ALBERT

Description: The paper describes the architecture for a data repository and distribution system to be used in the case of a SETI detection event. This system is conceptually modelled after the Deep Space Network, although the hardware and infrastructure involved are different and substantially less expensive to operate. The system is designed to accommodate a large number of users from a variety of fields who wish to contribute to the analysis and comprehension effort that would follow the detection of an information-bearing signal.

Description: Under the potential to reconstruct the past climatic and atmospheric conditions from a deep ice core in the coastal Antarctic site (Styx Glacier), an 8.84 m long firn core (73°50.975′ S, 163°41.640′ E; 1623 m a.s.l.) was initially studied to propose a reliable age scale for the local estimation of snow accumulation rate. The seasonal variations of δ18O, methanesulfonic acid (MSA) and non-sea-salt sulfate (nssSO42–) were used for the firn core dating and revealed 25 annual peaks (from 1990 to 2014) with volcanic sulfate signal. The observed declining trend in annual accumulation rate with a mean value of 146 ± 60 kg m–2 a–1 is likely to be linked to the changes of sea-ice extent in the Ross Sea region. Moreover, the temporal variation of the annual mean δ18O, an annual flux of MSA and nssSO42– also likely to be under the influence of ice-covered and open water area. This study suggests a potential to recover past changes in an oceanic environment and will be useful for the interpretation of the long ice core drilled at the same site.

Description: Clouds play an important role in the Arctic surface radiative budget, impacting the seasonal evolution of Arctic sea-ice cover. We explore the large-scale impacts of springtime and early summer (March through July) cloud and radiative fluxes on sea ice by comparing these fluxes to seasonal ice volume losses over the central Arctic basin, calculated for available observational years 2004–2007 (ICESat) and 2011–2017 (CryoSat-2). We also supplement observation data with sea-ice volume computed from the Pan-Arctic Ice–Ocean Modeling and Assimilation System (PIOMAS) during summer months. We find that the volume of sea ice lost over the melt season is most closely related to observed downwelling longwave radiation in March and early summer (June and July) longwave cloud radiative forcing, which together explain a large fraction of interannual variability in seasonal sea-ice volume loss (R2 = 0.71, p = 0.007). We show that downwelling longwave fluxes likely impact the timing of melt onset near the sea-ice edge, and can limit the magnitude of ice thickening from March to April. Radiative fluxes in June and July are likely critical to seasonal volume loss because modeled data show the greatest ice volume reductions occur during these months.

Description: The terpenoid (−)-Istanbulin A is a natural product isolated from Senecio filaginoides DC, one of the 270 species of Senecio (Asteraceae) which occurs in Argentina. The structure and absolute configuration of this compound [9a-hydroxy-3,4a,5-trimethyl-4a,6,7,8a,9,9a-hexahydro-4H,5H-naphtho[2,3-b]-furan-2,8-dione or (4S,5R,8R,10S)-1-oxo-8β-hydroxy-10βH-eremophil-7(11)-en-12,8β-olide, C15H20O4] were determined by single-crystal X-ray diffraction studies. It proved to be a sesquiterpene lactone showing an eremophilanolide skeleton whose chirality is described as 4S,5R,8R,10S. Structural results were also in agreement with the one- and two-dimensional (1D and 2D) NMR and HR–ESI–MS data, and other complementary spectroscopic information. In addition, (−)-Istanbulin A is a polymorph of the previously reported form of (−)-Istanbulin A, form I; thus, the title compound is denoted form II or polymorph II. Structural data and a literature search allowed the chirality of Istanbulin A to be revisited. The antimicrobial and antifungal activities of (−)-Istanbulin A, form II, were evaluated in order to establish a reference for future comparisons and applications related to specific crystal forms of Istanbulins.

Description: Two conformational polymorphs of (N,N-dibutyldithiocarbamato-κ2 S,S′)[tris(3,5-diphenylpyrazol-1-yl-κN 2)hydroborato]cobalt(II), [Co(C45H34BN6)(C9H18NS2)] or [TpPh2Co(S2CNBu2)], 1, are accessible by recrystallization from dichloromethane–methanol to give orthorhombic polymorph 1a, while slow evaporation from acetonitrile produces triclinic polymorph 1b. The two polymorphs have been characterized by IR spectroscopy and single-crystal X-ray crystallography at 150 K. Polymorphs 1a and 1b crystallize in the orthorhombic space group Pbca and the triclinic space group P-1, respectively. The polymorphs have a trans (1a) and cis (1b) orientation of the butyl groups with respect to the S2CN plane of the dithiocarbamate ligand, which results in an intermediate five-coordinate geometry for 1a and a square-pyramidal geometry for 1b. Hirshfeld surface analysis reveals minor differences between the two polymorphs, with 1a exhibiting stronger C—H...S interactions and 1b favouring C—H...π interactions.

