Low temperature hydrolysis of laboratory tholins in ammonia-water solutions: Implications for prebiotic chemistry on Titan

Laboratory tholins react rapidly in 13 wt% ammonia-water at low temperature, producing complex organic molecules containing both oxygen and altered nitrogen functional groups. These reactions display first-order kinetics with half-lives between 0.3 and 14 days at 253 K. The reaction timescales are much shorter than the freezing timescales of impact melts and volcanic sites on Titan, providing ample time for the formation of oxygenated, possibly prebiotic, molecules on its surface. Comparing the rates of the hydrolysis reactions in ammonia-water to those measured in pure water [Neish, C.D, Somogyi, A., Imanaka, H., Lunine, J.I., Smith, M.A., 2008a. Astrobiology 8, 273-287], we find that incorporation of oxygen into the tholins is faster in the presence of ammonia. The rate increases could be due to the increased pH of the solution, or to the availability of new reaction pathways made possible by the presence of ammonia. Using labeled ¹⁵NH₃ water, we find that ammonia does incorporate into some products, and that the reactions with ammonia are largely independent of those with water. A related study in confirms water as the source of the oxygen incorporated into the oxygen containing products.     

A menagerie of graphite morphologies in the Acapulco meteorite with diverse carbon and nitrogen isotopic signatures: Implications for the evolution history of acapulcoite meteorites

Morphologies, petrographic settings and carbon and nitrogen isotopic compositions of graphites in the Acapulco meteorite, the latter determined by secondary ionization mass spectrometry, are reported. Seven different graphite morphologies were recognized, the majority of which occur enclosed exclusively in kamacite. Individual graphite grains also rarely occur in the silicate matrix. Kamacite rims surrounding taenite cores of metal grains are separated from the Ni-rich metal cores by graphite veneers. These graphite veneers impeded or prevented Ni-Fe interdiffusion during cooling. In addition, matrix FeNi metal contains considerable amounts of phosphorous (≈ 700 ppm) and silicon (≈ 300 ppm) (Pack et al., 2005 in preparation) thus indicating that results of laboratory cooling experiments in the Fe-Ni binary system are inapplicable to Acapulco metals. Graphites of different morphologies display a range of carbon and nitrogen isotopic compositions, indicating a diversity of source regions before accretion in the Acapulco parent body. The isotopic compositions point to at least three isotopic reservoirs from which the graphites originated: (1) A reservoir with heavy carbon, represented by graphite in silicates (δ¹³C = 14.3 ± 2.4 ‰ and δ¹⁵N = −103.4 ± 10.9 ‰), (2) A reservoir with isotopically light carbon and nitrogen, characteristic for the metals. Its C- and N-isotopic compositions are probably preserved in the graphite exsolutions that are isotopically light in carbon and lightest in nitrogen (δ¹³C = −17 to −23 ‰ δ¹⁵N = −141 to −159 ‰). (3) A reservoir with an assumed isotopic composition (δ¹³C ∼ −5 ‰; δ¹⁵N ∼ −50 ‰). A detailed three-dimensional tomography in reflected light microscopy of the decorations of metal-troilite spherules in the cores of orthopyroxenes and olivines and metal-troilite veins was conducted to clarify their origin. Metal and troilite veins are present only near the fusion crust. Hence, these veins are not pristine to Acapulco parent body but resulted during passage of Acapulco in Earth’s atmosphere. A thorough search for symplectite-type silicate-troilite liquid quench textures was conducted to determine the extent of closed-system partial silicate melting in Acapulco.Metal-troilite spherules in orthopyroxenes and olivines are not randomly distributed but decorate ferromagnesian silicate restite cores, indicating that the metal-spherule decoration around restite silicates took place in a silicate partial melt. Graphite inclusions in these spherules have C- and N- isotopic compositions (δ¹³C = −2.9 ± 2.5 ‰ and δ¹⁵N = −101.2 ± 32 ‰) close to the average values of graphite in metals and in the silicate matrix, thus strongly suggesting that they originated from a mixture of graphite inclusions in metals and silicate matrix graphite during a closed system crystallization process subsequent to silicate-metal-sulfide partial melting. Troilite-orthopyroxene quench symplectite textures in orthopyroxene rims are clear evidence that silicate-sulfide partial melting took place in Acapulco. Due to petrographic heterogeneity on a centimeter scale, bulk REE abundances of individual samples or of individual minerals provide only limited information and the REE abundances alone are not entirely adequate to unravel the formational processes that prevailed in the acapulcoite-lodranite parent body. The present investigations demonstrate the complexity of the evolutionary stages of acapulcoites from accretion to parent body processes.     

