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Organic substances can adopt an amorphous solid or semisolid state, influencing the rate of heterogeneous reactions and multiphase processes in atmospheric aerosols. Here we demonstrate how molecular diffusion in the condensed phase affects the gas uptake and chemical transformation of semisolid organic particles. Flow tube experiments show that the ozone uptake and oxidative aging of amorphous protein is kinetically limited by bulk diffusion. The reactive gas uptake exhibits a pronounced increase with relative humidity, which can be explained by a decrease of viscosity and increase of diffusivity due to hygroscopic water uptake transforming the amorphous organic matrix from a glassy to a semisolid state (moisture-induced phase transition). The reaction rate depends on the condensed phase diffusion coefficients of both the oxidant and the organic reactant molecules, which can be described by a kinetic multilayer flux model but not by the traditional resistor model approach of multiphase chemistry. The chemical lifetime of reactive compounds in atmospheric particles can increase from seconds to days as the rate of diffusion in semisolid phases can decrease by multiple orders of magnitude in response to low temperature or low relative humidity. The findings demonstrate that the occurrence and properties of amorphous semisolid phases challenge traditional views and require advanced formalisms for the description of organic particle formation and transformation in atmospheric models of aerosol effects on air quality, public health, and climate.

Research on the link between educational leadership and student learning employs a variety of quantitative and qualitative research designs. Surprisingly, there are relatively few studies on methods for researching educational leadership practices. This article addresses this gap in research and discusses how the experiences of different participants can constitute potential starting points for learning processes. This leads to the question, how and to what extent the educational leadership practices manifest in students’ experiences and how “Leadership for Learning as Experience” can be empirically researched. The phenomenologically oriented vignette as research method for studying educational leadership practices will be introduced. Vignettes are narratives that are based on the experiences of participants. In vignettes, the co-experienced observations in the field are captured in form of vivid narratives. Vignettes thus open up a new, supplementary perspective, in which the traces that leadership practices have left on school participants are revealed.

This article, the seventh in the series, presents kinetic and photochemical data sheets evaluated by the IUPAC Task Group on Atmospheric Chemical Kinetic Data Evaluation. It covers an extension of the gas-phase and photochemical reactions related to Criegee intermediates previously published in Atmospheric Chemistry and Physics (ACP) in 2006 and implemented on the IUPAC website up to 2020. The article consists of an introduction, description of laboratory measurements, a discussion of rate coefficients for reactions of O3 with alkenes producing Criegee intermediates, rate coefficients of unimolecular and bimolecular reactions and photochemical data for reactions of Criegee intermediates, and an overview of the atmospheric chemistry of Criegee intermediates. Summary tables of the recommended kinetic and mechanistic parameters for the evaluated reactions are provided. Data sheets summarizing information upon which the recommendations are based are given in two files, provided as a Supplement to this article.

Compared to stratospheric SO2 injection for climate intervention, alumina particle injection could reduce stratospheric warming and associated adverse impacts. However, heterogeneous chemistry on alumina particles, especially chlorine activation via ClONO2+HCl→surfCl2+HNO3${\\text{ClONO}}_{2}+\\text{HCl}\\stackrel{\\text{surf}}{\\to }{\\text{Cl}}_{2}+{\\text{HNO}}_{3}$ , is poorly constrained under stratospheric conditions, such as low temperature and humidity. This study quantifies the uncertainty in modeling the ozone response to alumina injection. We show that extrapolating the limited experimental data for ClONO2 + HCl to stratospheric conditions leads to uncertainties in heterogeneous reaction rates of almost two orders of magnitude. Implementation of injection of 5 Mt/yr of particles with 240 nm radius in an aerosol‐chemistry‐climate model shows that resulting global total ozone depletions range between negligible and as large as 9%, that is more than twice the loss caused by chlorofluorocarbons, depending on assumptions on the degree of dissociation and interaction of the acids HCl, HNO3, and H2SO4 on the alumina surface. Plain Language Summary Global warming caused by increasing greenhouse gases could be temporarily reduced by introducing aerosol particles into the stratosphere. The most frequently studied approach to climate intervention uses H2SO4‐H2O aerosols, which, however, could result in undesirably strong warming of the stratosphere and significant ozone depletion. This might be improved by injecting solid particles, for example, made of aluminum oxide. However, here we show that the extremely limited availability of experimental studies on heterogeneous chemistry on alumina under the influence of stratospheric concentrations of HCl, HNO3, H2SO4, and H2O leads to large uncertainties in the impact of alumina injection on stratospheric ozone. In order to quantify these uncertainties, we integrated the currently available knowledge about the most important heterogeneous reaction ClONO2+HCl→surfCl2+HNO3${\\text{ClONO}}_{2}+\\text{HCl}\\stackrel{\\text{surf}}{\\to }{\\text{Cl}}_{2}+{\\text{HNO}}_{3}$into an aerosol‐chemistry‐climate model. We conclude that the uncertainty in the resulting heterogeneous reaction rate is more than two orders of magnitude depending on the partitioning of HCl, H2SO4, and HNO3 on the alumina surface. This could lead to global ozone column depletion ranging between almost negligible and up to 9%, which would be more than twice as much as the ozone loss caused by chlorofluorocarbons in the late 1990s. Key Points Heterogeneous chemistry on solid alumina particles is highly uncertain and depends strongly on the partitioning of acids onto the surface The reaction rate of ClONO2 with HCl on alumina particles is uncertain by up to two orders of magnitude under stratospheric conditions Injection of 5 Mt/yr of alumina particles could double global ozone reductions compared to chlorofluorocarbons in the late 1990s

