New insights on electrochemical hydrogen storage in nanoporous carbons by in situ Raman spectroscopy

In situ Raman spectroscopy was exploited to analyze the interaction between carbon and hydrogen during electrochemical hydrogen storage at cathodic conditions. Two different activated carbons were used and characterized by different electrochemical techniques in two electrolytes (6 M KOH and 0.5 M Na2SO4). The in situ Raman spectra collected showed that, in addition to the D and G bands associated to the graphitic carbons, two bands appear simultaneously at about 1110 and 1500 cm−1 under cathodic conditions, and then they disappear when the potential increases to more positive values. This indicates that carbon–hydrogen bonds are formed reversibly in both electrolytes during cathodic conditions. Comparing the two activated carbons, it was confirmed that, in both electrolytes, the hydrogenation of carbon atoms is produced more easily for the sample with lower amount of surface oxygen groups. In KOH medium, for the two samples, the formation of carbon–hydrogen bonds proceeds at more positive potential with respect to the thermodynamic potential value for hydrogen evolution. Furthermore, changes in the shape of the D band (due to an intensity increase of the D1 band) during the formation of carbon–hydrogen bonds suggest that hydrogenation of the carbon atoms increases the number of edge planes.

Exploring several nonconventional interactions of ice-binding proteins

Traditionally, ice-binding proteins (IBPs), also known as antifreeze proteins (AFPs), have been defined by two universal activities: ice recrystallization inhibition and thermal hysteresis. However, there remains the possibility IBPs have other complementary functions given the diversity found within this protein group. This thesis explores some of these in both natural and applied settings, in the hopes of furthering our understanding of this remarkable group of proteins. Plant IBPs could function as part of a defensive strategy against ice nucleators produced by certain pathogens. To assess this hypothesis, recombinant IBPs from perennial ryegrass and purple false brome were combined with the ice nucleation protein (INP) from the plant pathogen, Pseudomonas syringae. Strikingly, the plant proteins depressed the freezing point of the bacterial INP, while a fish AFP could not, nor did the INPs have any effect on IBP activity. Thus, the interaction between these two different proteins suggests a role in plant defensive strategies against pathogenic bacteria as another IBP function. In addition, the potential use of hyperactive insect IBPs in organ preservation was investigated. Current kidney preservation techniques involve storing the organ at 4 °C for a maximum of 24 h prior to transplantation. Extending this “safe” time would have profound effects on renal transplants, however, ischemic injury is prevalent when storage periods are prolonged. Experiments described here allowed subzero preservation for 72 h with the addition of a beetle IBP to CryoStasis® solution. Kidneys stored using the traditional technique for 24 h and the method developed here for 72 h showed similar levels of biomarker enzymes, underscoring the potential utility of insect IBPs for future transplant purposes. Finally, IBP function in the freeze-tolerant gall fly, Eurosta solidaginis, was examined. Larvae representing the mid-autumn stage displayed ice-binding activity, suggesting an IBP is being expressed, possibly as a protective measure against freezing damage when fall temperatures can unpredictably drop. IBP activity was also observed in the larvae’s host plant, Solidago spp. Mass spectrometry analysis of ice-affinity purified plant extracts provided three candidate pathogenesis-related proteins that could be responsible for the detected activity, further demonstrating additional functions of IBPs.

Comment on “Low time resolution analysis of polar ice cores cannot detect impulsive nitrate events” by D.F. Smart et al.

Smart et al. (2014) suggested that the detection of nitrate spikes in polar ice cores from solar energetic particle (SEP) events could be achieved if an analytical system with sufficiently high resolution was used. Here we show that the spikes they associate with SEP events are not reliably recorded in cores from the same location, even when the resolution is clearly adequate. We explain the processes that limit the effective resolution of ice cores. Liquid conductivity data suggest that the observed spikes are associated with sodium or another nonacidic cation, making it likely that they result from deposition of sea salt or similar aerosol that has scavenged nitrate, rather than from a primary input of nitrate in the troposphere. We consider that there is no evidence at present to support the identification of any spikes in nitrate as representing SEP events. Although such events undoubtedly create nitrate in the atmosphere, we see no plausible route to using nitrate spikes to document the statistics of such events.

Spatial distribution patterns of ascidians (Ascidiacea: Tunicata) in combination with information on bathymetry, oceanography, chlorophyll-a, and sea-ice on the continental shelves off the northern Antarctic Peninsula during POLARSTERN cruise ANT-XXIX/3

Ascidians (Ascidiacea: Tunicata) are sessile suspension feeders that represent dominant epifaunal components of the Southern Ocean shelf benthos and play a significant role in the pelagic-benthic coupling. Here, we report the results of a first study on the relationship between the distribution patterns of eight common and/or abundant (putative) ascidian species, and environmental drivers in the waters off the northern Antarctic Peninsula. During RV Polarstern cruise XXIX/3 (PS81) in January-March 2013, we used seabed imaging surveys along 28 photographic transects of 2 km length each at water depths from 70 to 770 m in three regions (northwestern Weddell Sea, southern Bransfield Strait and southern Drake Passage), differing in their general environmental setting, primarily oceanographic characteristics and sea-ice dynamics, to comparatively analyze the spatial patterns in the abundance of the selected ascidians, reliably to be identified in the photographs, at three nested spatial scales. At a regional (100-km) scale, the ascidian assemblages of the Weddell Sea differed significantly from those of the other two regions, whereas at an intermediate 10-km scale no such differences were detected among habitat types (bank, upper slope, slope, deep/canyon) on the shelf and at the shelf break within each region. These spatial patterns were superimposed by a marked small-scale (10-m) patchiness of ascidian distribution within the 2-km-long transects. Among the environmental variables considered in our study, a combination of water-mass characteristics, sea-ice dynamics (approximated by 5-year averages in sea-ice cover in the region of or surrounding the photographic stations), as well as the seabed ruggedness, was identified as explaining best the distribution patterns of the ascidians.