Shikimic acid ozonolysis kinetics of the transition from liquid aqueous solution to highly viscous glass.

Ageing of particulate organic matter affects the composition and properties of atmospheric aerosol particles. Driven by temperature and humidity, the organic fraction can vary its physical state between liquid and amorphous solid, or rarely even crystalline. These transitions can influence the reaction kinetics due to limitations of mass transport in such (semi-) solid states, which in turn may influence the chemical ageing of particles containing such compounds. We have used coated wall flow tube experiments to investigate the reaction kinetics of the ozonolysis of shikimic acid, which serves as a proxy for oxygenated, water-soluble organic matter and can form a glass at room temperature. Particular attention was paid to how the presence of water influences the reaction, since it acts a plasticiser and thereby induces changes in the physical state. We analysed the results by means of a traditional resistor model, which assumes steady-state conditions. The ozonolysis rate of shikimic acid is strongly increased in the presence of water, a fact we attribute to the increased transport of O3 and shikimic acid through the condensed phase at lower viscosities. The analysis using the resistor model suggests that the system undergoes both surface and bulk reaction. The second-order rate coefficient of the bulk reaction is 3.7 (+1.5/-3.2) × 10(3) L mol(-1) s(-1). At low humidity and long timescales, the resistor model fails to describe the measurements appropriately. The persistent O3 uptake at very low humidity suggests contribution of a self-reaction of O3 on the surface.

What evidence exists relating the impact of different grassland management practices to soil carbon in livestock systems? A systematic map protocol.

Background: Grasslands are essential for providing vital resources in the livestock sector and delivering invaluable ecosystem services such as biodiversity and soil carbon (C) sequestration. Despite their critical importance, these ecosystems face escalating threats from human disturbances, human degradation, and climate change, compromising their ability to effectively stock C. Restoring degraded grasslands emerges as a pragmatic and cost-effective approach to tackling climate change. However, the successful implementation of grassland management toward this goal, faces significant challenges. A systematic mapping approach will help to compile a comprehensive global inventory of studies investigating the impact of differing grassland management practices on soil carbon. In addition, the potential for trade-offs with other greenhouse gas emissions further underlines the value of a systematic assessment. This approach aims to identify knowledge clusters (i.e., well-represented subtopics that are amenable to full synthesis) for potential systematic reviews and pinpoint knowledge gaps requiring further primary research efforts, all contributing to a better understanding of the evidence surrounding this topic. Methods: Following systematic evidence synthesis standards, we developed the question to address in the systematic map protocol using the PICO framework. We established a preliminary search string by combining search terms for the Population (Grasslands), Intervention (management) and Outcome (soil carbon) categories, as well as with one additional group (Study types-to focus on farm and field experiments). We will conduct a comprehensive literature search of relevant peer-reviewed and grey literature using Web of Science, Scopus, CABI platforms, Google Scholar, and specialised websites (e.g., Agrotrop). Searches will be conducted in the English, Spanish, Portuguese, French, German, and Mongolian languages, as per the linguistic capabilities of the research team. The comprehensiveness of the search will be assessed by comparing the literature collected to a test-list of forty relevant articles. The repeatability of the literature screening process will be ensured by a list of inclusion/exclusion criteria and inter-reviewer consistency statistical tests. Data extraction will be organised into four complementary sections (article information, PICO categories, study characteristics, measurable parameters), on which we will perform queries to produce the tables, figures and evidence maps that will compose the systematic map. The results will identify and describe knowledge gaps and clusters. Supplementary Information: The online version contains supplementary material available at 10.1186/s13750-024-00345-2.

A surface-stabilized ozonide triggers bromide oxidation at the aqueous solution-vapour interface.

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.