Catalytic peptide hydrolysis by mineral surface: Implications for prebiotic chemistry

The abiotic polymerization of amino acids may have been important for the origin of life, as peptides may have been components of the first self-replicating systems. Though amino acid concentrations in the primitive oceans may have been too dilute for significant oligomerization to occur, mineral surface adsorption may have provided a concentration mechanism. As unactivated amino acid polymerization is thermodynamically unfavorable and kinetically slow in aqueous solution, we studied mainly the reverse reaction of polymer degradation to measure the impact of mineral surface catalysis on peptide bonds.Aqueous glycine (G), diglycine (GG), diketopiperazine (DKP), and triglycine (GGG) were reacted with minerals (calcite, hematite, montmorillonite, pyrite, rutile, or amorphous silica) in the presence of 0.05 M, pH 8.1, KHCO₃ buffer and 0.1 M NaCl as background electrolyte in a thermostatted oven at 25, 50 or 70 °C. Below 70 °C, reaction kinetics were too sluggish to detect catalytic activity over amenable laboratory time-scales. Minerals were not found to have measurable effects on the degradation or elongation of G, GG or DKP at 70 °C in solution. At 70 °C pyrite was the most catalytic mineral with detectible effects on the degradation of GGG, although several others also displayed catalytic behavior. GGG degraded ∼1.5-4 times faster in the presence of pyrite than in control reactions, depending on the ratio of solution concentration to mineral surface area. The rate of pyrite catalysis of GGG hydrolysis was found to be saturable, suggesting the presence of discrete catalytic sites on the mineral surface. The mineral-catalyzed degradation of GGG appears to occur via a GGG → DKP + G mechanism, rather than via GGG → GG + G, as in solution-phase reactions. These results are compatible with many previous findings and suggest that minerals may have assisted in peptide synthesis in certain geological settings, specifically by speeding the approach to equilibrium in environments where amino acids were already highly concentrated, but that minerals may not significantly alter the expected solution-phase equilibria. Thus the abiotic synthesis of long peptides may have required activating agents, dry heating at higher temperatures, or some form of phase separation.     

Downscaling reveals diverse effects of anthropogenic climate warming on the potential for local environments to support malaria transmission

The potential impact of climate warming on patterns of malaria transmission has been the subject of keen scientific and policy debate. Standard climate models (GCMs) characterize climate change at relatively coarse spatial and temporal scales. However, malaria parasites and the mosquito vectors respond to diurnal variations in conditions at very local scales. Here we bridge this gap by downscaling a series of GCMs to provide high-resolution temperature data for four different sites and show that although outputs from both the GCM and the downscaled models predict diverse but qualitatively similar effects of warming on the potential for adult mosquitoes to transmit malaria, the predicted magnitude of change differs markedly between the different model approaches. Raw GCM model outputs underestimate the effects of climate warming at both hot (3-fold) and cold (8–12 fold) extremes, and overestimate (3-fold) the change under intermediate conditions. Thus, downscaling could add important insights to the standard application of coarse-scale GCMs for biophysical processes driven strongly by local microclimatic conditions.     

Geological controls on submarine groundwater discharge in Long Bay,South Carolina (USA)

A combination of geophysical methods including continuous electrical resistivity and high-resolution Chirp sub-bottom profiling were utilized to characterize geologic controls on pore fluid salinity in the nearshore of Long Bay, SC. Resistivity values ranged from less than 1 Ω m to greater than 40 Ω m throughout the bay. Areas of elevated electrical resistivity suggest the influence of relatively fresher water on pore water composition. Geophysical evidence alone does not eliminate all ambiguity associated with lithological and porosity variations that may also contribute to electrical structure of shallow marine sediments. The anomalous field is of sufficient magnitude that lithological variation alone does not control the spatial distribution of elevated electrical resistivity zones. Geographical distribution of electrical anomalies and structures interpreted from nearby sub-bottom profiles indicates abrupt changes in shallow geologic units control preferential pathways for discharge of fresh water into the marine environment. Shore parallel resistivity profiles show dramatic decreases in magnitude with increasing distance from shore, suggesting a significant portion of the terrestrially driven fresh SGD in Long Bay is occurring via the surficial aquifer within a few hundred meters of shore.     

A surface complexation model for sulfate and selenate on iron oxides consistent with spectroscopic and theoretical molecular evidence

Sulfate and selenate adsorption on iron oxides are important reactions in natural systems under a very wide range of pH values, ionic strengths, and electrolyte compositions. Under such conditions, spectroscopic and theoretical calculations have demonstrated the potential importance of a variety of surface species. Understanding the variations in the surface speciation of these oxyanions is fundamental to prediction of their partitioning between minerals and aqueous solutions. In the present study, published experimental spectroscopic and theoretical molecular evidence of the identity of sulfate/selenate surface species are integrated with a surface complexation model consistent with a wide variety of experimental adsorption, surface titration, and proton coadsorption data to define the surface speciation of sulfate and selenate on iron oxides under a wide range of conditions. The analysis was carried out with the extended triple layer model (ETLM) taking into account the electrostatics of water dipole desorption during ligand exchange reactions. On seven out of eight goethites studied, sulfate and selenate surface reactions can be represented by the formation of a monodentate-mononuclear inner-sphere and a bidentate-binuclear outer-sphere (or H-bonded) species according to

     

Explicit evolution relations with orbital elements for eccentric,inclined, elliptic and hyperbolic restricted few-body problems

