United States Environmental Protection Agency guidance on the use of photochemical models for assessing the efficacy of an emissions control strategy for ozone requires that modeling be used in a relative sense. Consequently, testing a modeling system's ability to predict changes in ozone resulting from emission changes is critical. We evaluate model simulations for precursor species (NOx, CO, and volatile organic compounds [VOCs]), radicals (OH and HO2), a secondary pollutant (O3), and the model response of these compounds to weekend/weekday emission changes during California Nexus study in 2010. The modeling system correctly simulated the broad spatial and temporal variation of NOx and O3 in California South Coast. Although the model generally underpredicted the daytime mixing ratios of NO2 at the surface and overpredicted the NO2 column, the simulated weekend to weekday ratios are consistent with each other and match the observed ratios well. The modeling system exhibited reasonable performance in simulating the VOC compounds with fossil fuel origins but has larger bias in simulating certain species associated with noncombustion sources. The modeling system successfully captured the weekend changes of the enhancement ratios for various VOC species to CO and the relative changes of HOx, which are indicators of faster chemical processing on weekends. This work demonstrates satisfactory model performances for O3 and most relevant chemical compounds with more robust performance in simulating weekend versus weekday changes. Improved planetary boundary layer height simulations, a better understanding of OH-HO2 cycling, continued improvement of emissions, especially urban biogenic emissions and emissions of oxygenated VOCs, are important for future model improvement.

The hydroxyl radical (OH) is the dominant oxidant in the outdoor environment, controlling the lifetimes of volatile organic compounds (VOCs) and contributing to the growth of secondary organic aerosols. Despite its importance outdoors, there have been relatively few measurements of the OH radical in indoor environments. During the House Observations of Microbial and Environmental Chemistry (HOMEChem) campaign, elevated concentrations of OH were observed near a window during cooking events, in addition to elevated mixing ratios of nitrous acid (HONO), VOCs, and nitrogen oxides (NO_X). Particularly high concentrations were measured during the preparation of a traditional American Thanksgiving dinner, which required the use of a gas stove and oven almost continually for 6 h. A zero-dimensional chemical model underpredicted the measured OH concentrations even during periods when direct sunlight illuminated the area near the window, which increases the rate of OH production by photolysis of HONO. Interferences with measurements of nitrogen dioxide (NO₂) and ozone (O₃) suggest that unmeasured photolytic VOCs were emitted during cooking events. The addition of a VOC that photolyzes to produce peroxy radicals (RO₂), similar to pyruvic acid, into the model results in better agreement with the OH measurements. These results highlight our incomplete understanding of the nature of oxidation in indoor environments.

Historically air constituents have been assumed to be well mixed in indoor environments, with single point measurements and box modeling representing a room or a house. Here we demonstrate that this fundamental assumption needs to be revisited through advanced model simulations and extensive measurements of bleach cleaning. We show that inorganic chlorinated products, such as hypochlorous acid and chloramines generated via multiphase reactions, exhibit spatial and vertical concentration gradients in a room, with short-lived ⋅OH radicals confined to sunlit zones, close to windows. Spatial and temporal scales of indoor constituents are modulated by rates of chemical reactions, surface interactions and building ventilation, providing critical insights for better assessments of human exposure to hazardous pollutants, as well as the transport of indoor chemicals outdoors.

Tropicalization is a term used to describe the transformation of temperate ecosystems by poleward-moving tropical organisms in response to warming temperatures. In North America, decreases in the frequency and intensity of extreme winter cold events are expected to allow the poleward range expansion of many cold-sensitive tropical organisms, sometimes at the expense of temperate organisms. Although ecologists have long noted the critical ecological role of winter cold temperature extremes in tropical-temperate transition zones, the ecological effects of extreme cold events have been understudied, and the influence of warming winter temperatures has too often been left out of climate change vulnerability assessments. Here, we examine the influence of extreme cold events on the northward range limits of a diverse group of tropical organisms, including terrestrial plants, coastal wetland plants, coastal fishes, sea turtles, terrestrial reptiles, amphibians, manatees, and insects. For these organisms, extreme cold events can lead to major physiological damage or landscape-scale mass mortality. Conversely, the absence of extreme cold events can foster population growth, range expansion, and ecological regime shifts. We discuss the effects of warming winters on species and ecosystems in tropical-temperate transition zones. In the 21st century, climate change-induced decreases in the frequency and intensity of extreme cold events are expected to facilitate the poleward range expansion of many tropical species. Our review highlights critical knowledge gaps for advancing understanding of the ecological implications of the tropicalization of temperate ecosystems in North America.