KLi2RE(BO3)2 (RE = Dy, Ho, Er, Tm, Yb, and Y): Structural, Spectroscopic, And Thermogravimetric Studies on a Series of Mixed-Alkali Rare-Earth Orthoborates.

We report a detailed structural, spectroscopic, and thermogravimetric investigation of a new series of mixed-alkali rare-earth orthoborates KLi2RE(BO3)2 (RE = Dy, Ho, Er, Tm, Yb, and Y). Single crystals were directly prepared by a flux method as well as mechanically separated from the polycrystalline powder obtained from the conventional solid-state reactions. All KLi2RE(BO3)2 members are isotypic and crystallize in the space group P21/n. The novel structure type is comprised of [RE2(BO3)4O4]14- anionic clusters where the edge-sharing REO7 pentagonal bipyramids are connected by BO3 groups and both K+ and Li+ cations are located at the interstitial voids of the 3D network. The metric parameters and crystal structural features obtained from the single-crystal data are in excellent agreement with those refined from the powder data. The change of the lattice parameters and unit cell volumes can be explained in terms of the lanthanide contraction effect. A comparison between KLi2RE(BO3)2 and other rare-earth borates with similar chemical compositions indicates that the sum of the ionic radii of the alkali-metal cations governs the symmetry of the crystals. Diffuse reflectance UV-vis spectra display the characteristic absorption behaviors of the RE3+ cations and the fundamental absorption edge. Both the Tauc's and derivation of absorption spectrum fitting (DASF) methods were used to identify the magnitude and type of bandgap, respectively, which are compared with those obtained from density functional theory (DFT) calculations. The calculated phonon density of states and the vibrational frequency at the gamma point help explain the Fourier transform infrared and Raman spectra of KLi2RE(BO3)2. The incongruent melting behavior and the thermal stability of each member of the KLi2RE(BO3)2 series were also studied by thermogravimetric analyses.

An astronomically dated record of Earth's climate and its predictability over the last 66 million years.

Much of our understanding of Earth's past climate comes from the measurement of oxygen and carbon isotope variations in deep-sea benthic foraminifera. Yet, long intervals in existing records lack the temporal resolution and age control needed to thoroughly categorize climate states of the Cenozoic era and to study their dynamics. Here, we present a new, highly resolved, astronomically dated, continuous composite of benthic foraminifer isotope records developed in our laboratories. Four climate states-Hothouse, Warmhouse, Coolhouse, Icehouse-are identified on the basis of their distinctive response to astronomical forcing depending on greenhouse gas concentrations and polar ice sheet volume. Statistical analysis of the nonlinear behavior encoded in our record reveals the key role that polar ice volume plays in the predictability of Cenozoic climate dynamics.

Temperate rainforests near the South Pole during peak Cretaceous warmth.

The mid-Cretaceous period was one of the warmest intervals of the past 140 million years1-5, driven by atmospheric carbon dioxide levels of around 1,000 parts per million by volume6. In the near absence of proximal geological records from south of the Antarctic Circle, it is disputed whether polar ice could exist under such environmental conditions. Here we use a sedimentary sequence recovered from the West Antarctic shelf-the southernmost Cretaceous record reported so far-and show that a temperate lowland rainforest environment existed at a palaeolatitude of about 82° S during the Turonian-Santonian age (92 to 83 million years ago). This record contains an intact 3-metre-long network of in situ fossil roots embedded in a mudstone matrix containing diverse pollen and spores. A climate model simulation shows that the reconstructed temperate climate at this high latitude requires a combination of both atmospheric carbon dioxide concentrations of 1,120-1,680 parts per million by volume and a vegetated land surface without major Antarctic glaciation, highlighting the important cooling effect exerted by ice albedo under high levels of atmospheric carbon dioxide.

Limited grounding-line advance onto the West Antarctic continental shelf in the easternmost Amundsen Sea Embayment during the last glacial period.

Precise knowledge about the extent of the West Antarctic Ice Sheet (WAIS) at the Last Glacial Maximum (LGM; c. 26.5-19 cal. ka BP) is important in order to 1) improve paleo-ice sheet reconstructions, 2) provide a robust empirical framework for calibrating paleo-ice sheet models, and 3) locate potential shelf refugia for Antarctic benthos during the last glacial period. However, reliable reconstructions are still lacking for many WAIS sectors, particularly for key areas on the outer continental shelf, where the LGM-ice sheet is assumed to have terminated. In many areas of the outer continental shelf around Antarctica, direct geological data for the presence or absence of grounded ice during the LGM is lacking because of post-LGM iceberg scouring. This also applies to most of the outer continental shelf in the Amundsen Sea. Here we present detailed marine geophysical and new geological data documenting a sequence of glaciomarine sediments up to ~12 m thick within the deep outer portion of Abbot Trough, a palaeo-ice stream trough on the outer shelf of the Amundsen Sea Embayment. The upper 2-3 meters of this sediment drape contain calcareous foraminifera of Holocene and (pre-)LGM age and, in combination with palaeomagnetic age constraints, indicate that continuous glaciomarine deposition persisted here since well before the LGM, possibly even since the last interglacial period. Our data therefore indicate that the LGM grounding line, whose exact location was previously uncertain, did not reach the shelf edge everywhere in the Amundsen Sea. The LGM grounding line position coincides with the crest of a distinct grounding-zone wedge ~100 km inland from the continental shelf edge. Thus, an area of ≥6000 km2 remained free of grounded ice through the last glacial cycle, requiring the LGM grounding line position to be re-located in this sector, and suggesting a new site at which Antarctic shelf benthos may have survived the last glacial period.

Evidence for a palaeo-subglacial lake on the Antarctic continental shelf.

Subglacial lakes are widespread beneath the Antarctic Ice Sheet but their control on ice-sheet dynamics and their ability to harbour life remain poorly characterized. Here we present evidence for a palaeo-subglacial lake on the Antarctic continental shelf. A distinct sediment facies recovered from a bedrock basin in Pine Island Bay indicates deposition within a low-energy lake environment. Diffusive-advection modelling demonstrates that low chloride concentrations in the pore water of the corresponding sediments can only be explained by initial deposition of this facies in a freshwater setting. These observations indicate that an active subglacial meltwater network, similar to that observed beneath the extant ice sheet, was also active during the last glacial period. It also provides a new framework for refining the exploration of these unique environments.