Nighttime air quality under desert conditions

Nighttime concentrations of the gas phase nitrate radical (NO3) were successfully measured during a four week field campaign in an arid urban location, Reno Nevada, using long-path Differential Optical Absorbance Spectrometry (DOAS). While typical concentrations of NO3 ranged from 5 to 20ppt, elevated concentrations were observed during a wildfire event. Horizontal mixing in the free troposphere was considerable because the sampling site was above the stable nocturnal boundary layer every night and this justified a box modeling approach. Process analysis of box model simulations showed NO3 accounted for approximately half of the loss of internal olefins, 60% of the isoprene loss, and 85% of the α-pinene loss during the nighttime hours during a typical night of the field study. The NO3+aldehyde reactions were not as important as anticipated. On a polluted night impacted by wildfires upwind of the sampling location, NO3 reactions were more important. Model simulations overpredicted NO2 concentrations for both case studies and inorganic chemistry was the biggest influence on NO3 concentrations and on nitric acid formation. The overprediction may be due to additional NO2 loss processes that were not included in the box model, as deposition and N2O5 uptake had no significant effect on NO2 levels

A comparison of atmospheric composition using the Carbon Bond and Regional Atmospheric Chemistry Mechanisms

We incorporate the recently developed Regional Atmospheric Chemistry Mechanism (version 2, RACM2) into the Community Multiscale Air Quality modeling system for comparison with the existing 2005 Carbon Bond mechanism with updated toluene chemistry (CB05TU). Compared to CB05TU, RACM2 enhances the domain-wide monthly mean hydroxyl radical concentrations by 46% and nitric acid by 26%. However, it reduces hydrogen peroxide by 2%, peroxyacetic acid by 94%, methyl hydrogen peroxide by 19%, peroxyacetyl nitrate by 40%, and organic nitrate by 41%. RACM2 enhances ozone compared to CB05TU at all ambient levels. Although it exhibited greater overestimates at lower observed concentrations, it displayed an improved performance at higher observed concentrations. The RACM2 ozone predictions are also supported by increased ozone production efficiency that agrees better with observations. Compared to CB05TU, RACM2 enhances the domain-wide monthly mean sulfate by 10%, nitrate by 6%, ammonium by 10%, anthropogenic secondary organic aerosols by 42%, biogenic secondary organic aerosols by 5%, and in-cloud secondary organic aerosols by 7%. Increased inorganic and organic aerosols with RACM2 agree better with observed data. Any air pollution control strategies developed using the two mechanisms do not differ appreciably

Evaluation of simulated photochemical partitioning of oxidized nitrogen in the upper troposphere

Regional and global chemical transport models underpredict NOx (NO + NO2) in the upper troposphere where it is a precursor to the greenhouse gas ozone. The NOx bias has been shown in model evaluations using aircraft data (Singh et al., 2007) and total column NO2 (molecules cm−2) from satellite observations (Napelenok et al., 2008). The causes of NOx underpredictions have yet to be fully understood due to the interconnected nature of simulated emission, transport, and chemistry processes. Recent observation-based studies, in the upper troposphere, identify chemical rate coefficients as a potential source of error (Olson et al., 2006; Ren et al., 2008). Since typical chemistry evaluation techniques are not available for upper tropospheric conditions, this study develops an evaluation platform from in situ observations, stochastic convection, and deterministic chemistry. We derive a stochastic convection model and optimize it using two simulated datasets of time since convection, one based on meteorology, and the other on chemistry. The chemistry surrogate for time since convection is calculated using seven different chemical mechanisms, all of which predict shorter time since convection than our meteorological analysis. We evaluate chemical simulations by inter-comparison and by pairing results with observations based on NOx:HNO3, a photochemical aging indicator. Inter-comparison reveals individual chemical mechanism biases and recommended updates. Evaluation against observations shows that all chemical mechanisms overpredict NOx removal relative to long-lived methanol and carbon monoxide. All chemical mechanisms underpredict observed NOx by at least 30%, and further evaluation is necessary to refine simulation sensitivities to initial conditions and chemical rate uncertainties

Evaluation of simulated photochemical partitioning of oxidized nitrogen in the upper troposphere

