Ozone Production Efficiencies in the Three Largest United States Cities from Airborne Measurements.

Despite ongoing reductions in emissions of ozone (O) precursors, nitrogen oxides (NO = NO + NO) and volatile organic compounds (VOCs), the three largest urban areas in the United States ─ New York City (NYC), Chicago, and Los Angeles (LA) ─ continue to exceed national air quality standards for O. Airborne measurements during the 2023 Atmospheric Emissions and Reactions Observed from Megacities to Marine Areas (AEROMMA) campaign investigated nonlinear O photochemistry in these cities. We report mean ozone production efficiency (OPE), the enhancement ratio of O (= O + NO) to NO oxidation products, of 9 ± 4 (1σ), 6 ± 3, and 6 ± 3 ppbv ppbv in NYC, Chicago, and LA, respectively.

Role of chemical production and depositional losses on formaldehyde in the Community Regional Atmospheric Chemistry Multiphase Mechanism (CRACMM).

Formaldehyde (HCHO) is an important air pollutant with direct cancer risk and ozone-forming potential. HCHO sources are complex because HCHO is both directly emitted and produced from oxidation of most gas-phase reactive organic carbon. We update the secondary production of HCHO in the Community Regional Atmospheric Chemistry Multiphase Mechanism (CRACMM) in the Community Multiscale Air Quality (CMAQ) model.

Incorporating Cooking Emissions To Better Simulate the Impact of Zero-Emission Vehicle Adoption on Ozone Pollution in Los Angeles.

Despite decades of emission control measures aimed at improving air quality, Los Angeles (LA) continues to experience severe ozone pollution during the summertime. We incorporate cooking volatile organic compound (VOC) emissions in a chemical transport model and evaluate it against observations in order to improve the model representation of the present-day ozone chemical regime in LA. Using this updated model, we investigate the impact of adopting zero-emission vehicles (ZEVs) on ozone pollution with increased confidence.

COVID-19 perturbation on US air quality and human health impact assessment.

The COVID-19 stay-at-home orders issued in the United States caused significant reductions in traffic and economic activities. To understand the pandemic's perturbations on US emissions and impacts on urban air quality, we developed near-real-time bottom-up emission inventories based on publicly available energy and economic datasets, simulated the emission changes in a chemical transport model, and evaluated air quality impacts against various observations. The COVID-19 pandemic affected US emissions across broad-based energy and economic sectors and the impacts persisted to 2021.

Leveraging scientific community knowledge for air quality model chemistry parameterizations.

An introduction to atmospheric chemical mechanisms: development, usage, and future needs.

Improved Spatial Resolution in Modeling of Nitrogen Oxide Concentrations in the Los Angeles Basin.

The extent to which emission control technologies and policies have reduced anthropogenic NO emissions from motor vehicles is large but uncertain. We evaluate a fuel-based emission inventory for southern California during the June 2021 period, coinciding with the Re-Evaluating the Chemistry of Air Pollutants in CAlifornia (RECAP-CA) field campaign. A modified version of the Fuel-based Inventory of Vehicle Emissions (FIVE) is presented, incorporating 1.

Sensitivity of northeastern US surface ozone predictions to the representation of atmospheric chemistry in the Community Regional Atmospheric Chemistry Multiphase Mechanism (CRACMMv1.0).

Chemical mechanisms describe how emissions of gases and particles evolve in the atmosphere and are used within chemical transport models to evaluate past, current, and future air quality. Thus, a chemical mechanism must provide robust and accurate predictions of air pollutants if it is to be considered for use by regulatory bodies. In this work, we provide an initial evaluation of the Community Regional Atmospheric Chemistry Multiphase Mechanism (CRACMMv1.

Linking gas, particulate, and toxic endpoints to air emissions in the Community Regional Atmospheric Chemistry Multiphase Mechanism (CRACMM).

Chemical mechanisms describe the atmospheric transformations of organic and inorganic species and connect air emissions to secondary species such as ozone, fine particles, and hazardous air pollutants (HAPs) like formaldehyde. Recent advances in our understanding of several chemical systems and shifts in the drivers of atmospheric chemistry warrant updates to mechanisms used in chemical transport models such as the Community Multiscale Air Quality (CMAQ) modeling system. This work builds on the Regional Atmospheric Chemistry Mechanism version 2 (RACM2) and develops the Community Regional Atmospheric Chemistry Multiphase Mechanism (CRACMM) version 1.

Influence of Wildfire on Urban Ozone: An Observationally Constrained Box Modeling Study at a Site in the Colorado Front Range.

Increasing trends in biomass burning emissions significantly impact air quality in North America. Enhanced mixing ratios of ozone (O) in urban areas during smoke-impacted periods occur through transport of O produced within the smoke or through mixing of pyrogenic volatile organic compounds (PVOCs) with urban nitrogen oxides (NO = NO + NO) to enhance local O production. Here, we analyze a set of detailed chemical measurements, including carbon monoxide (CO), NO, and speciated volatile organic compounds (VOCs), to evaluate the effects of smoke transported from relatively local and long-range fires on O measured at a site in Boulder, Colorado, during summer 2020.

Evaluating the Impact of Chemical Complexity and Horizontal Resolution on Tropospheric Ozone Over the Conterminous US With a Global Variable Resolution Chemistry Model.

A new configuration of the Community Earth System Model (CESM)/Community Atmosphere Model with full chemistry (CAM-chem) supporting the capability of horizontal mesh refinement through the use of the spectral element (SE) dynamical core is developed and called CESM/CAM-chem-SE. Horizontal mesh refinement in CESM/CAM-chem-SE is unique and novel in that pollutants such as ozone are accurately represented at human exposure relevant scales while also directly including global feedbacks. CESM/CAM-chem-SE with mesh refinement down to ∼14 km over the conterminous US (CONUS) is the beginning of the Multi-Scale Infrastructure for Chemistry and Aerosols (MUSICAv0).

