Quantification of adamantane in organic media via infrared attenuated total reflection spectroscopy

In the present study, the quantitative determination of the diamondoid compound adamantane in organic solvents via infrared attenuated total reflection (IR-ATR) spectroscopy at unmodified waveguide surfaces was established. Limits of detection (LOD) and quantification (LOQ) of adamantane in dichloromethane, hexane and carbon tetrachloride were determined. Quantitative IR-ATR measurements additionally facilitated the determination of adamantane solubility limit in dichloromethane, hexane and carbon tetrachloride. The developed analytical strategy further enabled the successful detection and quantification of adamantane in crude oil matrices. Consequently, IR-ATR spectroscopy provides a promising strategy for on ship and in situ diamondoid analysis in harsh real world environments.     

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.     

Spectroscopy, morphometry, and photoclinometry of Titan's dunefields from Cassini/VIMS

Fine-resolution (500 m/pixel) Cassini Visual and Infrared Mapping Spectrometer (VIMS) T20 observations of Titan resolve that moon's sand dunes. The spectral variability in some dune regions shows that there are sand-free interdune areas, wherein VIMS spectra reveal the exposed dune substrate. The interdunes from T20 are, variously, materials that correspond to the equatorial bright, 5-μm-bright, and dark blue spectral units. Our observations show that an enigmatic “dark red” spectral unit seen in T5 in fact represents a macroscopic mixture with 5-μm-bright material and dunes as its spectral endmembers. Looking more broadly, similar mixtures of varying amounts of dune and interdune units of varying composition can explain the spectral and albedo variability within the dark brown dune global spectral unit that is associated with dunes. The presence of interdunes indicates that Titan's dunefields are both mature and recently active. The spectrum of the dune endmember reveals the sand to be composed of less water ice than the rest of Titan; various organics are consistent with the dunes' measured reflectivity. We measure a mean dune spacing of 2.1 km, and find that the dunes are oriented on the average in an east-west direction, but angling up to 10° from parallel to the equator in specific cases. Where no interdunes are present, we determine the height of one set of dunes photoclinometrically to be between 30 and 70 m. These results pave the way for future exploration and interpretation of Titan's sand dunes.     

Difference in petrophysical properties between foliated and dilatant fault rocks in deeply buried clastics: The case of the Grès d'Annot Formation,SW French Alps

This study describes normal fault zones formed in foreland arkosic turbidites (the Grès d'Annot Formation, SW French Alps) under deep diagenesis conditions (~200 °C) and highlights the occurrence of two markedly different fault‐rock types: (1) the foliated fault rocks of the Moutière‐Restefond area; and (2) the dilatant fault rocks of the Estrop area. The deformation of (1) is dominated by intra‐ and transgranular fracturing, pressure solution of quartz and feldspar grains and syn‐kinematic phyllosilicate precipitation resulting from feldspar alteration. The combination of these mechanisms results in a strongly anisotropic strain with intense shortening normal to the foliation (pressure solution) and extension parallel to the foliation (quartz‐ and calcite‐sealed extension veins). This deformation implies local mass transfer that may be achieved without (or with limited) volume change. The deformation of (2) is expressed as dilatant quartz‐sealed veins and breccia textures in which the main mechanisms are transgranular fracturing and quartz precipitation. Type (2) implies fault volume increase, isotropy of deformation and mass transfer at distances larger than in type (1). This study discusses the origins of (1) and (2) and shows that the permeability of (1) is anisotropic, with higher values than the host rocks parallel to the Y main deformation axis (i.e. perpendicular to the slip vector), whereas the permeability of (2) is isotropic and equivalent to that of the host rocks.     

The Upper Oligocene of Antigua: the volcanic to limestone transition in a limestone Caribbee

Antigua is a small island at the northern end of the Lesser Antilles chain. Its geology is largely limited to the Upper Oligocene and it records with unusual fidelity the transition from island arc volcanism to quiescence and limestone deposition. Despite the apparent limitation of a rock record confined to a short stratigraphical interval, Antigua has a geodiversity that ranges from thick andesites through silicified logs and freshwater snails in cherts to limestones that include both shallow and deeper water facies, and fine karstic features.     

Refining the ice flow chronology and subglacial dynamics across the migrating Labrador Divide of the Laurentide Ice Sheet with age constraints on deglaciation

The Laurentide Ice Sheet was characterized by a dynamic polythermal base. However, important data and knowledge gaps have led to contrasting reconstructions in areas such as the Labrador Ice Divide. In this study, detailed fieldwork was conducted at the southeastern edge of a major landform boundary to resolve the relative ice flow chronology and constrain the evolution of the subglacial dynamics, including the migration and collapse of the Labrador Ice Divide. Surficial mapping and analysis of 94 outcrop‐scale ice flow indicators were used to develop a relative ice flow chronology. ¹⁰Be exposure ages were used with optical ages to confine the timing of deglaciation within the study area. Four phases of ice flow were identified. Flow 1 was a northeasterly ice flow preserved under non‐erosive subglacial conditions associated with the development of an ice divide. Flow 2 was a northwest ice flow, which we correlate to the Ungava Bay Ice Stream and led to a westward migration of the ice divide, preserving Flow 2 features and resulting in Flow 3's eastward‐trending indicators. Flow 4 is limited to sparse fine striations within and around the regional uplands. The new optical ages and ¹⁰Be exposure ages add to the regional geochronology dataset, which further constrains the timing of ice margin retreat in the area to around 8.0 ka. Copyright © 2019 The Authors. Journal of Quaternary Science Published by John Wiley & Sons Ltd.     

