pacific using a tagged version of the GEOS-Chem global 3-D atmospheric chemistry model and a Maximum A Posteriori inverse model. The distribution of a priori ocean emissions of these gases are reasonably consistent with observed atmospheric mole fractions of CHBr3 (r = 0.62) and CH2Br2 (r = 0.38). These a priori emissions result in a positive model bias in CHBr3 peaking in the marine boundary layer, but capture observed values of CH2Br2 with no significant bias by virtue of its longer atmospheric lifetime. Using GEOS-Chem, we find that observed variations in atmospheric CHBr3 are determined equally by sources over the western Pacific and those outside the study region, but observed variations in CH2Br2 are determined mainly by sources outside the western Pacific. Numerical closed-loop experiments show that the spatial and temporal distribution of boundary layer aircraft data have the potential to substantially improve current knowledge of these fluxes, with improvements related to data density. Using the aircraft data, we estimate aggregated regional fluxes of 3.6 ± 0.3 × 108 g/month and 0.7 ± 0.1 × 108 g/month for CHBr3 and CH2Br2 over 130°–155° E and 0°–12° N, respectively, which represent reductions of 20–40 % and substantial spatial deviations from the a priori inventory. We find no evidence to support a robust linear relationship between CHBr3 and CH2Br2 oceanic emissions, as used by previous studies.


2017 ◽  
Author(s):  
Ben Newsome ◽  
Mat Evans

Abstract. Chemical rate constants determine the composition of the atmosphere and how this composition has changed over time. They are central to our understanding of climate change and air quality degradation. Atmospheric chemistry models, whether online or offline, box, regional or global use these rate constants. Expert panels synthesise laboratory measurements, making recommendations for the rate constants that should be used. This results in very similar or identical rate constants being used by all models. The inherent uncertainties in these recommendations are, in general, therefore ignored. We explore the impact of these uncertainties on the composition of the troposphere using the GEOS-Chem chemistry transport model. Based on the JPL and IUPAC evaluations we assess 50 mainly inorganic rate constants and 10 photolysis rates, through simulations where we increase the rate of the reactions to the 1σ upper value recommended by the expert panels. We assess the impact on 4 standard metrics: annual mean tropospheric ozone burden, surface ozone and tropospheric OH concentrations, and tropospheric methane lifetime. Uncertainty in the rate constants for NO2 + OH    M →  HNO3, OH + CH4 → CH3O2 + H2O and O3 + NO → NO2 + O2 are the three largest source of uncertainty in these metrics. We investigate two methods of assessing these uncertainties, addition in quadrature and a Monte Carlo approach, and conclude they give similar outcomes. Combining the uncertainties across the 60 reactions, gives overall uncertainties on the annual mean tropospheric ozone burden, surface ozone and tropospheric OH concentrations, and tropospheric methane lifetime of 11, 12, 17 and 17 % respectively. These are larger than the spread between models in recent model inter-comparisons. Remote regions such as the tropics, poles, and upper troposphere are most uncertain. This chemical uncertainty is sufficiently large to suggest that rate constant uncertainty should be considered when model results disagree with measurement. Calculations for the pre-industrial allow a tropospheric ozone radiative forcing to be calculated of 0.412 ± 0.062 Wm−2. This uncertainty (15 %) is comparable to the inter-model spread in ozone radiative forcing found in previous model-model inter-comparison studies where the rate constants used in the models are all identical or very similar. Thus the uncertainty of tropospheric ozone radiative forcing should expanded to include this additional source of uncertainty. These rate constant uncertainties are significant and suggest that refinement of supposedly well known chemical rate constants should be considered alongside other improvements to enhance our understanding of atmospheric processes.


2013 ◽  
Vol 443 ◽  
pp. 920-931 ◽  
Author(s):  
Ulas Im ◽  
Selahattin Incecik ◽  
Meltem Guler ◽  
Adil Tek ◽  
Sema Topcu ◽  
...  

2018 ◽  
Author(s):  
Detlev Helmig ◽  
Daniel Liptzin ◽  
Jacques Hueber ◽  
Joel Savarino

Abstract. Continuous measurements of reactive gases in the snowpack and above the snowpack surface were conducted at Concordia Station (Dome C), Antarctica, from December 2012–January 2014. Measured species included ozone, nitrogen oxides, gaseous elemental mercury, and formaldehyde, for study of photochemical reactions, surface exchange, and the seasonal cycles and atmospheric chemistry of these gases. The experiment was installed ~ 1 km from the main station infrastructure inside the station clean air sector and within the station electrical power grid boundary. Air was sampled continuously from three inlets on a 10 m meteorological tower, as well as from two above and four below the surface sampling inlets from within the snowpack. Despite being in the clean air sector, over the course of the 1.2-year study, we observed on the order of 15 occasions when exhaust plumes from the camp, most notably from the power generation system, were transported to the study site. Highly elevated levels of nitrogen oxides (up to 1000 x background) and lowered ozone (down to ~ 50 %), most likely from titration with nitric oxide, were measured in the exhaust plumes. Within 5–15 minutes from observing elevated pollutant levels above the snow, rapidly increasing and long-lasting concentration enhancements were measured in snowpack air. While pollution events typically lasted only a few minutes to an hour above the snow surface, elevated nitrogen oxides levels were observed in the snowpack lasting from a few days to one week. These observations add important new insight to the discussion of if and how snow-photochemical experiments within reach of the power grid of polar research sites are possibly compromised by the snowpack being chemically influenced (contaminated) by gaseous and particulate emissions from the research camp activities. This question is critical for evaluating if snowpack trace chemical measurements from within the camp boundaries are representative for the vast polar ice sheets.


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