Description: A supramolecular complex, formed by encapsulation of C60 fullerene in a molecular container built from two resorcin[4]arene rims zipped together by peptidic arms hydrogen bonded into a cylindrical β-sheet, was studied by X-ray crystallography, solid-state and solution NMR, EPR spectroscopy and differential scanning calorimetry (DSC). The crystal structure, determined at 100 K, reveals that the complex occupies 422 site symmetry, which is compatible with the molecular symmetry of the container but not of the fullerene molecule, which has only 222 symmetry. The additional crystallographic symmetry leads to a complicated but discrete disorder, which could be resolved and modelled using advanced features of the existing refinement software. Solid-state NMR measurements at 184–333 K indicate that the thermal motion of C60 in this temperature range is fast but has different activation energies at different temperatures, which was attributed to a phase transition, which was confirmed by DSC. Intriguingly, the activation energy for reorientations of C60 in the solid state is very similar for the free and encaged molecules. Also, the rotational diffusion coefficients seem to be very similar or even slightly higher for the encaged fullerene compared to the free molecule. We also found that chemical shift anisotropy (CSA) is not the main relaxation mechanism for the 13C spins of C60 in the studied complex.

Description: A series of related acetylacetonate–carbonyl–rhodium compounds substituted by functionalized phosphines has been prepared in good to excellent yields by the reaction of [Rh(acac)(CO)2] (acac is acetylacetonate) with the corresponding allyl-, cyanomethyl- or cyanoethyl-substituted phosphines. All compounds were fully characterized by 31P, 1H, 13C NMR and IR spectroscopy. The X-ray structures of (acetylacetonato-κ2 O,O′)(tert-butylphosphanedicarbonitrile-κP)carbonylrhodium(I), [Rh(C5H7O2)(CO)(C8H13N2)] or [Rh(acac)(CO)(tBuP(CH2CN)2}] (2b), (acetylacetonato-κ2 O,O′)carbonyl[3-(diphenylphosphanyl)propanenitrile-κP]rhodium(I), [Rh(C5H7O2)(C15H14N)(CO)] or [Rh(acac)(CO){Ph2P(CH2CH2CN)}] (2h), and (acetylacetonato-κ2 O,O′)carbonyl[3-(di-tert-butylphosphanyl)propanenitrile-κP]rhodium(I), [Rh(C5H7O2)(C11H22N)(CO)] or [Rh(acac)(CO){tBu2P(CH2CH2CN)}] (2i), showed a square-planar geometry around the Rh atom with a significant trans influence over the acetylacetonate moiety, evidenced by long Rh—O bond lengths as expected for poor π-acceptor phosphines. The Rh—P distances displayed an inverse linear dependence with the coupling constants J P-Rh and the IR ν(C[triple-bond]O) bands, which accounts for the Rh—P electronic bonding feature (poor π-acceptors) of these complexes. A combined study from density functional theory (DFT) calculations and an evaluation of the intramolecular H...Rh contacts from X-ray diffraction data allowed a comparison of the conformational preferences of these complexes in the solid state versus the isolated compounds in the gas phase. For 2b, 2h and 2i, an energy-framework study evidenced that the crystal structures are mainly governed by dispersive energy. In fact, strong pairwise molecular dispersive interactions are responsible for the columnar arrangement observed in these complexes. A Hirshfeld surface analysis employing three-dimensional molecular surface contours and two-dimensional fingerprint plots indicated that the structures are stabilized by H...H, C...H, H...O, H...N and H...Rh intermolecular interactions.