Preface

Earth, Moon, and Planets -     

Diurnal and tidal patterns of carbon uptake and calcification in geniculate inter‐tidal coralline algae

Research on coralline algal responses to ocean acidification and other environmental stressors has increased in recent years as coralline algae is thought to stand a higher chance of being affected by acidification stress than other macroalgae. To provide context and enhance the existing eco‐physiological framework for climate change studies, it is important to understand the effects of non‐extreme stressors experienced regularly by inter‐tidal coralline algae. In this study, we tested the potentially interacting effects of diurnal and tidal treatments on calcification in the geniculate coralline algae Corallina frondescens and Corallina vancouveriensis using ¹³C‐labeled bicarbonate. Both species deposited more calcium carbonate during the day than at night, and also when submerged (high tide) compared with when emerged (low tide) in their apical and mature segments (intergenicula). These results indicate that inter‐tidal coralline algae do in fact pay a cost for living inter‐tidally at the edge of an adaptive zone.     

Sedimentation within and among mangrove forests along a gradient of geomorphological settings

Coastal wetlands provide important ecological services to the coastal zone, one of which is sediment retention. In this study we investigated sediment retention across a range of geomorphological settings and across vegetation zones comprising coastal wetlands. We selected six coastal wetlands dominated by mangroves over a gradient from riverine to tidal settings in Southeast Queensland, Australia. Each site was comprised of three distinct vegetation communities distributed as parallel zones to the coast line: seaward fringe mangroves, landward scrub mangroves and saltmarsh/ cyanobacteria mat of the high intertidal zone. We measured suspended sediment retention and sedimentation rates. Additionally, in order to assess the origin of sediment transported and deposited in the mangroves, glomalin, a novel terrestrial soil carbon tracer, was used. Our results show a mean average sedimentation of 0.64 ± 0.01 mg cm⁻² spring tide⁻¹, which was variable within sites, regardless of geomorphological setting. However, geomorphological setting influenced spatial patterns of sediment deposition. Riverine mangroves had a more homogeneous distribution of sediments across the intertidal zone than tidal mangroves, where most sedimentation occurred in the fringe zone. Overall, the fringe zone retained the majority of sediment entering the coastal wetland during a tidal cycle with 0.90 ± 0.22 mg cm⁻² spring tide⁻¹, accounting for 52.5 ± 12.5% of the total sedimentation. The presence of glomalin in suspended sediments, and thus the relative importance of terrigenous sediment, was strongly influenced by geomorphological setting, with riverine mangroves receiving more glomalin in suspended solids than tidal mangroves. Glomalin was also differentially deposited within the vegetation zones at different geomorphological settings: primarily at the fringe zone of tidal mangroves and within the scrub zone of riverine mangroves. The differences we observed in the spatial distribution of sedimentation and the difference in the origin of the sediment deposited in riverine and tidal mangroves are likely to have an impact on ecological processes.     

