New experimental constraints on the composition and structure of tholins

Powdered samples of carbon-nitrogen-hydrogen “tholins” that mimic Titan's atmosphere aerosols were produced under levitation conditions in the laboratory with a dusty plasma (PAMPRE experiment) using different initial N₂:CH₄ gas mixtures and studied using UV Raman and infrared spectroscopy, X-ray diffraction and high resolution transmission electron microscopy (HRTEM). Comparison between the tholins produced in the PAMPRE experiments and samples prepared by other techniques reveal that they form a fairly homogeneous family of hydrogenated carbon nitride materials. Wall effects during the PAMPRE deposition experiments and other were found to have little effect on the chemical structure of tholins. The first-order UV Raman bands of the disordered carbonaceous materials point to a large contribution of sp² clusters present compared with olefinic CN or CC groupings, whereas features at 690 and 980 cm⁻¹ suggest C₃N₃ rings are present as a species inserted in the macromolecular network. Diffraction techniques do not indicate the presence of large polyaromatic species in any of the tholins studied, whatever their nitrogen concentration, in disagreement with certain previous observations. This precludes the idea that the nature and degree of absorption in the visible range is controlled by the size of polyaromatic species, as has been observed in series of carbon-based materials obtained via thermal processing. Infrared spectroscopy analysis of the tholins has confirmed earlier identifications of chemical groups present including primary amines, nitriles, and alkyl moieties such as CH₂/CH₃, but has ruled out CH₂/CH₃ branches appearing on secondary or tertiary amines. Similar analyses were also performed on a polymeric (HCN)_x material, which was found to present several similarities with the tholins, hence suggesting similar polymerization processes.     

Evolution of Çamlık fissure-ridge travertines in the Başkale basin (Van,Eastern Anatolia)

Fissure-ridge travertines (FRTs) are of great importance for the determination and comparison of tectonic deformation in a region. The coeval development of these travertines with active fault zones supplies significant information about regional dynamics in terms of deformation pattern and evolution. In this paper, the characteristics of FRTs of the Ba?kale basin (eastern Turkey) and responsible regional tectonism are discussed for the first time. The Ba?kale basin is located between the Ba?kale Fault Zone (BFZ) characterised by Çaml?k fault and I??kl?–Zirani? fault. It is located between dextral Yüksekova Fault Zone and southern end of dextral Guilato–Siahcheshmeh–Khoy Fault system (Iran). Various morphological features indicating recent activity are exposed along the BFZ, including offsetting rivers, fissure-ridge travertine and fault scarps. The Çaml?k fissure-ridge travertine composing of three different depositions is observed along the eastern edge of the BFZ with approximately parallel orientations. The Çaml?k fissure-ridge travertine has been formed and developed on fault zone related to strike-slip or oblique movements. We explain how kinematic changes of faults can influence the fissure-ridge development.     

Coral skeleton P/Ca proxy for seawater phosphate: Multi-colony calibration with a contemporaneous seawater phosphate record

A geochemical proxy for surface ocean nutrient concentrations recorded in coral skeleton could provide new insight into the connections between sub-seasonal to centennial scale nutrient dynamics, ocean physics, and primary production in the past. Previous work showed that coralline P/Ca, a novel seawater phosphate proxy, varies synchronously with annual upwelling-driven cycles in surface water phosphate concentration. However, paired contemporaneous seawater phosphate time-series data, needed for rigorous calibration of the new proxy, were lacking. Here we present further development of the P/Ca proxy in Porites lutea and Montastrea sp. corals, showing that skeletal P/Ca in colonies from geographically distinct oceanic nutrient regimes is a linear function of seawater phosphate (PO_4 SW) concentration. Further, high-resolution P/Ca records in multiple colonies of Pavona gigantea and Porites lobata corals grown at the same upwelling location in the Gulf of Panamá were strongly correlated to a contemporaneous time-series record of surface water PO_4 SW at this site (r² = 0.7-0.9). This study supports application of the following multi-colony calibration equations to down-core records from comparable upwelling sites, resulting in ±0.2 and ±0.1 μmol/kg uncertainties in PO_4 SW reconstructions from P. lobata and P. gigantea, respectively.

