High-pressure melting experiments of Fe3S and a thermodynamic model of the Fe-S liquids for the Earth's core.

Melting experiments on Fe3S were conducted to 75 GPa and 2800 K in laser-heated and internally resistive-heated diamond anvil cells within-situx-ray diffraction and/or post-mortem textural observation. From the constrained melting curve, we assessed the thermal equation of state for Fe3S liquid. Then we constructed a thermodynamic model of melting of the system Fe-Fe3S including the eutectic relation under high pressures based on our new experimental data. The mixing properties of Fe-S liquids under high pressures were evaluated in order to account for existing experimental data on eutectic temperature. The results demonstrate that the mixing of Fe and S liquids are nonideal at any core pressure. The calculated sulphur content in eutectic point decreases with increasing pressure to 120 GPa and is fairly constant of 8 wt% at greater pressures. From the Gibbs free energy, we derived the parameters to calculate the crystallising point of an Fe-S core and its isentrope, and then we calculated the density and the longitudinal seismic wave velocity (Vp) of these liquids along each isentrope. While Fe3S liquid can account for the seismologically constrained density andVpprofiles over the outer core, the density of the precipitating phase is too low for the inner core. On the other hand, a hypothetical Fe-S liquid core with a bulk composition on the Fe-rich side of the eutectic point cannot represent the density andVpprofiles of the Earth's outer core. Therefore, Earth's core cannot be approximated by the system Fe-S and it should include another light element.

An Ultrahigh CO2-Loaded Silicalite-1 Zeolite: Structural Stability and Physical Properties at High Pressures and Temperatures.

We report the formation of an ultrahigh CO2-loaded pure-SiO2 silicalite-1 structure at high pressure (0.7 GPa) from the interaction of empty zeolite and fluid CO2 medium. The CO2-filled structure was characterized in situ by means of synchrotron powder X-ray diffraction. Rietveld refinements and Fourier recycling allowed the location of 16 guest carbon dioxide molecules per unit cell within the straight and sinusoidal channels of the porous framework to be analyzed. The complete filling of pores by CO2 molecules favors structural stability under compression, avoiding pressure-induced amorphization below 20 GPa, and significantly reduces the compressibility of the system compared to that of the parental empty one. The structure of CO2-loaded silicalite-1 was also monitored at high pressures and temperatures, and its thermal expansivity was estimated.

Exploring the Chemical Reactivity between Carbon Dioxide and Three Transition Metals (Au, Pt, and Re) at High-Pressure, High-Temperature Conditions.

The role of carbon dioxide, CO2, as oxidizing agent at high pressures and temperatures is evaluated by studying its chemical reactivity with three transition metals: Au, Pt, and Re. We report systematic X-ray diffraction measurements up to 48 GPa and 2400 K using synchrotron radiation and laser-heating diamond-anvil cells. No evidence of reaction was found in Au and Pt samples in this pressure-temperature range. In the Re + CO2 system, however, a strongly-driven redox reaction occurs at P > 8 GPa and T > 1500 K, and orthorhombic ß-ReO2 is formed. This rhenium oxide phase is stable at least up to 48 GPa and 2400 K and was recovered at ambient conditions. Raman spectroscopy data confirm graphite as a reaction product. Ab-initio total-energy structural and compressibility data of the ß-ReO2 phase shows an excellent agreement with experiments, altogether accurately confirming CO2 reduction P-T conditions in the presence of rhenium metal and the ß-ReO2 equation of state.

Elevation-dependent temperature trends in the Rocky Mountain Front Range: changes over a 56- and 20-year record.

Determining the magnitude of climate change patterns across elevational gradients is essential for an improved understanding of broader climate change patterns and for predicting hydrologic and ecosystem changes. We present temperature trends from five long-term weather stations along a 2077-meter elevational transect in the Rocky Mountain Front Range of Colorado, USA. These trends were measured over two time periods: a full 56-year record (1953-2008) and a shorter 20-year (1989-2008) record representing a period of widely reported accelerating change. The rate of change of biological indicators, season length and accumulated growing-degree days, were also measured over the 56 and 20-year records. Finally, we compared how well interpolated Parameter-elevation Regression on Independent Slopes Model (PRISM) datasets match the quality controlled and weather data from each station. Our results show that warming signals were strongest at mid-elevations over both temporal scales. Over the 56-year record, most sites show warming occurring largely through increases in maximum temperatures, while the 20-year record documents warming associated with increases in maximum temperatures at lower elevations and increases in minimum temperatures at higher elevations. Recent decades have also shown a shift from warming during springtime to warming in July and November. Warming along the gradient has contributed to increases in growing-degree days, although to differing degrees, over both temporal scales. However, the length of the growing season has remained unchanged. Finally, the actual and the PRISM interpolated yearly rates rarely showed strong correlations and suggest different warming and cooling trends at most sites. Interpretation of climate trends and their seasonal biases in the Rocky Mountain Front Range are dependent on both elevation and the temporal scale of analysis. Given mismatches between interpolated data and the directly measured station data, we caution against an over-reliance on interpolation methods for documenting local patterns of climatic change.