Stable isotopes and trace elements in modern ostracod shells: implications for reconstructing past environments on the Tibetan Plateau,China

Stable isotopes and trace elements in ostracod shells have been used widely in paleolimnological investigations of past lake hydrochemistry and climate because they provide insights into past water balance and solute evolution of lakes. Regional differences in lake characteristics and species-specific element fractionation, however, do not permit generalization of results from other regions or ostracod species to the southern Tibetan Plateau, in part because most common taxa from the southern Tibetan Plateau are endemic to the area. This study evaluated relations between present-day environmental conditions and the geochemical composition of modern ostracod shells from the southern Tibetan Plateau, to assess the suitability of using shell chemistry to infer hydrological conditions. We studied nine lakes and their catchments, located along a west–east transect in the south-central part of the Tibetan Plateau. Stable oxygen and carbon isotope values and trace element concentrations in recent shells from the four most abundant ostracod species (Leucocytherella sinensis, ?Leucocythere dorsotuberosa, Limnocythere inopinata, Tonnacypris gyirongensis) were measured, together with hydrochemical properties of host waters at the time of sampling. Results revealed significant between-species differences in stable isotope fractionation and trace element incorporation into shell calcite. Stable oxygen and carbon isotope values of ostracod shells were correlated significantly with the stable isotope composition of the respective water body \( \left( {\updelta^{18} {\text{O}}_{{{\text{H}}_{ 2} {\text{O}}}} \,{\text{and }}\updelta^{13} {\text{C}}_{{{\text{H}}_{ 2} {\text{O}}}} } \right) \), reflecting salinity and productivity, respectively. Offsets between δ¹⁸O_shell and δ¹³C_shell and inorganic calcite, the latter representing isotopic equilibrium, suggest shell formation of T. gyirongensis during spring melt. L. sinensis reproduces throughout the monsoon season until September and shows several consecutive generations, and L. inopinata molts to the adult stage after the monsoon season in August/September. The influence of pore water δ¹³C was displayed by L. inopinata, suggesting shell calcification within the sediment. Mg/Ca_shell is primarily influenced by water Mg/Ca ratios and salinity and confirms the use of this shell ratio as a proxy for precipitation-evaporation balance and lake level. In addition, Sr/Ca and Ba/Ca can be used to infer changes in salinity, at least in closed-basin lakes with calcite saturation. Observed effects of water Sr/Ca and salinity on Sr/Ca incorporation are biased by the presence of aragonite precipitation in the lakes, which removes bioavailable Sr from the host water, resulting in low Sr/Ca_shell values. Changes in carbonate mineralogy affect the bioavailability of trace elements, a process that should be considered in paleoclimate reconstructions. Oxygen isotopes and Mg/Ca_shell ratios were unaffected by water temperature. Positive correlations among Fe/Ca, Mn/Ca and U/Ca in ostracod shells, and their negative correlation with δ¹³C, which reflects organic matter decay, show the potential to infer changes in redox conditions that can be used to reconstruct past oxygen supply to bottom waters and thus past water-circulation changes within lakes. The intensity of microbial activity, associated with organic matter decomposition, can be inferred from U/Ca ratios in ostracod shells. These findings highlight the value of fossil ostracod records in lake deposits for inferring paleoenvironmental conditions on the southern Tibetan Plateau.     

Probabilistic reasoning about measurements of equilibrium climate sensitivity: combining disparate lines of evidence

Where policy and science intersect, there are always issues of ambiguous and conflicting lines of evidence. Combining disparate information sources is mathematically complex; common heuristics based on simple statistical models easily lead us astray. Here, we use Bayesian Nets (BNs) to illustrate the complexity in reasoning under uncertainty. Data from joint research at Resources for the Future and NASA Langley are used to populate a BN for predicting equilibrium climate sensitivity (ECS). The information sources consist of measuring the rate of decadal temperature rise (DTR) and measuring the rate of percentage change in cloud radiative forcing (CRF), with both the existing configuration of satellites and with a proposed enhanced measuring system. The goal of all measurements is to reduce uncertainty in equilibrium climate sensitivity. Subtle aspects of probabilistic reasoning with concordant and discordant measurements are illustrated. Relative to the current prior distribution on ECS, we show that after 30 years of observing with the current systems, the 2σ uncertainty band for ECS would be shrunk on average to 73% of its current value. With the enhanced systems over the same time, it would be shrunk to 32% of its current value. The actual shrinkage depends on the values actually observed. These results are based on models recommended by the Social Cost of Carbon methodology and assume a Business as Usual emissions path.