Nature of polymerization and properties of silicate melts and glasses at high pressure

The structures of sodium silicate and aluminosilicate glasses quenched from melts at high pressure (6-10 GPa) with varying degrees of polymerization (fractions of nonbridging oxygen) were explored using solid-state NMR [¹⁷O and ²⁷Al triple-quantum magic-angle spinning (3QMAS) NMR]. The bond connectivity in melts among four and highly coordinated network polyhedra, such as ^[4]Al, ^[5,6]Al, ^[4]Si, and ^[5,6]Si, at high pressure is shown to be significantly different from that at ambient pressure. In particular, in the silicate and aluminosilicate melts, the proportion of nonbridging oxygen (NBO) generally decreases with increasing pressure, leading to the formation of new oxygen clusters that include 5- and 6-coordinated Si and Al in addition to 4-coordinated Al and Si, such as ^[4]Si-O-^[5,6]Si, ^[4]Si-O-^[5,6]Al and Na-O-^[5,6]Si. While the fractions of ^[5,6]Al increase with pressure, the magnitude of this increase diminishes with increasing degrees of ambient-pressure polymerization under isobaric conditions. Incorporating the above structural information into models of melt properties reproduces the anomalous pressure-dependence of O²⁻ diffusivity and viscosity often observed in silicate melts.     

Solution mechanisms of H2O in depolymerized peralkaline melts

Solubility mechanisms of water in depolymerized silicate melts quenched from high temperature (1000°-1300°C) at high pressure (0.8-2.0 GPa) have been examined in peralkaline melts in the system Na₂O-SiO₂-H₂O with Raman and NMR spectroscopy. The Na/Si ratio of the melts ranged from 0.25 to 1. Water contents were varied from ∼3 mol% and ∼40 mol% (based on O = 1). Solution of water results in melt depolymerization where the rate of depolymerization with water content, ∂(NBO/Si)/∂X_H2O, decreases with increasing total water content. At low water contents, the influence of H₂O on the melt structure resembles that of adding alkali oxide. In water-rich melts, alkali oxides are more efficient melt depolymerizers than water. In highly polymerized melts, Si-OH bonds are formed by water reacting with bridging oxygen in Q⁴-species to form Q³ and Q² species. In less polymerized melts, Si-OH bonds are formed when bridging oxygen in Q³-species react with water to form Q²-species. In addition, the presence of Na-OH complexes is inferred. Their importance appears to increase with Na/Si. This apparent increase in importance of Na-OH complexes with increasing Na/Si (which causes increasing degree of depolymerization of the anhydrous silicate melt) suggests that water is a less efficient depolymerizer of silicate melts, the more depolymerized the melt. This conclusion is consistent with recently published ¹H and ²⁹Si MAS NMR and ¹H-²⁹Si cross polarization NMR data.     

Rapid incorporation of lipids into macromolecules during experimental decay of invertebrates: Initiation of geopolymer formation

Diagenetic alteration is critical for the preservation of fossil cuticles of plant and animal origin and to the formation of kerogen. The process takes place over millions of years, but the stage at which it is initiated is not known. Laboratory decay experiments were carried out on shrimps, scorpions and cockroaches to monitor changes in the chitin–protein of the arthropod cuticle and associated lipids. The cockroach and scorpion exoskeleton remained largely unaltered morphologically, but the shrimp experienced rapid decomposition within a month, which progressed through the 44 week duration of the experiment as revealed using electron microscopy. Mass spectrometry and ¹³C NMR (nuclear magnetic resonance) spectroscopy revealed the association of an n-alkyl component with labile lipids, such as fatty acids with up to 24 carbon atoms, which were incorporated into the decaying macromolecule. The scorpion and cockroach cuticle did not reveal the incorporation of additional lipids, indicating that decay is important in initiating in situ lipid association. This experiment provides evidence that lipids can become associated with carbohydrate and proteinaceous macromolecules during the very early stages of decay, representing the first stage in the transformation process that contributes to the aliphatic rich composition ubiquitous in organic fossils and kerogen.     

Characterization of permineralized kerogen from an Eocene fossil fern

The processes of organic maturation that occur during the permineralization of fossils and the detailed chemistry of the resulting products are incompletely understood. Primary among such processes is the geochemical alteration of biological matter to produce kerogen, such as that which comprises the cell walls of the fossils studied here: essentially unmetamorphosed, Eocene plant axes (specimens of the fossil fern Dennstaedtiopsis aerenchymata cellularly permineralized in cherts of the Clarno Formation of Oregon and the Allenby Formation of British Columbia). The composition and molecular structure of the kerogen that comprises the cell walls of such axes were analyzed using ultraviolet Raman spectroscopy (UV–Raman), solid state ¹³C nuclear magnetic resonance spectroscopy (¹³C NMR) and pyrolysis–gas chromatography–mass spectrometry (py–GC–MS).Cellularly well-preserved fern axes from both geologic units exhibit similar overall molecular structure, being composed primarily of networks of aromatic rings and polyene chains that, unlike more mature kerogens, lack large polycyclic aromatic hydrocarbon (PAH) constituents. The cell walls of the Allenby Formation specimens are, however, less altered than those of the Clarno chert, exhibiting more prevalent oxygen-containing and alkyl functional groups and comprising a greater fraction of rock mass.The study represents the first demonstration of the effectiveness (and limitations) of the combined use of UV–Raman, ¹³C NMR and py–GC–MS for the analysis of the kerogenous cell walls of chert-permineralized vascular plants.     

