Stability of clay particle-coated microbubbles in alkanes against dissolution induced by heating

We investigated the dissolution and morphological dynamics of air bubbles in alkanes stabilized by fluorinated colloidal clay particles when subjected to temperature changes. A quasi-steady model for bubble dissolution with time-dependent temperature reveals that increasing the temperature enhances the bubble dissolution rate in alkanes, opposite to the behavior in water, due to the differing trends in gas solubility. Experimental results for uncoated air bubbles in decane and hexadecane confirm this prediction. Clay-coated bubbles in decane and hexadecane are shown to be stable in air-saturated oil at constant temperature, where dissolution is driven mainly by the Laplace pressure. When the temperature increases from ambient, the particle-coated bubbles are prone to dissolution as the oil phase becomes under-saturated. The interfacial layer of particles is observed to undergo buckling and crumpling, without shedding of clay particles. Increasing the concentration of particles is shown to enhance the bubble stability by providing a higher resistance to dissolution and buckling. When subjected to complex temperature cycles, the clay-coated bubbles can remain stable in conditions for which uncoated bubbles dissolve completely. These results underpin the design of ultra-stable oil foams stabilized by solid particles with improved shelf life under changing environmental conditions

Importance of relative humidity in the oxidative ageing of organic aerosols: case study of the ozonolysis of maleic acid aerosol

Many important atmospheric aerosol processes depend on the chemical composition of the aerosol, e.g. water uptake and particle cloud interactions. Atmospheric ageing processes, such as oxidation reactions, significantly and continuously change the chemical composition of aerosol particles throughout their lifetime. These ageing processes are often poorly understood. In this study we utilize an aerosol flow tube set up and an ultra-high resolution mass spectrometer to explore the effect of relative humidity (RH) in the range of <5–90% on the ozonolysis of maleic acid aerosol which is employed as model organic aerosol system. Due to the slow reaction kinetics relatively high ozone concentrations of 160–200 ppm were used to achieve an appreciable degree of oxidation of maleic acid. The effect of oxidative ageing on the hygroscopicity of maleic acid particles is also investigated using an electrodynamic balance and thermodynamic modelling. RH has a profound effect on the oxidation of maleic acid particles. Very little oxidation is observed at RH < 50% and the only observed reaction products are glyoxylic acid and formic acid. In comparison, when RH > 50% there are about 15 oxidation products identified. This increased oxidation was observed even when the particles were exposed to high humidities long after a low RH ozonolysis reaction. This result might have negative implications for the use of water as an extraction solvent for the analysis of oxidized organic aerosols. These humidity-dependent differences in the composition of the ozonolyzed aerosol demonstrate that water is both a key reactant in the oxidation scheme and a determinant of particle phase and hence diffusivity. The measured chemical composition of the processed aerosol is used to model the hygroscopic growth, which compares favourably with water uptake results from the electrodynamic balance measurements. A reaction mechanism is presented which takes into account the RH dependent observations. This study emphasises the importance of studying the combined effects of several atmospheric parameters such as oxidants and RH to accurately describe the complex oxidation scheme of organic aerosols

Understanding the glacial methane cycle.

Atmospheric methane (CH4) varied with climate during the Quaternary, rising from a concentration of 375 p.p.b.v. during the last glacial maximum (LGM) 21,000 years ago, to 680 p.p.b.v. at the beginning of the industrial revolution. However, the causes of this increase remain unclear; proposed hypotheses rely on fluctuations in either the magnitude of CH4 sources or CH4 atmospheric lifetime, or both. Here we use an Earth System model to provide a comprehensive assessment of these competing hypotheses, including estimates of uncertainty. We show that in this model, the global LGM CH4 source was reduced by 28-46%, and the lifetime increased by 2-8%, with a best-estimate LGM CH4 concentration of 463-480 p.p.b.v. Simulating the observed LGM concentration requires a 46-49% reduction in sources, indicating that we cannot reconcile the observed amplitude. This highlights the need for better understanding of the effects of low CO2 and cooler climate on wetlands and other natural CH4 sources

Uncertainties in Isoprene Photochemistry and Emissions: Implications for the Oxidative Capacity of Past and Present Atmospheres and for Climate Forcing Agents

