That water can exist in two distinct ‘glassy’ forms — low- and high-density amorphous ice — may provide the key to understanding some of the puzzling characteristics of cold and supercooled water, of which the glassy solids are more-viscous counterparts. Recent experimental and theoretical studies of both liquid and glassy water are now starting to offer the prospect of a coherent picture of the unusual properties of this ubiquitous substance.

https://polymer.bu.edu/hes/articles/ms98.pdf

The relationship between liquid, supercooled and glassy water

Oxygen thermobarometry measurements on spinel peridotite rocks indicate that the oxygen fugacity at the top of the upper mantle falls within ±2 log units of the fayalite-magnetite-quartz (FMQ) oxygen buffer. Measurements on garnet peridotites from cratonic lithosphere reveal a general decrease in fo2 with depth, which appears to result principally from the effect of pressure on the controlling Fe3+/Fe2+ equilibria. Modeling of experimental data indicates that at approximately 8 GPa, mantle fo2 will be 5 log units below FMQ and at a level where Ni-Fe metal becomes stable. Fe-Ni alloy and an Fe2O3-garnet component will be formed as a result of the disproportionation of FeO, which is experimentally demonstrated through observations of high Fe3+/ΣFe ratios in minerals in equilibrium with metallic Fe. In the lower mantle, the favorable coupled substitution of Al and Fe3+ into (Fe,Mg)SiO3 perovskite results in very high perovskite Fe3+/ΣFe ratios in equilibrium with metallic Fe. As a result, the lower mantle sh...

The Redox State of Earth's Mantle

Biogenic calcium carbonate forms the inorganic component of seashells, otoliths, and many marine skeletons, and its formation is directed by an ordered template of macromolecules. Classical nucleation theory considers crystal formation to occur from a critical nucleus formed by the assembly of ions from solution. Using cryotransmission electron microscopy, we found that template-directed calcium carbonate formation starts with the formation of prenucleation clusters. Their aggregation leads to the nucleation of amorphous nanoparticles in solution. These nanoparticles assemble at the template and, after reaching a critical size, develop dynamic crystalline domains, one of which is selectively stabilized by the template. Our findings have implications for template-directed mineral formation in biological as well as in synthetic systems.

The initial stages of template-controlled CaCO3 formation revealed by Cryo-TEM

El Nino events are characterized by surface warming of the tropical Pacific Ocean and weakening of equatorial trade winds that occur every few years Such conditions are accompanied by changes in atmospheric and oceanic circulation, affecting global climate, marine and terrestrial ecosystems, fisheries and human activities The alternation of warm El Nino and cold La Nina conditions, referred to as the El Nino–Southern Oscillation (ENSO), represents the strongest year-to-year fluctuation of the global climate system Here we provide a synopsis of our current understanding of the spatio-temporal complexity of this important climate mode and its influence on the Earth system

/pdf/el-nino-southern-oscillation-complexity-5alyl3svf7.pdf

El Niño–Southern Oscillation complexity

Layered double hydroxides (LDHs) have been known for a considerable time and have been widely studied. The basic features of their structure, involving positively charged brucite-like layers together with charge-balancing anions and water in interlayer galleries are well understood, but some detailed aspects of their structure have been the subject of controversy in the literature. In this article we review the wide range of experimental and theoretical studies of the structure of LDHs, highlighting areas of consensus and currently unresolved issues. We focus on the range of composition for which LDHs may be formed, possible layer stacking polytypes, arrangement of guest species in the interlayer galleries and the extent of order-disorder phenomena, both long-range and short-range, in the layers and interlayer galleries.

Structural aspects of layered double hydroxides

Angle dispersive powder X-ray diffraction experiments using a flat imaging plate (IP) are one of the most popular methods in high-pressure material science. In order to support such experiments, we developed two software, IPAnalyzer and PDIndexer. IPAnalyzer can convert a two-dimensional Debye-ring pattern to one-dimensional (Bragg-Brentano) geometry. IPAnalyzer can also calibrate experimental parameters (wave length, camera length, and so on) automatically. PDIndexer can display the converted pattern(s) and diffraction peaks calculated for any crystals.