     

Bimodal distribution of the solid products in a magmatic chamber: Modelling by fractional crystallization and coupling of the chemical exchanges with the differential melt/solid transport

Our aim is to explain the possible bimodality of the compositions of the magmatic rocks of the same province. In order to do so, we present a model for the crystallization of a magmatic chamber, coupling the three phenomena: solidification, sedimentation, chemical reactions between the solid and the liquid. These three phenomena make two independent dimensionless parameters appear: the ratios of the solidification rate to the transport velocity, and of the chemical kinetics to the transport velocity. The model is written for one independent chemical component. It is shown that, for certain values of the dimensionless parameters, the chemical composition of the chamber can present a bimodal distribution, starting from uniform initial conditions. This model shows that the coupling between three elementary phenomena is enough to explain the bimodality, or more generally the appearance of discontinuities of chemical compositions, without making any additional assumption.     

Michigan basin regional ground water flow discharge to three Great Lakes

Ground water discharge to the Great Lakes around the Lower Peninsula of Michigan is primarily from recharge in riparian basins and proximal upland areas that are especially important to the northern half of the Lake Michigan shoreline. A steady-state finite-difference model was developed to simulate ground water flow in four regional aquifers in Michigan's Lower Peninsula: the Glaciofluvial, Saginaw, Parma-Bayport, and Marshall aquifers interlayered with the Till/"red beds," Saginaw, and Michigan confining units, respectively. The model domain was laterally bound by a continuous specified-head boundary, formed from lakes Michigan, Huron, St. Clair, and Erie, with the St. Clair and Detroit River connecting channels. The model was developed to quantify regional ground water flow in the aquifer systems using independently determined recharge estimates. According to the flow model, local stream stages and discharges account for 95% of the overall model water budget; only 50% enters the lakes directly from the ground water system. Direct ground water discharge to the Great Lakes' shorelines was calculated at 36 m3/sec, accounting for 5% of the overall model water budget. Lowland areas contribute far less ground water discharge to the Great Lakes than upland areas. The model indicates that Saginaw Bay receives only approximately 1.13 m3/sec ground water; the southern half of the Lake Michigan shoreline receives only approximately 2.83 m3/sec. In contrast, the northern half of the Lake Michigan shoreline receives more than 17 m3/sec from upland areas.     

Coral skeletal delta(15)N reveals isotopic traces of an agricultural revolution

This study introduces a new method of tracing the history of nutrient loading in coastal oceans via delta(15)N analysis of organic nitrogen preserved in the skeleton of the massive Porites coral. Four coral cores were collected in Bali, Indonesia, from reefs exposed to high levels of fertilizers in agricultural run-off, from lagoonal corals impacted by sewage, and from a reef located 30 km offshore. Skeletal delta(15)N in the agriculturally exposed coral declined from 10.7+/-0.4 per thousand in 1970-1971, when synthetic fertilizers (-0.8 per thousand+/-0.2 per thousand) were introduced to Bali, to a depleted "anthropogenic" baseline of 3.5 per thousand+/-0.4% in the mid-1990s. delta(15)N values were negatively correlated with rainfall, suggesting that marine delta(15)N lowers during flood-bourn influxes of waste fertilizers. Reef cores exposed to untreated sewage in terrestrial discharge were enriched (7.8 and 7.3+/-0.4 per thousand), while the offshore core reflected background oceanic signals (6.2+/-0.4 per thousand). delta(15)N, N concentration, and C:N systematics indicate that the N isotopic composition of skeletal organic matter was generally well preserved over 30 years. We suggest that skeletal organic delta(15)N can serve as a recorder of past nitrogen sources. In Bali, this tracer suggests that the intensification of Western style agricultural practices since 1970 are contributing to the degradation of coastal coral reefs.     

Photochemistry of flourine in the mesosphere of Venus

In the laboratory, reactions with flourine species proceed rapidly with high rates but under mesospheric conditions the effeciency of these compounds is low due to the rapid formation of HF and to the lack of reactivity of this species. Even if diffusion processes are included, the result of calculations leads to fluorie concentrations typically less than 20 cm^?3. The low photodissociation coeffecient of HF leads to the expectation of a scale height of HF greater than or equal to the mean scale height. If the troposphere appears to be a sink for hydrofluoric acid, the maximum value of fluorine is obtained with a downward flux of 1.3 × 10⁸ HF atoms cm^?2 sec^?1 at the level of the clouds.