Current understanding of the factors controlling biogenic isoprene emissions and of the fate of isoprene oxidation products in the atmosphere has been evolving rapidly. We use a climate-biosphere-chemistry modeling framework to evaluate the sensitivity of estimates of the tropospheric oxidative capacity to uncertainties in isoprene emissions and photochemistry. Our work focuses on trends across two time horizons: from the Last Glacial Maximum (LGM, 21 000 years BP) to the preindustrial (1770s); and from the preindustrial to the present day (1990s). We find that different oxidants have different sensitivities to the uncertainties tested in this study, with OH being the most sensitive: changes in the global mean OH levels for the LGM-to-preindustrial transition range between -29 and +7, and those for the preindustrial-to-present day transition range between -8 and +17, across our simulations. Our results suggest that the observed glacial-interglacial variability in atmospheric methane concentrations is predominantly driven by changes in methane sources as opposed to changes in OH, the primary methane sink. However, the magnitudes of change are subject to uncertainties in the past isoprene global burdens, as are estimates of the change in the global burden of secondary organic aerosol (SOA) relative to the preindustrial. We show that the linear relationship between tropospheric mean OH and tropospheric mean ozone photolysis rates, water vapor, and total emissions of NOx and reactive carbon first reported in Murray et al. (2014) does not hold across all periods with the new isoprene photochemistry mechanism. Our results demonstrate that inadequacies in our understanding of present-day OH and its controlling factors must be addressed in order to improve model estimates of the oxidative capacity of past and present atmospheres

Particulate matter-attributable mortality and relationships with carbon dioxide in 250 urban areas worldwide

Urban air pollution is high on global health and sustainability agendas, but information is limited on associated city-level disease burdens. We estimated fine particulate matter (PM2.5) mortality in the 250 most populous cities worldwide using PM2.5 concentrations, population, disease rates, and concentration-response relationships from the Global Burden of Disease 2016 Study. Only 8% of these cities had population-weighted mean concentrations below the World Health Organization guideline for annual average PM2.5. City-level PM2.5-attributable mortality rates ranged from 13–125 deaths per 100,000 people. PM2.5 mortality rates and carbon dioxide (CO2) emission rates were weakly positively correlated, with regional influences apparent from clustering of cities within each region. Across 82 cities globally, PM2.5 concentrations and mortality rates were negatively associated with city gross domestic product (GDP) per capita, but we found no relationship between GDP per capita and CO2 emissions rates. While results provide only a cross-sectional snapshot of cities worldwide, they point to opportunities for cities to realize climate, air quality, and health co-benefits through low-carbon development. Future work should examine drivers of the relationships (e.g. development stage, fuel mix for electricity generation and transportation, sector-specific PM2.5 and CO2 emissions) uncovered here and explore uncertainties to test the robustness of our conclusions

Drought-sensitivity of fine dust in the U.S. Southwest: Implications for air quality and public health under future climate change

We investigate the present-day sensitivity of fine dust levels in the U.S. Southwest to regional drought conditions and use the observed relationships to assess future changes in fine dust levels and associated health impacts under climate change. Empirical Orthogonal Function analysis reveals that the most dominant mode of fine dust interannual variability for each season consists of a pattern of large-scale co-variability across the Southwest. This mode is strongly correlated to the Standardized Precipitation-Evapotranspiration Index (SPEI) accumulated over 1-6 months in local and surrounding regions spanning the major North American deserts. Across the seasons, a unit decrease in 2-month SPEI averaged over the U.S. Southwest and northern Mexico is significantly associated with increases in Southwest fine dust of 0.22-0.43 μg m-3. We apply these sensitivities to statistically downscaled meteorological output from 22 climate models following two Representative Concentration Pathways (RCPs), and project future increases in seasonal mean fine dust of 0.04-0.10 μg m-3 (5-8%) under RCP2.6 and 0.15-0.55 μg m-3 (26-46%) under RCP8.5 relative to the present-day (2076-2095 vs. 1996-2015). Combined with the same projections of future population and baseline incidence rates, annual premature mortality attributable to fine dust exposure could increase by 140 (24%) deaths under RCP2.6 and 750 (130%) deaths under RCP8.5 for adults aged ≥30 years, and annual hospitalizations due to cardiovascular and respiratory illnesses could increase by 170 (59%) admissions under RCP2.6 and 860 (300%) admissions under RCP8.5 for adults aged ≥65 years in the Southwest relative to the present-day. Our results highlight a climate penalty that has important socioeconomic and policy implications for the U.S. Southwest but is not yet widely recognized