Effect of anorthite on granite phase relations: Experimental data and models

New experimental data on the effect of anorthite (An) on liquidus phase equilibria in the system Qz–Ab–Or are presented. The data were obtained for 5 wt% An added to variable Qz/Ab/Or compositions at 300 MPa and under H₂O-saturated conditions. Crystal–liquid equilibria were determined for 13 synthetic glass compositions made from gels in experiments performed between 660 and 750 °C in cold-seal pressure vessels. Forward and reversal experiments were systematically conducted on each composition to demonstrate equilibrium. A total of 51 charges was examined. Three crystalline phases, quartz, alkali feldspar and plagioclase appear on the H₂O-saturated liquidus surface. The determined minimum liquidus 5 wt% An “piercing” point (39% Qz, 33% Ab, 28% Or) is shifted away from the Ab apex toward the Qz–Or sideline when compared with the An-free 300 MPa H₂O-saturated minimum. This shift is of the same type as that observed at 100 MPa in the same system and at 200 MPa in a rhyolitic system. The new experimental results are used to test both empirical and thermodynamic models for silicic magmas. Empirical models reproduce reasonably well the new experimental data, although more sophisticated calculations schemes appear to be required to improve their accuracy. The new experimental results in the haplogranodiorite system are not well reproduced with the model of Holland and Powell (2001), mainly because plagioclase stability appears greatly enhanced in the model. Rhyolite-MELTS satisfactorily reproduces the Qz-, Pl- and Af-liquid phase equilibria, but model H₂O solubilities are significantly lower and crystallization temperatures higher than in experiments.     

Assessing the use of global land cover data for guiding large area population distribution modelling

Gridded population distribution data are finding increasing use in a wide range of fields, including resource allocation, disease burden estimation and climate change impact assessment. Land cover information can be used in combination with detailed settlement extents to redistribute aggregated census counts to improve the accuracy of national-scale gridded population data. In East Africa, such analyses have been done using regional land cover data, thus restricting application of the approach to this region. If gridded population data are to be improved across Africa, an alternative, consistent and comparable source of land cover data is required. Here these analyses were repeated for Kenya using four continent-wide land cover datasets combined with detailed settlement extents and accuracies were assessed against detailed census data. The aim was to identify the large area land cover dataset that, combined with detailed settlement extents, produce the most accurate population distribution data. The effectiveness of the population distribution modelling procedures in the absence of high resolution census data was evaluated, as was the extrapolation ability of population densities between different regions. Results showed that the use of the GlobCover dataset refined with detailed settlement extents provided significantly more accurate gridded population data compared to the use of refined AVHRR-derived, MODIS-derived and GLC2000 land cover datasets. This study supports the hypothesis that land cover information is important for improving population distribution model accuracies, particularly in countries where only coarse resolution census data are available. Obtaining high resolution census data must however remain the priority. With its higher spatial resolution and its more recent data acquisition, the GlobCover dataset was found as the most valuable resource to use in combination with detailed settlement extents for the production of gridded population datasets across large areas.     

On the coattails of climate? Opportunities and threats of a warming Earth for biodiversity conservation

The relationship between climate change and biodiversity was a central issue at the 10th Conference of the Parties (COP 10) to the Convention on Biological Diversity (CBD). In this paper we draw from participant observation data collected at COP 10, and related policy documentation, to examine how concerns about climate change are shaping the conservation policy landscape – in terms of the knowledge and rationales used as inputs, networks of actors involved, objectives sought, and actions proposed. We find that debates at the intersection of climate and biodiversity were overwhelmingly framed in relation to, or through the lens of carbon. Through a discussion of four core Climate-Motivated Responses, we illustrate how “carbon-logic”, and the initiatives that it generates, simultaneously creates threats to the objectives sought by some actors, and opportunities for the objectives sought by others. We situate our observations in the context of some of the historical dilemmas that have faced conservation, and discuss this current moment in the dynamic trajectory of conservation governance: a moment when decisions about conserving biodiversity are becoming entangled with carbon-logic and the market. In this case, while some actors seek opportunities for biodiversity ends by riding the coattails of the climate agenda, the threats of doing so may undermine the biological and social objectives of the CBD convention itself.