Description: Seilacherian Ichnofacies have been established, to date, for characterizing relatively stable depositional settings. Environments characterized by temporally and spatially varying physico-chemical stresses, however, have languished and been described ichnologically in the context of their “departures” from the archetypal expressions of otherwise ambient environments. Correspondingly, discrimination between shoreface and marine deltaic deposits have been addressed mainly by identifying variations in the individual trace-fossil suites without an over-arching ichnological model. Based on trace-fossil suites reported from globally distributed strata throughout the Phanerozoic, the case can now be made for erecting two new temporally and geographically recurring Seilacherian Ichnofacies for marine deltaic successions—the Phycosiphon Ichnofacies for muddy prodelta environments and the Rosselia Ichnofacies for sandy delta-front settings. The Phycosiphon Ichnofacies is characterized by variable bioturbation intensities (BI 0–5), although many sandstone and mudstone beds may have very low bioturbation intensities (BI 0–1), pointing to their rapid, event-style deposition. Most biogenic structures record grazing or deposit-feeding behaviors, with subordinate horizontal dwellings that reflect deposit feeding and/or carnivory. Meiofaunal cryptic bioturbation is locally present in tempestites. Episodic deposition is accompanied by common escape structures and locally, sediment-swimming structures. The Phycosiphon Ichnofacies typically shows beds characterized by diverse, fully marine trace-fossil suites intercalated with discrete beds dominated by low-diversity, facies-crossing traces. Such bed-scale juxtaposition points to short-term but recurring alternations between stable marine conditions and physico-chemically stressed conditions. The Rosselia Ichnofacies is also characterized by variable (BI 0–5; though typically BI 0–3) bioturbation intensities and sporadically distributed burrows. Most ichnogenera record deposit-feeding behaviors, many associated with vertically and horizontally oriented permanent dwelling structures. Dwelling structures commonly display re-equilibration and escape structures are typically abundant, both characteristic of elevated sedimentation rates and sporadic deposition. Most spreitenated structures are markedly retrusive, also attesting to elevated rates of sedimentation. Cryptic bioturbation is only locally abundant, particularly associated with erosionally amalgamated tempestites lacking mudstone drapes. While many of the trace fossils constitute facies-crossing elements, fully marine (ambient) ichnogenera also occur in some suites. Associated mudstone interbeds display low BI values, sediment-swimming structures, and top-down bioturbation, consistent with their rapid deposition as fluid mud. The two ichnofacies may pass gradationally into one another vertically, associated with lobe progradation or autogenic lobe abandonment. Further, the two ichnofacies may pass along depositional strike into their non-deltaic counterparts—the Phycosiphon Ichnofacies grading into the Cruziana Ichnofacies in distal positions, and the Rosselia Ichnofacies passing into the Skolithos Ichnofacies in shallow-water locales. The erection of these new ichnofacies will enhance the reliable identification of deltaic successions, particularly in wave-dominated settings, and their differentiation from classical strandplain shoreface deposits. As well, the two ichnofacies better explain animal–substrate relations in the context of the detailed sedimentological characteristics of delta deposits, refining the overall facies characterization of shallow-marine environments.

Description: Microbioerosion structures are a common sign of microbial activity known mainly from marine environments and calcareous substrates, or from pollen records. However, the same phenomenon has been overlooked in animal fossils preserved in lake sediments. We studied 430 fragments of chitinous microfossils from three central European glacial lakes and detected microboring structures in approximately 10%. The microfossils belong to two size groups: (1) spherical objects with lengths ranging from 50 to 300 μm that are probably microturbelarian (Turbellaria: Rhabdocoela) cocoons, and (2) larger remnants (up to 2 mm long) of caddisfly (Insecta: Trichoptera) frontoclypeal apotomes. Four microbioerosion morphotypes were distinguished: (1) small holes (〈 0.6 μm) oriented perpendicular to microfossil walls, likely produced by bacteria or fungi; (2) simple meandering tunnels and; (3) asterisk-like tunnel structures produced by fungi and/or fungus-like organisms; and (4) abrasions caused by biofilms. The maximum diameter of the simple holes and both tunnel structures depended on host-microfossil size: a higher diversity of microbioerosions was found on larger chitinous fragments. We propose that the good preservation of microfossils in the studied sediment samples might be due to rapid transport to the anoxic profundal zone or by rapid burial in anoxic sediments.

Description: Stromatolites are domes, columns, or nearly flat crusts of laminated sedimentary rocks, usually consisting of Ca-Mg carbonates. Stromatolites result from lithification of microbial mats, which are benthic microbial ecosystems where microorganisms arrange themselves in layers according to their physiology. Despite a century of research, the hypothesis of stromatolite genesis by lithification of microbial mats remains controversial, and a convincing explanation for how stromatolites arise from microbial mats is still lacking. In this work, we analyze in detail a stromatolite from Lagoa Vermelha, a coastal hypersaline lagoon in Rio de Janeiro State, Brazil. The stromatolite presents a laminated core and thrombolitic regions at the periphery. Both thrombolitic and laminated facies consist of fine-grained authigenic minerals with minor contributions of bioclasts and quartz grains. X-ray diffraction shows aragonite, high-magnesium calcite (HMC) containing about 17% MgCO3, a very-high-Mg calcite (VHMC) containing 29–46% MgCO3, and small amounts of quartz and pyrite. Scanning electron microscopy of polished samples coupled to energy-dispersive X-ray analysis (EDS) showed that each lamina was composed of 1–4 distinct mineral phases embedded within each other, indicating sequential steps of precipitation of Ca-Mg carbonates under distinct biogeochemical conditions. The coexistence of different phases in a single lamina suggests that several processes contribute to mineral deposition as the incipient stromatolite laminae are left behind by microorganisms from the lower layers of the microbial mat when they grow and/or move upwards.