Oxygen Reduction Reaction on Pt Overlayers Deposited onto a Gold Film: Ligand, Strain, and Ensemble Effect

We study the oxygen reduction reaction (ORR), the catalytic process occurring at the cathode in fuel cells, on Pt layers prepared by electrodeposition onto an Au substrate. Using a nominal Pt layer by layer deposition method previously proposed, imperfect layers of Pt on Au are obtained. The ORR on deposited Pt layers decreases with increasing Pt thickness. In the submonolayer region, however, the ORR activity is superior to that of bulk Pt. Using density functional theory (DFT) calculations, we correlate the observed activity trend to strain, ligand, and ensemble effects. At submonolayer coverage certain atom configurations weaken the binding energies of reaction intermediates due to a ligand and ensemble effect, thus effectively increasing the ORR activity. At higher Pt coverage the activity is governed by a strain effect, which lowers the activity by decreasing the oxidation potential of water. This study is a nice example of how the influence of strain, ligand, and ensemble effects on the ORR can be deconvoluted.

Ocean acidification alters the material properties of Mytilus edulis shells

Ocean acidification (OA) and the resultant changing carbonate saturation states is threatening the formation of calcium carbonate shells and exoskeletons of marine organisms. The production of biominerals in such organisms relies on the availability of carbonate and the ability of the organism to biomineralize in changing environments. To understand how biomineralizers will respond to OA the common blue mussel, Mytilus edulis, was cultured at projected levels of pCO2 (380, 550, 750, 1000 µatm) and increased temperatures (ambient, ambient plus 2°C). Nanoindentation (a single mussel shell) and microhardness testing were used to assess the material properties of the shells. Young's modulus (E), hardness (H) and toughness (KIC) were measured in mussel shells grown in multiple stressor conditions. OA caused mussels to produce shell calcite that is stiffer (higher modulus of elasticity) and harder than shells grown in control conditions. The outer shell (calcite) is more brittle in OA conditions while the inner shell (aragonite) is softer and less stiff in shells grown under OA conditions. Combining increasing ocean pCO2 and temperatures as projected for future global ocean appears to reduce the impact of increasing pCO2 on the material properties of the mussel shell. OA may cause changes in shell material properties that could prove problematic under predation scenarios for the mussels; however, this may be partially mitigated by increasing temperature.

Analysis of spatial microbial properties from experimental plots of the Jena experiment (September 2010)

The study was carried out on the main plots (Main Experiment) of a large grassland biodiversity experiment, the Jena Experiment. In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. This data set consists of standard deviation (SD), mean and stability (stab) of soil microbial basal respiration (µl O2/h/g dry soil) and microbial biomass carbon (µg C/g dry soil). Data were derived by taking soil samples and measuring basal and substrate-induced microbial respiration with an oxygen-consumption apparatus. Samples for calculating the spatial stability of soil microbial properties were taken on the 20th of September in 2010. Oxygen consumption of soil microorganisms in fresh soil equivalent to 3.5 g dry weight was measured at 22°C over a period of 24 h. Basal respiration (µlO2/g dry soil/h) was calculated as mean of the oxygen consumption rates of hours 14 to 24 after the start of measurements. Substrate- induced respiration was determined by adding D-glucose to saturate catabolic enzymes of microorganisms according to preliminary studies (4 mg g-1 dry soil solved in 400 µl deionized water). Maximum initial respiratory response (µl O2/g dry soil/ h) was calculated as mean of the lowest three oxygen consumption values within the first 10 h after glucose addition. Microbial biomass carbon (µg C/g dry soil) was calculated as 38 × Maximum initial respiratory response according to prelimiray studies.

Analysis of temporal microbial properties from experimental plots of the Jena experiment (2003-2014)

The study was carried out on the main plots (Main Experiment) of a large grassland biodiversity experiment, the Jena Experiment. In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. This data set consists of standard deviation (SD), mean and stability (stab) of soil microbial basal respiration (µl O2/h/g dry soil) and microbial biomass carbon (µg C/g dry soil). Data were derived by taking soil samples and measuring basal and substrate-induced microbial respiration with an oxygen-consumption apparatus. Samples for calculating the temporal stability were taken every year in May/June from 2003 to 2014, except in 2005. Oxygen consumption of soil microorganisms in fresh soil equivalent to 3.5 g dry weight was measured at 22°C over a period of 24 h. Basal respiration (µlO2/g dry soil/h) was calculated as mean of the oxygen consumption rates of hours 14 to 24 after the start of measurements. Substrate- induced respiration was determined by adding D-glucose to saturate catabolic enzymes of microorganisms according to preliminary studies (4 mg g-1 dry soil solved in 400 µl deionized water). Maximum initial respiratory response (µl O2/g dry soil/h) was calculated as mean of the lowest three oxygen consumption values within the first 10 h after glucose addition. Microbial biomass carbon (µg C/g dry soil) was calculated as 38 × Maximum initial respiratory response according to prelimiray studies.

Table 1: Soil chemical properties of the analysed depth profiles in the Venice lagoon

Visual traces of iron reduction and oxidation are linked to the redox status of soils and have been used to characterise the quality of agricultural soils.We tested whether this feature could also be used to explain the spatial pattern of the natural vegetation of tidal habitats. If so, an easy assessment of the effect of rising sea level on tidal ecosystems would be possible. Our study was conducted at the salt marshes of the northern lagoon of Venice, which are strongly threatened by erosion and rising sea level and are part of the world heritage 'Venice and its lagoon'. We analysed the abundance of plant species at 255 sampling points along a land-sea gradient. In addition, we surveyed the redox morphology (presence/absence of red iron oxide mottles in the greyish topsoil horizons) of the soils and the presence of disturbances. We used indicator species analysis, correlation trees and multivariate regression trees to analyse relations between soil properties and plant species distribution. Plant species with known sensitivity to anaerobic conditions (e.g. Halimione portulacoides) were identified as indicators for oxic soils (showing iron oxide mottles within a greyish soil matrix). Plant species that tolerate a low redox potential (e.g. Spartina maritima) were identified as indicators for anoxic soils (greyish matrix without oxide mottles). Correlation trees and multivariate regression trees indicate the dominant role of the redox morphology of the soils in plant species distribution. In addition, the distance from the mainland and the presence of disturbances were identified as tree-splitting variables. The small-scale variation of oxygen availability plays a key role for the biodiversity of salt marsh ecosystems. Our results suggest that the redox morphology of salt marsh soils indicates the plant availability of oxygen. Thus, the consideration of this indicator may enable an understanding of the heterogeneity of biological processes in oxygen-limited systems and may be a sensitive and easy-to-use tool to assess human impacts on salt marsh ecosystems.