Regional and global chemical transport models underpredict NO<sub>x</sub> (NO + NO<sub>2</sub>) in the upper troposphere where it is a precursor to the greenhouse gas ozone. The NO<sub>x</sub> bias has been shown in model evaluations using aircraft data (Singh et al., 2007) and total column NO<sub>2</sub> (molecules cm<sup>−2</sup>) from satellite observations (Napelenok et al., 2008). The causes of NO<sub>x</sub> underpredictions have yet to be fully understood due to the interconnected nature of simulated emission, transport, and chemistry processes. Recent observation-based studies, in the upper troposphere, identify chemical rate coefficients as a potential source of error (Olson et al., 2006; Ren et al., 2008). Since typical chemistry evaluation techniques are not available for upper tropospheric conditions, this study develops an evaluation platform from in situ observations, stochastic convection, and deterministic chemistry. We derive a stochastic convection model and optimize it using two simulated datasets of time since convection, one based on meteorology, and the other on chemistry. The chemistry surrogate for time since convection is calculated using seven different chemical mechanisms, all of which predict shorter time since convection than our meteorological analysis. We evaluate chemical simulations by inter-comparison and by pairing results with observations based on NO<sub>x</sub>:HNO<sub>3</sub>, a photochemical aging indicator. Inter-comparison reveals individual chemical mechanism biases and recommended updates. Evaluation against observations shows that all chemical mechanisms overpredict NO<sub>x</sub> removal relative to long-lived methanol and carbon monoxide. All chemical mechanisms underpredict observed NO<sub>x</sub> by at least 30%, and further evaluation is necessary to refine simulation sensitivities to initial conditions and chemical rate uncertainties

Prenatal exposures and exposomics of asthma

This review examines the causal investigation of preclinical development of childhood asthma using exposomic tools. We examine the current state of knowledge regarding early-life exposure to non-biogenic indoor air pollution and the developmental modulation of the immune system. We examine how metabolomics technologies could aid not only in the biomarker identification of a particular asthma phenotype, but also the mechanisms underlying the immunopathologic process. Within such a framework, we propose alternate components of exposomic investigation of asthma in which, the exposome represents a reiterative investigative process of targeted biomarker identification, validation through computational systems biology and physical sampling of environmental medi

Perspective on Mechanism Development and Structure‐Activity Relationships for Gas‐Phase Atmospheric Chemistry

This perspective gives our views on general aspects and future directions of gas‐phase atmospheric chemical kinetic mechanism development, emphasizing on the work needed for the sustainable development of chemically detailed mechanisms that reflect current kinetic, mechanistic, and theoretical knowledge. Current and future mechanism development efforts and research needs are discussed, including software‐aided autogeneration and maintenance of kinetic models as a future‐proof approach for atmospheric model development. There is an overarching need for the evaluation and extension of structure‐activity relationships (SARs) that predict the properties and reactions of the many multifunctionalized compounds in the atmosphere that are at the core of detailed mechanisms, but for which no direct chemical data are available. Here, we discuss the experimental and theoretical data needed to support the development of mechanisms and SARs, the types of SARs relevant to atmospheric chemistry, the current status and limitations of SARs for various types of atmospheric reactions, the status of thermochemical estimates needed for mechanism development, and our outlook for the future. The authors have recently formed a SAR evaluation working group to address these issues

Exploring Resonance and Identity in Contemporary Dance Improvisation

The project I am presenting is a series of improvisational dance works that I have edited together into a dance film. A large percentage of dance training emphasizes set choreography: “knowing what they were doing in the moment and being certain of what movement came next,” meanwhile improvisation is “the act of spontaneous dance composition comprised of implicit (habitual/prereflective actions) and explicit (consciously directed) choreographic actions” (Martin, 2017). The current project explores the continuum that exists between choreography and improvisation. To drive and inspire the movement, I utilize a score of ideas that internationally renowned dancer/educator Anya Cloud helped me create. The current score includes explorations of physical movement prompts, emotional prompts, imagery and imagination, relationship to time, space, and light, perceptions of gender, performativity and internalization, fantasy and reality, as well as anything else that may arise in a specific moment in time and how that moment relates to infinite other moments. The current dance film is also a part of a broader ongoing project. Two other Dance BFA students and I take videos of our dancing once a week, then share a snippet of that performance each week for eight weeks. The version of this project that I am currently sharing is an edited film that includes dancing from the first three weeks out of the total eight. Another cumulative version of the dance film will be edited and shared at the end of the eight weeks

A Review of Tropospheric Atmospheric Chemistry and Gas-Phase Chemical Mechanisms for Air Quality Modeling

Gas-phase chemical mechanisms are vital components of prognostic air quality models. The mechanisms are incorporated into modules that are used to calculate the chemical sources and sinks of ozone and the precursors of particulates. Fifty years ago essential atmospheric chemical processes, such as the importance of the hydroxyl radical, were unknown and crude air quality models incorporated only a few parameterized reactions obtained by fitting observations. Over the years, chemical mechanisms for air quality modeling improved and became more detailed as more experimental data and more powerful computers became available. However it will not be possible to incorporate a detailed treatment of the chemistry for all known chemical constituents because there are thousands of organic compounds emitted into the atmosphere. Some simplified method of treating atmospheric organic chemistry is required to make air quality modeling computationally possible. The majority of the significant differences between air quality mechanisms are due to the differing methods of treating this organic chemistry. The purpose of this review is to present an overview of atmospheric chemistry that is incorporated into air quality mechanisms and to suggest areas in which more research is needed