Titan's lakes chemical composition: sources of uncertainties and variability

Between 2004 and 2007 the instruments of the CASSINI spacecraft discovered hydrocarbon lakes in the polar regions of Titan. We have developed a lake-atmosphere equilibrium model allowing the determination of the chemical composition of these liquid areas. The model is based on uncertain thermodynamic data and precipitation rates of organic species predicted to be present in the lakes and seas that are subject to spatial and temporal variations. Here we explore and discuss the influence of these uncertainties and variations. The errors and uncertainties relevant to thermodynamic data are simulated via Monte-Carlo simulations. Global Circulation Models (GCM) are also employed in order to investigate the possibility of chemical asymmetry between the south and the north poles, due to differences in precipitation rates. We find that mole fractions of compounds in the liquid phase have a high sensitivity to thermodynamic data used as inputs, in particular molar volumes and enthalpies of vaporization. When we combine all considered uncertainties, the ranges of obtained mole fractions are rather large (up to ~8500%) but the distributions of values are narrow. The relative standard deviations remain between 10% and ~300% depending on the compound considered. Compared to other sources of uncertainties and variability, deviation caused by surface pressure variations are clearly negligible, remaining of the order of a few percent up to ~20%. Moreover no significant difference is found between the composition of lakes located in north and south poles. Because the theory of regular solutions employed here is sensitive to thermodynamic data and is not suitable for polar molecules such as HCN and CH3CN, our work strongly underlines the need for experimental simulations and the improvement of Titan's atmospheric models.Comment: Accepted in Planetary and Space Scienc

Variability of the chemical index of alteration (CIA) in the Paraná River suspended load

Variability of the chemical index of alteration (CIA) in the Paraná River suspended loa

Controls on dissolved organic carbon quantity and chemical character in temperate rivers of North America

Understanding the processes controlling the transfer and chemical composition of dissolved organic carbon (DOC) in freshwater systems is crucial to understanding the carbon cycle and the effects of DOC on water quality. Previous studies have identified watershed‐scale controls on bulk DOC flux and concentration among small basins but fewer studies have explored controls among large basins or simultaneously considered the chemical composition of DOC. Because the chemical character of DOC drives riverine biogeochemical processes such as metabolism and photodegradation, accounting for chemical character in watershed‐scale studies will improve the way bulk DOC variability in rivers is interpreted. We analyzed DOC quantity and chemical character near the mouths of 17 large North American rivers, primarily between 2008 and 2010, and identified watershed characteristics that controlled variability. We quantified DOC chemical character using both specific ultraviolet absorbance at 254 nm (SUVA254) and XAD‐resin fractionation. Mean DOC concentration ranged from 2.1 to 47 mg C L−1 and mean SUVA254 ranged from 1.3 to 4.7 L mg C−1 m−1. We found a significant positive correlation between basin wetland cover and both bulk DOC concentration (R2 = 0.78; p \u3c 0.0001) and SUVA254 (R2 = 0.91; p \u3c 0.0001), while other land use characteristics were not correlated. The strong wetland relationship with bulk DOC concentration is similar to that found by others in small headwater catchments. However, two watersheds with extremely long surface water residence times, the Colorado and St. Lawrence, diverged from this wetland relationship. These results suggest that the role of riverine processes in altering the terrestrial DOC signal at the annual scale was minimal except in river systems with long surface water residence times. However, synoptic DOC sampling of both quantity and character throughout river networks will be needed to more rigorously test this finding. The inclusion of DOC chemical character will be vital to achieving a more complete understanding of bulk DOC dynamics in large river systems

A binary nature of the marginal CP star Sigma Sculptoris

The A2 V star σ Scl was suspected of being a low-amplitude rotating variable of the Ap-type star by several authors. Aiming to decide whether the star is a variable chemically peculiar (CP) star, we searched for the photometric and spectroscopic variability, and determined chemical abundances of σ Scl. The possible variability was tested using several types of periodograms applied to the photometry from Long-Term Photometry of Variables project (LTPV) and Hipparcos. Sixty spectrograms of high signal-to-noise (S/N) were obtained and used for chemical analysis of the stellar atmosphere and for looking for spectral variability that is symptomatic for the CP stars. We did not find any signs of the light variability or prominent chemical peculiarity, that is specific for the CP stars. The only exception is the abundance of scandium, which is significantly lower than the solar one and yttrium and barium, which are strongly overabundant. As a by-product of the analysis, and with the addition of 29 further spectra, we found that σ Scl is a single-lined spectroscopic binary with orbital period of 46.877(8) d. We argue that σ Scl is not an Ap star, but rather a marginal Am star in SB1 system. The spectral energy distribution of the binary reveals infrared excess due to circumstellar material.Fil: Janík, Jan. Masaryk University; República ChecaFil: Krtička, Jiří. Masaryk University; República ChecaFil: Mikulášek, Zdeněk. Masaryk University; República ChecaFil: Zverko, Juraj. Masaryk University; República ChecaFil: Pintado, Olga Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto Superior de Correlación Geológica. Universidad Nacional de Tucumán. Facultad de Ciencias Naturales e Instituto Miguel Lillo. Departamento de Geología. Cátedra Geología Estructural. Instituto Superior de Correlación Geológica; Argentin