Grasshopper community response to climatic change: variation along an elevational gradient.

BACKGROUND: The impacts of climate change on phenological responses of species and communities are well-documented; however, many such studies are correlational and so less effective at assessing the causal links between changes in climate and changes in phenology. Using grasshopper communities found along an elevational gradient, we present an ideal system along the Front Range of Colorado USA that provides a mechanistic link between climate and phenology. METHODOLOGY/PRINCIPAL FINDINGS: This study utilizes past (1959-1960) and present (2006-2008) surveys of grasshopper communities and daily temperature records to quantify the relationship between amount and timing of warming across years and elevations, and grasshopper timing to adulthood. Grasshopper communities were surveyed at four sites, Chautauqua Mesa (1752 m), A1 (2195 m), B1 (2591 m), and C1 (3048 m), located in prairie, lower montane, upper montane, and subalpine life zones, respectively. Changes to earlier first appearance of adults depended on the degree to which a site warmed. The lowest site showed little warming and little phenological advancement. The next highest site (A1) warmed a small, but significant, amount and grasshopper species there showed inconsistent phenological advancements. The two highest sites warmed the most, and at these sites grasshoppers showed significant phenological advancements. At these sites, late-developing species showed the greatest advancements, a pattern that correlated with an increase in rate of late-season warming. The number of growing degree days (GDDs) associated with the time to adulthood for a species was unchanged across the past and present surveys, suggesting that phenological advancement depended on when a set number of GDDs is reached during a season. CONCLUSIONS: Our analyses provide clear evidence that variation in amount and timing of warming over the growing season explains the vast majority of phenological variation in this system. Our results move past simple correlation and provide a stronger process-oriented and predictive framework for understanding community level phenological responses to climate change.

Pea3 expression is regulated by FGF signaling in developing retina.

FGF signaling has been implicated as an important regulator of retinal development. As a first step in characterizing potential downstream targets of FGF signaling in the retina, we have analyzed expression of Pea3, a member of the Pea3 class of Ets-domain transcription factors, in the developing eye. We find that Pea3 is expressed in the developing retina, and its transcription is regulated by FGF receptor activation. In addition, FGF signaling activates Cath5, a gene necessary for retinal ganglion cell differentiation. These results suggest that FGF signaling via MAPK up-regulates transcription factors that in turn control retinal ganglion cell differentiation.

Potential of fermentation profiling via rapid measurement of amino acid metabolism by liquid chromatography-tandem mass spectrometry.

Monitoring amino acid metabolism during fermentation has significant potential from the standpoint of strain selection, optimizing growth and production in host strains, and profiling microbial metabolism and growth state. A method has been developed based on rapid quantification of underivatized amino acids using liquid chromatography-electrospray tandem mass spectrometry (LC-MS-MS) to monitor the metabolism of 20 amino acids during microbial fermentation. The use of a teicoplanin-based chiral stationary phase coupled with electrospray tandem mass spectrometry allows complete amino acid analyses in less than 4 min. Quantification is accomplished using five isotopically labeled amino acids as internal standards. Because comprehensive chromatographic separation and derivatization are not required, analysis time is significantly less than traditional reversed- or normal-phase LC-based amino acid assays. Intra-sample precisions for amino acid measurements in fermentation supernatants using this method average 4.9% (R.S.D.). Inter-day (inter-fermentation) precisions for individual amino acid measurements range from 4.2 to 129% (R.S.D.). Calibration curves are linear over the range 0-300 microg/ml, and detection limits are estimated at 50-450 ng/ml. Data visualization techniques for constructing semi-quantitative fermentation profiles of nitrogen source utilization have also been developed and implemented, and demonstrate that amino acid profiles generally correlate with observed growth profiles. Further, cellular growth events, such as lag-time and cell lysis can be detected using this methodology. Correlation coefficients for the time profiles of each amino acid measured illustrate that while several amino acids are differentially metabolized in similar fermentations, a select group of amino acids display strong correlations in these samples, indicating a sub-population of analytes that may be most useful for fermentation profiling.

Identification of ciliary epithelial-specific genes using subtractive libraries and cDNA arrays in the avian eye.

The ciliary epithelium of the ciliary body is derived from the anterior rim of the developing optic cup. Several recent studies have found that developmental abnormalities in this tissue can underlie congenital glaucoma. However, there is little known about the development of the ciliary epithelium. To better understand the developmental events responsible for the specification of this domain of the optic cup, we used a subtractive library, differential screening approach along with the construction of cDNA arrays to identify genes expressed in the ciliary epithelium of the chicken. We identified many genes specifically expressed in the ciliary epithelium, including a number that had been described previously as enriched in the ciliary epithelium of other species. By analyzing the expression of these genes during eye development, we were able to correlate the onset of ciliary epithelial gene expression with a reduction in mitotic activity in this region. We propose that the mechanisms that regulate the expression of ciliary epithelial genes are linked to the reduction in proliferation that results in the epithelial monolayer in this region.