Airborne Emission Rate Measurements Validate Remote Sensing Observations and Emission Inventories of Western U.S. Wildfires.

Carbonaceous emissions from wildfires are a dynamic mixture of gases and particles that have important impacts on air quality and climate. Emissions that feed atmospheric models are estimated using burned area and fire radiative power (FRP) methods that rely on satellite products. These approaches show wide variability and have large uncertainties, and their accuracy is challenging to evaluate due to limited aircraft and ground measurements.

Volatile chemical product emissions enhance ozone and modulate urban chemistry.

Decades of air quality improvements have substantially reduced the motor vehicle emissions of volatile organic compounds (VOCs). Today, volatile chemical products (VCPs) are responsible for half of the petrochemical VOCs emitted in major urban areas. We show that VCP emissions are ubiquitous in US and European cities and scale with population density.

Variability and Time of Day Dependence of Ozone Photochemistry in Western Wildfire Plumes.

Understanding the efficiency and variability of photochemical ozone (O) production from western wildfire plumes is important to accurately estimate their influence on North American air quality. A set of photochemical measurements were made from the NOAA Twin Otter research aircraft as a part of the Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) experiment. We use a zero-dimensional (0-D) box model to investigate the chemistry driving O production in modeled plumes.

Gas-Phase Reactions of Isoprene and Its Major Oxidation Products.

Isoprene carries approximately half of the flux of non-methane volatile organic carbon emitted to the atmosphere by the biosphere. Accurate representation of its oxidation rate and products is essential for quantifying its influence on the abundance of the hydroxyl radical (OH), nitrogen oxide free radicals (NO ), ozone (O), and, via the formation of highly oxygenated compounds, aerosol. We present a review of recent laboratory and theoretical studies of the oxidation pathways of isoprene initiated by addition of OH, O, the nitrate radical (NO), and the chlorine atom.

Alkoxy Radical Bond Scissions Explain the Anomalously Low Secondary Organic Aerosol and Organonitrate Yields From α-Pinene + NO.

Oxidation of monoterpenes (CH) by nitrate radicals (NO) constitutes an important source of atmospheric secondary organic aerosol (SOA) and organonitrates. However, knowledge of the mechanisms of their formation is incomplete and differences in yields between similar monoterpenes are poorly understood. In particular, yields of SOA and organonitrates from α-pinene + NO are low, while those from Δ-carene + NO are high.

Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms, and organic aerosol.

Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol.

Real-Time Studies of Iron Oxalate-Mediated Oxidation of Glycolaldehyde as a Model for Photochemical Aging of Aqueous Tropospheric Aerosols.

The complexation of iron(III) with oxalic acid in aqueous solution yields a strongly absorbing chromophore that undergoes efficient photodissociation to give iron(II) and the carbon dioxide anion radical. Importantly, iron(III) oxalate complexes absorb near-UV radiation (λ > 350 nm), providing a potentially powerful source of oxidants in aqueous tropospheric chemistry. Although this photochemical system has been studied extensively, the mechanistic details associated with its role in the oxidation of dissolved organic matter within aqueous aerosol remain largely unknown.

Atmospheric fates of Criegee intermediates in the ozonolysis of isoprene.

We use a large laboratory, modeling, and field dataset to investigate the isoprene + O3 reaction, with the goal of better understanding the fates of the C1 and C4 Criegee intermediates in the atmosphere. Although ozonolysis can produce several distinct Criegee intermediates, the C1 stabilized Criegee (CH2OO, 61 ± 9%) is the only one observed to react bimolecularly. We suggest that the C4 Criegees have a low stabilization fraction and propose pathways for their decomposition.

Isoprene NO3 Oxidation Products from the RO2 + HO2 Pathway.

We describe the products of the reaction of the hydroperoxy radical (HO(2)) with the alkylperoxy radical formed following addition of the nitrate radical (NO(3)) and O(2) to isoprene. NO(3) adds preferentially to the C(1) position of isoprene (>6 times more favorably than addition to C(4)), followed by the addition of O(2) to produce a suite of nitrooxy alkylperoxy radicals (RO(2)). At an RO(2) lifetime of ∼30 s, δ-nitrooxy and β-nitrooxy alkylperoxy radicals are present in similar amounts.

Mechanism of the hydroxyl radical oxidation of methacryloyl peroxynitrate (MPAN) and its pathway toward secondary organic aerosol formation in the atmosphere.

Methacryloyl peroxynitrate (MPAN), the acyl peroxynitrate of methacrolein, has been suggested to be an important secondary organic aerosol (SOA) precursor from isoprene oxidation. Yet, the mechanism by which MPAN produces SOA through reaction with the hydroxyl radical (OH) is unclear. We systematically evaluate three proposed mechanisms in controlled chamber experiments and provide the first experimental support for the theoretically-predicted lactone formation pathway from the MPAN + OH reaction, producing hydroxymethyl-methyl-α-lactone (HMML).

The PHD3 domain of MLL acts as a CYP33-regulated switch between MLL-mediated activation and repression .

The mixed lineage leukemia (MLL) gene plays a critical role in epigenetic regulation of gene expression and is a frequent target of chromosomal translocations leading to leukemia. MLL plant homeodomain 3 (PHD3) is lost in all MLL translocation products, and reinsertion of PHD3 into MLL fusion proteins abrogates their transforming activity. PHD3 has been shown to interact with the RNA-recognition motif (RRM) domain of human nuclear Cyclophilin33 (CYP33).