Low‐accommodation and backwater effects on sequence stratigraphic surfaces and depositional architecture of fluvio‐deltaic settings (Cretaceous Mesa Rica Sandstone,Dakota Group,USA)

The adequate documentation and interpretation of regional‐scale stratigraphic surfaces is paramount to establish correlations between continental and shallow marine strata. However, this is often challenged by the amalgamated nature of low‐accommodation settings and control of backwater hydraulics on fluvio‐deltaic stratigraphy. Exhumed examples of full‐transect depositional profiles across river‐to‐delta systems are key to improve our understanding about interacting controlling factors and resultant stratigraphy. This study utilizes the ~400 km transect of the Cenomanian Mesa Rica Sandstone (Dakota Group, USA), which allows mapping of down‐dip changes in facies, thickness distribution, fluvial architecture and spatial extent of stratigraphic surfaces. The two sandstone units of the Mesa Rica Sandstone represent contemporaneous fluvio‐deltaic deposition in the Tucumcari sub‐basin (Western Interior Basin) during two regressive phases. Multivalley deposits pass down‐dip into single‐story channel sandstones and eventually into contemporaneous distributary channels and delta‐front strata. Down‐dip changes reflect accommodation decrease towards the paleoshoreline at the Tucumcari basin rim, and subsequent expansion into the basin. Additionally, multi‐storey channel deposits bound by erosional composite scours incise into underlying deltaic deposits. These represent incised‐valley fill deposits, based on their regional occurrence, estimated channel tops below the surrounding topographic surface and coeval downstepping delta‐front geometries. This opposes criteria offered to differentiate incised valleys from flood‐induced backwater scours. As the incised valleys evidence relative sea‐level fall and flood‐induced backwater scours do not, the interpretation of incised valleys impacts sequence stratigraphic interpretations. The erosional composite surface below fluvial strata in the continental realm represents a sequence boundary/regional composite scour (RCS). The RCS’ diachronous nature demonstrates that its down‐dip equivalent disperses into several surfaces in the marine part of the depositional system, which challenges the idea of a single, correlatable surface. Formation of a regional composite scour in the fluvial realm throughout a relative sea‐level cycle highlights that erosion and deposition occur virtually contemporaneously at any point along the depositional profile. This contradicts stratigraphic models that interpret low‐accommodation settings to dominantly promote bypass, especially during forced regressions. Source‐to‐sink analyses should account for this in order to adequately resolve timing and volume of sediment storage in the system throughout a complete relative sea‐level cycle.     

A spatiotemporal analysis of tropical cyclone tracks in the Atlantic Basin and their relationship to El Niño-Southern Oscillation

There has been an enhanced focus on Atlantic tropical cyclone climatologies with the significant cyclones of the past decade and the associated loss of life and property. This study examines the geographic location of cyclone tracks and their relationship to El Niño-Southern Oscillation (ENSO). The average annual cyclone track latitude and longitude correlate positively with hurricane-season El Niño indices, indicating that during El Niño conditions, tropical cyclone tracks are shifted northward and eastward. June–November indices explain 11–22% and 3–11% of the variance in cyclone track latitude and longitude, respectively. Examination of the strongest and weakest El Niño years yields similar results. Higher sea level pressure over North America, a slight contraction of the Bermuda High, and a slight decrease in 500 mb heights during El Niño years helps to explain the observed northward and eastward movement of tropical cyclone tracks during El Niño years. Additionally, weaker easterly and stronger southerly winds on the western side of the North Atlantic Basin exist during El Niño years. Although future tropical cyclone track projection is beyond the scope of this research, these results may provide insight into forecast improvement and ultimately better responses for coastal communities.     

Deuterium enrichments in chondritic macromolecular material—Implications for the origin and evolution of organics, water and asteroids

Here we report the elemental and isotopic compositions of the insoluble organic material (IOM) isolated from several previously unanalyzed meteorites, as well as the reanalyses of H isotopic compositions of some previously measured samples (Alexander et al., 2007). The IOM in ordinary chondrites (OCs) has very large D enrichments that increase with increasing metamorphism and decreasing H/C, the most extreme δD value measured being almost 12,000‰. We propose that such large isotopic fractionations could be produced in the OC parent bodies through the loss of isotopically very light H₂ generated when Fe was oxidized by water at low temperatures (<200 °C). We suggest that similar isotopic fractionations were not generated in the IOM of CV and CO chondrites with similar metamorphic grades and IOM H/C ratios because proportionately less water was consumed during metamorphism, and the remaining water buffered the H isotopic composition of the IOM even a H was being lost from it.Hydrogen would also have been generated during the alteration of CI, CM and CR carbonaceous chondrites. The IOM in these meteorites exhibit a considerable range in isotopic compositions, but all are enriched in D, as well as ¹⁵N, relative to terrestrial values. We explore whether these enrichments could also have been produced by the loss of H₂, but conclude that the most isotopically anomalous IOM compositions in meteorites from these groups are probably closest to their primordial values. The less isotopically anomalous IOM has probably been modified by parent body processes. The response of IOM to these processes was complex and varied, presumably reflecting differences in conditions within and between parent bodies.The D enrichments associated with H₂ generation, along with exchange between D-rich IOM and water in the parent bodies, means that it is unlikely that any chondrites retain the primordial H isotopic composition of the water ice that they accreted. The H isotopic compositions of the most water-rich chondrites, the CMs and CIs, are probably the least modified and their compositions (δD ? −25‰) suggest that their water did not form at large radial distances from the Sun where ice is predicted to be very D-rich. Yet models to explain the O isotopic composition of inner Solar System bodies require that large amounts of ice were transported from the outer to the inner Solar System.