Planetary, stellar and galactic physics often rely on the general restricted gravitational $N$ -body problem to model the motion of a small-mass object under the influence of much more massive objects. Here, I formulate the general restricted problem entirely and specifically in terms of the commonly used orbital elements of semimajor axis, eccentricity, inclination, longitude of ascending node, argument of pericentre, and true anomaly, without any assumptions about their magnitudes. I derive the equations of motion in the general, unaveraged case, as well as specific cases, with respect to both a bodycentric and barycentric origin. I then reduce the equations to three-body systems, and present compact singly- and doubly-averaged expressions which can be readily applied to systems of interest. This method recovers classic Lidov–Kozai and Laplace–Lagrange theory in the test particle limit to any order, but with fewer assumptions, and reveals a complete analytic solution for the averaged planetary pericentre precession in coplanar circular circumbinary systems to at least the first three nonzero orders in semimajor axis ratio. Finally, I show how the unaveraged equations may be used to express resonant angle evolution in an explicit manner that is not subject to expansions of eccentricity and inclination about small nor any other values.     

Effects of water use on arsenic release to well water in a confined aquifer

Field-based experiments were designed to investigate the release of naturally occurring, low to moderate (< 50 microg/L) arsenic concentrations to well water in a confined sandstone aquifer in northeastern Wisconsin. Geologic, geochemical, and hydrogeologic data collected from a 115 m2 site demonstrate that arsenic concentrations in ground water are heterogeneous at the scale of the field site, and that the distribution of arsenic in ground water correlates to solid-phase arsenic in aquifer materials. Arsenic concentrations in a test well varied from 1.8 to 22 microg/L during experiments conducted under no, low, and high pumping rates. The quality of ground water consumed from wells under typical domestic water use patterns differs from that of ground water in the aquifer because of reactions that occur within the well. Redox conditions in the well can change rapidly in response to ground water withdrawals. The well borehole is an environment conducive to microbiological growth, and biogeochemical reactions also affect borehole chemistry. While oxidation of sulfide minerals appears to release arsenic to ground water in zones within the aquifer, reduction of arsenic-bearing iron (hydr)oxides is a likely mechanism of arsenic release to water having a long residence time in the well borehole.     

Structural properties of pseudo-bulges, classical bulges and elliptical galaxies: a Sloan Digital Sky Survey perspective

We have performed 2D bulge/bar/disc decompositions using g , r and i -band images of a representative sample of nearly 1000 galaxies from the Sloan Digital Sky Survey. We show that the Petrosian concentration index is a better proxy for the bulge-to-total ratio than the global Sérsic index. We show that pseudo-bulges can be distinguished from classical bulges as outliers in the Kormendy relation. We provide the structural parameters and distributions of stellar masses of ellipticals, classical bulges, pseudo-bulges, discs and bars, and find that 32 per cent of the total stellar mass in massive galaxies in the local universe is contained in ellipticals, 36 per cent in discs, 25 per cent in classical bulges, 3 per cent in pseudo-bulges and 4 per cent in bars. Pseudo-bulges are currently undergoing intense star formation activity and populate the blue cloud of the colour–magnitude diagram. Most (though not all) classical bulges are quiescent and populate the red sequence of the diagram. Classical bulges follow a correlation between the bulge Sérsic index and bulge-to-total ratio, while pseudo-bulges do not. In addition, for a fixed bulge-to-total ratio, pseudo-bulges are less concentrated than classical bulges. Pseudo-bulges follow a mass–size relation similar to that followed by bars, and different from that followed by classical bulges. In the fundamental plane, pseudo-bulges occupy the same locus as discs. While these results point out different formation processes for classical and pseudo-bulges, we also find a significant overlap in their properties, indicating that the different processes might happen concomitantly. Finally, classical bulges and ellipticals follow offset mass–size relations, suggesting that high-mass bulges might not be simply high-mass ellipticals surrounded by discs.     

GETEMME—a mission to explore the Martian satellites and the fundamentals of solar system physics

GETEMME (Gravity, Einstein??s Theory, and Exploration of the Martian Moons?? Environment), a mission which is being proposed in ESA??s Cosmic Vision program, shall be launched for Mars on a Soyuz Fregat in 2020. The spacecraft will initially rendezvous with Phobos and Deimos in order to carry out a comprehensive mapping and characterization of the two satellites and to deploy passive Laser retro-reflectors on their surfaces. In the second stage of the mission, the spacecraft will be transferred into a lower 1500-km Mars orbit, to carry out routine Laser range measurements to the reflectors on Phobos and Deimos. Also, asynchronous two-way Laser ranging measurements between the spacecraft and stations of the ILRS (International Laser Ranging Service) on Earth are foreseen. An onboard accelerometer will ensure a high accuracy for the spacecraft orbit determination. The inversion of all range and accelerometer data will allow us to determine or improve dramatically on a host of dynamic parameters of the Martian satellite system. From the complex motion and rotation of Phobos and Deimos we will obtain clues on internal structures and the origins of the satellites. Also, crucial data on the time-varying gravity field of Mars related to climate variation and internal structure will be obtained. Ranging measurements will also be essential to improve on several parameters in fundamental physics, such as the Post-Newtonian parameter ?? as well as time-rate changes of the gravitational constant and the Lense-Thirring effect. Measurements by GETEMME will firmly embed Mars and its satellites into the Solar System reference frame.