Solar Impact on Climate: Modeling the Coupling Between the Middle and the Lower Atmosphere

Solar variability influences the earth's atmosphere on different time scales. In particular, the impact of the 11-year solar cycle is of interest as it provides the major contribution to natural climate variability. Observations show clear 11-year variations in meteorological variables such as temperature or geopotential height from the upper atmosphere down to the troposphere and the earth's surface. In this paper the mechanisms will be discussed which are assumed to be responsible for the downward transfer of the solar signal within the atmosphere. These involve radiative, dynamical and chemical processes which have been studied in detail in model simulations and will be presented here

Impact of multiscale dynamical processes and mixing on the chemical composition of the upper troposphere and lower stratosphere during the Intercontinental Chemical Transport Experiment–North America

We use high-frequency in situ observations made from the DC8 to examine fine-scale tracer structure and correlations observed in the upper troposphere and lower stratosphere during INTEX-NA. Two flights of the NASA DC-8 are compared and contrasted. Chemical data from the DC-8 flight on 18 July show evidence for interleaving and mixing of polluted and stratospheric air masses in the vicinity of the subtropical jet in the upper troposphere, while on 2 August the DC-8 flew through a polluted upper troposphere and a lowermost stratosphere that showed evidence of an intrusion of polluted air. We compare data from both flights with RAQMS 3-D global meteorological and chemical model fields to establish dynamical context and to diagnose processes regulating the degree of mixing on each day. We also use trajectory mapping of the model fields to show that filamentary structure due to upstream strain deformation contributes to tracer variability observed in the upper troposphere. An Eulerian measure of strain versus rotation in the large-scale flow is found useful in predicting filamentary structure in the vicinity of the jet. Higher-frequency (6–24 km) tracer variability is attributed to buoyancy wave oscillations in the vicinity of the jet, whose turbulent dissipation leads to efficient mixing across tracer gradients

Evaluation of the inter-annual variability of stratospheric chemical composition in chemistry-climate models using ground-based multi species time series

The variability of stratospheric chemical composition occurs on a broad spectrum of timescales, ranging from day to decades. A large part of the variability appears to be driven by external forcings such as volcanic aerosols, solar activity, halogen loading, levels of greenhouse gases (GHG), and modes of climate variability (quasi-biennial oscillation (QBO), El Niño-Southern Oscillation (ENSO)). We estimate the contributions of different external forcings to the interannual variability of stratospheric chemical composition and evaluate how well 3-D chemistry-climate models (CCMs) can reproduce the observed response-forcing relationships. We carry out multivariate regression analyses on long time series of observed and simulated time series of several traces gases in order to estimate the contributions of individual forcings and unforced variability to their internannual variability. The observations are typically decadal time series of ground-based data from the international Network for the Detection of Atmospheric Composition Change (NDACC) and the CCM simulations are taken from the CCMVal-2 REF-B1 simulations database. The chemical species considered are column O3, HCl, NO2, and N2O. We check the consistency between observations and model simulations in terms of the forced and internal components of the total interannual variability (externally forced variability and internal variability) and identify the driving factors in the interannual variations of stratospheric chemical composition over NDACC measurement sites. Overall, there is a reasonably good agreement between regression results from models and observations regarding the externally forced interannual variability. A much larger fraction of the observed and modelled interannual variability is explained by external forcings in the tropics than in the extratropics, notably in polar regions. CCMs are able to reproduce the amplitudes of responses in chemical composition to specific external forcings. However, CCMs tend to underestimate very substantially the internal variability and hence the total interannual variability for almost all species considered. This lack of internal variability in CCMs might partly originate from the surface forcing of these CCMs by analysed SSTs. The results illustrate the potential of NDACC ground-based observations for evaluating CCMs

NMR Studies of Escherichia Coli Acyl Carrier Protein: Dynamic and Structural Differences of the Apo- and Holo-forms

Two indicators of conformational variability of Escherichia coli acyl carrier protein (ACP) have been investigated, namely backbone dynamics and chemical shift variations of ACP. Hydrophobic interactions between the 4′-PP prosthetic group and the hydrophobic pocket enclosed by the amphipathic helices resulted in chemical shift perturbations in the residues near the prosthetic group binding sites and contact sites in the hydrophobic pockets upon conversion from apo- to holo-forms. At pH 7.9, destabilization of ACP due to negative charge repulsions and the deprotonated state of His 75 resulted in observed chemical shift changes in the C-terminal region. Model-free analysis showed that the α1α2 loop region near the prosthetic group binding site in ACP shows the greatest flexibility (lowest S2 values) and this result may suggest these flexibilities are required for structural rearrangements when the acyl chain binds to the prosthetic group of ACP. Flexibility of ACP shown in this study is essential for its ability to interact with functionally different enzyme partners specifically and weakly in the rapid delivery of acyl chain from one partner to another