In viscous, organic-rich aerosol particles containing iron, sunlight may induce anoxic conditions that stabilize reactive oxygen species (ROS) and carbon-centered radicals (CCRs). In laboratory experiments, we show mass loss, iron oxidation and radical formation and release from photoactive organic particles containing iron. Our results reveal a range of temperature and relative humidity, including ambient conditions, that control ROS build up and CCR persistence in photochemically active, viscous organic particles. We find that radicals can attain high concentrations, altering aerosol chemistry and exacerbating health hazards of aerosol exposure. Our physicochemical kinetic model confirmed these results, implying that oxygen does not penetrate such particles due to the combined effects of fast reaction and slow diffusion near the particle surface, allowing photochemically-produced radicals to be effectively trapped in an anoxic organic matrix. Sunlight can change the composition of atmospheric aerosol particles, but the mechanisms through which this happens are not well known. Here, the authors show that fast radical reaction and slow diffusion near viscous organic particle surfaces can cause oxygen depletion, radical trapping and humidity dependent oxidation.

Soot particles produced by incomplete combustion processes are one of the major components of urban air pollution. Chemistry at their surfaces lead to the heterogeneous conversion of several key trace gases; for example NO₂ interacts with soot and is converted into HONO, which rapidly photodissociates to form OH in the troposphere. In the dark, soot surfaces are rapidly deactivated under atmospheric conditions, leading to the current understanding that soot chemistry affects tropospheric chemical composition only in a minor way. We demonstrate here that the conversion of NO₂ to HONO on soot particles is drastically enhanced in the presence of artificial solar radiation, and leads to persistent reactivity over long periods. Soot photochemistry may therefore be a key player in urban air pollution.

Nitrous acid: the day job Nitrous acid is a major photochemical precursor of the hydroxyl radical, a key oxidant in the degradation of air pollutants in the lower atmosphere. The gas is known to accumulate in the lower troposphere at night, but the recent discovery of enhanced concentrations of nitrous acid measured at various sites both urban and rural during daytime was a surprise. Now the light-induced reaction between soil humic acid and nitrogen dioxide has been put forward as an explanation. The observed reaction rate of nitrous acid formation suggests that this production mechanism could be an important factor in the chemistry of the lower troposphere Nitrous acid is a significant photochemical precursor of the hydroxyl radical 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , the key oxidant in the degradation of most air pollutants in the troposphere. The sources of nitrous acid in the troposphere, however, are still poorly understood. Recent atmospheric measurements 7 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 revealed a strongly enhanced formation of nitrous acid during daytime via unknown mechanisms. Here we expose humic acid films to nitrogen dioxide in an irradiated tubular gas flow reactor and find that reduction of nitrogen dioxide on light-activated humic acids is an important source of gaseous nitrous acid. Our findings indicate that soil and other surfaces containing humic acid exhibit an organic surface photochemistry that produces reductive surface species, which react selectively with nitrogen dioxide. The observed rate of nitrous acid formation could explain the recently observed high daytime concentrations of nitrous acid in the boundary layer, the photolysis of which accounts for up to 60 per cent of the integrated hydroxyl radical source strengths 3 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 . We suggest that this photo-induced nitrous acid production on humic acid could have a potentially significant impact on the chemistry of the lowermost troposphere.