Development of a Software Suite on X-ray Diffraction Experiments

The El Nino/Southern Oscillation (ENSO) system during the Pliocene warm period (PWP; 3-5 million years ago) may have existed in a permanent El Nino state with a sharply reduced zonal sea surface temperature (SST) gradient in the equatorial Pacific Ocean. This suggests that during the PWP, when global mean temperatures and atmospheric carbon dioxide concentrations were similar to those projected for near-term climate change, ENSO variability--and related global climate teleconnections-could have been radically different from that today. Yet, owing to a lack of observational evidence on seasonal and interannual SST variability from crucial low-latitude sites, this fundamental climate characteristic of the PWP remains controversial. Here we show that permanent El Nino conditions did not exist during the PWP. Our spectral analysis of the δ(18)O SST and salinity proxy, extracted from two 35-year, monthly resolved PWP Porites corals in the Philippines, reveals variability that is similar to present ENSO variation. Although our fossil corals cannot be directly compared with modern ENSO records, two lines of evidence suggest that Philippine corals are appropriate ENSO proxies. First, δ(18)O anomalies from a nearby live Porites coral are correlated with modern records of ENSO variability. Second, negative-δ(18)O events in the fossil corals closely resemble the decreases in δ(18)O seen in the live coral during El Nino events. Prior research advocating a permanent El Nino state may have been limited by the coarse resolution of many SST proxies, whereas our coral-based analysis identifies climate variability at the temporal scale required to resolve ENSO structure firmly.

http://indiaenvironmentportal.org.in/files/Permanent%20El%20Nino.pdf

Permanent El Niño during the Pliocene warm period not supported by coral evidence

We report on high-pressure and high-temperature experiments involving carbonates and silicates at 30–80 GPa and 1,600–3,200 K, corresponding to depths within the Earth of approximately 800–2,200 km. The experiments are intended to represent the decomposition process of carbonates contained within oceanic plates subducted into the lower mantle. In basaltic composition, CaCO3 (calcite and aragonite), the major carbonate phase in marine sediments, is altered into MgCO3 (magnesite) via reactions with Mg-bearing silicates under conditions that are 200–300°C colder than the mantle geotherm. With increasing temperature and pressure, the magnesite decomposes into an assemblage of CO2 + perovskite via reactions with SiO2. Magnesite is not the only host phase for subducted carbon—solid CO2 also carries carbon in the lower mantle. Furthermore, CO2 itself breaks down to diamond and oxygen under geotherm conditions over 70 GPa, which might imply a possible mechanism for diamond formation in the lower mantle.

Fate of carbonates within oceanic plates subducted to the lower mantle, and a possible mechanism of diamond formation

The compression behaviors of δ-AlOOH and δ-AlOOD were investigated under quasi-hydrostatic conditions at pressures up to 63.5 and 34.9 GPa, respectively, using results from synchrotron X-ray diffraction experiments conducted at ambient temperature. Because of the geometric isotope effect, at ambient pressure, the a and b axes of δ-AlOOD, which define the plane in which the hydrogen bond lies, are longer than those of δ-AOOH. Under increasing pressure, the a and b axes of δ-AlOOH stiffen at 10 GPa, although the c axis shows no marked change. Identical behavior was found in δ-AlOOD, but the change in compressibility was observed at a slightly higher pressure of 12 GPa. Axial ratios a / c and b / c first decrease rapidly with increasing pressure, then begin to increase at pressures >10 GPa in δ-AlOOH and >12 GPa in δ-AlOOD. At these pressures, the pressure dependence of a / b also changes from increasing to decreasing. The unit-cell volumes of δ-AlOOH and δ-AlOOD become slightly less compressible at high pressures. Assuming K ′ = 4, the calculated bulk moduli of δ-AlOOH below and above 10 GPa are 152(2) and 219(3) GPa, respectively. Those of δ-AlOOD below and above 12 GPa are 151(1) and 207(2) GPa, respectively.

Change in compressibility of δ-AlOOH and δ-AlOOD at high pressure: A study of isotope effect and hydrogen-bond symmetrization

Synchrotron X-ray powder diffraction study of brucite, Mg(OH) 2 , was carried out in a diamond anvil cell with an imaging plate detector from 0.6 to 18.0 GPa at room temperature using the angular-dispersive technique on beamline BL-18C at the Photon Factory, KEK, Japan. Using Rietveld analysis, unit-cell parameters as well as atomic positions of the O atoms in brucite have been successfully refined, taking into account the effects of preferred orientation. Variation of the c / a ratio with pressure indicates that the compression mechanism changes around 10 GPa, above which the compression behavior is isotropic. Based on the changes of the refined atomic positions of the O atoms with pressure, we conclude that the shortening of the interlayer distance controls compression below 10 GPa, whereas above this pressure compression of the oxygen sublattice is the dominant mechanism. Results of the structural refinements also suggest that the MgO 6 octahedral regularity initially approaches a regular configuration with pressure, which then remains unchanged above 10 GPa.

Takaya Nagai

Papers

Development of a Software Suite on X-ray Diffraction Experiments

Permanent El Niño during the Pliocene warm period not supported by coral evidence

Fate of carbonates within oceanic plates subducted to the lower mantle, and a possible mechanism of diamond formation

Change in compressibility of δ-AlOOH and δ-AlOOD at high pressure: A study of isotope effect and hydrogen-bond symmetrization

Compression mechanism of brucite: An investigation by structural refinement under pressure