In this research, the oxidation of a series of benzoins, R-C(=O)-CH(OH)-R, where R = phenyl, 4-methoxyphenyl, 4-bromophenyl, and 2-naphthyl, by hydrogen peroxide in the presence of nanostructured ...HKUST-1 (suspension in acetonitrile/water mixture) was studied. The respective benzoic acids were the only products of the reactions. The initial average reaction rates were experimentally determined at different concentrations of benzoin, H
O
and an effective concentration of HKUST-1. The sorption of the isotherms of benzoin, dimethoxybenzoin and benzoic acid on HKUST-1, as well as their sorption kinetic curves, were measured. The increase in H
O
concentration expectedly led to an acceleration of the reaction. The dependencies of the benzoin oxidation rates on the concentrations of both benzoin and HKUST-1 passed through the maxima. This finding could be explained by a counterplay between the increasing reaction rate and increasing benzoin sorption on the catalyst with the increase in the concentration. The electronic effect of the substituent in benzoin had a significant influence on the reaction rate, while no relation between the size of the substrate molecule and the rate of its oxidation was found. It was confirmed by DFT modeling that the reaction could pass through the Baeyer-Villiger mechanism, involving an attack by the HOO
anion on the C atom of the activated C=O group.
Simulation of vegetation–climate feedbacks in high latitudes in the ORCHIDEE land surface model was improved by the addition of three new circumpolar plant functional types (PFTs), namely ...non-vascular plants representing bryophytes and lichens, Arctic shrubs and Arctic C3 grasses. Non-vascular plants are assigned no stomatal conductance, very shallow roots, and can desiccate during dry episodes and become active again during wet periods, which gives them a larger phenological plasticity (i.e. adaptability and resilience to severe climatic constraints) compared to grasses and shrubs. Shrubs have a specific carbon allocation scheme, and differ from trees by their larger survival rates in winter, due to protection by snow. Arctic C3 grasses have the same equations as in the original ORCHIDEE version, but different parameter values, optimised from in situ observations of biomass and net primary productivity (NPP) in Siberia. In situ observations of living biomass and productivity from Siberia were used to calibrate the parameters of the new PFTs using a Bayesian optimisation procedure. With the new PFTs, we obtain a lower NPP by 31 % (from 55° N), as well as a lower roughness length (−41 %), transpiration (−33 %) and a higher winter albedo (by +3.6 %) due to increased snow cover. A simulation of the water balance and runoff and drainage in the high northern latitudes using the new PFTs results in an increase of fresh water discharge in the Arctic ocean by 11 % (+140 km3 yr−1), owing to less evapotranspiration. Future developments should focus on the competition between these three PFTs and boreal tree PFTs, in order to simulate their area changes in response to climate change, and the effect of carbon–nitrogen interactions.
Biological diversity is the basis for, and an indicator of biosphere integrity. Together with climate change, its loss is one of the two most important planetary boundaries. A halt in biodiversity ...loss is one of the UN Sustainable Development Goals. Current changes in biodiversity in the vast landmass of Siberia are at an initial stage of inventory, even though the Siberian environment is experiencing rapid climate change, weather extremes and transformation of land use and management. Biodiversity changes affect traditional land use by Indigenous People and multiple ecosystem services with implications for local and national economies. Here we review and analyse a large number of scientific publications, which are little known outside Russia, and we provide insights into Siberian biodiversity issues for the wider international research community. Case studies are presented on biodiversity changes for insect pests, fish, amphibians and reptiles, birds, mammals and steppe vegetation, and we discuss their causes and consequences.
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