The multi-phase oxidation of S(IV) plays a crucial role in the atmosphere, leading to the formation of haze and severe pollution episodes. We here contribute to its understanding on a molecular level by reporting experimentally determined p K a values of the various S(IV) tautomers and reaction barriers for SO 2 formation pathways. Complementary state-of-the-art molecular-dynamics simulations reveal a depletion of bisulfite at low pH at the liquid-vapor interface, resulting in a different tautomer ratio at the interface compared to the bulk. On a molecular-scale level, we explain this with the formation of a stable contact ion pair between sulfonate and hydronium ions, and with the higher energetic barrier for the dehydration of sulfonic acid at the liquid-vapor interface. Our findings highlight the contrasting physicochemical behavior of interfacial versus bulk environments, where the pH dependence of the tautomer ratio reported here has a significant impact on both SO 2 uptake kinetics and reactions involving NO x and H 2 O 2 at aqueous aerosol interfaces. The complex equilibria of sulfur compounds at the liquid-vapor interface play key roles in atmospheric processes. Here, using X-ray photoelectron spectroscopy, Raman spectroscopy, and molecular dynamics simulations the authors determining pKa values and tautomer ratios at the air-vapor interface in a liquid microjet.

Oxidation of bromide in aqueous environments initiates the formation of molecular halogen compounds, which is important for the global tropospheric ozone budget. In the aqueous bulk, oxidation of bromide by ozone involves a [Br•OOO − ] complex as intermediate. Here we report liquid jet X-ray photoelectron spectroscopy measurements that provide direct experimental evidence for the ozonide and establish its propensity for the solution-vapour interface. Theoretical calculations support these findings, showing that water stabilizes the ozonide and lowers the energy of the transition state at neutral pH. Kinetic experiments confirm the dominance of the heterogeneous oxidation route established by this precursor at low, atmospherically relevant ozone concentrations. Taken together, our results provide a strong case of different reaction kinetics and mechanisms of reactions occurring at the aqueous phase-vapour interface compared with the bulk aqueous phase. Heterogeneous oxidation of bromide in atmospheric aqueous environments has long been suspected to be accelerated at the interface between aqueous solution and air. Here, the authors provide spectroscopic, kinetic and theoretical evidence for a rate limiting, surface active ozonide formed at the interface.

Accumulating evidence suggests that metabolic demands of the regenerating liver are met via lipid metabolism and critical regulators of this process. As such, glucagon-like peptide-1 (GLP-1) and glucagon-like peptide-2 (GLP-2) critically affect hepatic regeneration in rodent models. The present study aimed to evaluate potential alterations and dynamics of circulating GLP-1 and GLP-2 in patients undergoing liver resections, focusing on post-hepatectomy liver failure (PHLF). GLP-1, GLP-2, Interleukin-6 (IL-6) and parameters of lipid metabolism were determined perioperatively in fasting plasma of 46 patients, who underwent liver resection. GLP-1 and GLP-2 demonstrated a rapid and consistently inverse time course during hepatic regeneration with a significant decrease of GLP-1 and increase of GLP-2 on POD1. Importantly, these postoperative dynamics were significantly more pronounced when PHLF occurred. Of note, the extent of resection or development of complications were not associated with these alterations. IL-6 mirrored the time course of GLP-2. Assessing the main degradation protein dipeptidyl peptidase 4 (DPP4) no significant association with either GLP-1 or -2 could be found. Additionally, in PHLF distinct postoperative declines in plasma lipid parameters were present and correlated with GLP-2 dynamics. Our data suggest dynamic inverse regulation of GLP-1 and GLP-2 during liver regeneration, rather caused by an increase in expression/release than by changes in degradation capacity and might be associated with inflammatory responses. Their close association with circulating markers of lipid metabolism and insufficient hepatic regeneration after liver surgery suggest a critical involvement during these processes in humans.