Titan's atmospheric chemistry: Photolysis of gas mixtures containing hydrogen cyanide and carbon monoxide at 185 and 254 nm

The formation of organic compounds in the atmosphere of Titan is an ongoing process of the generation of complex organics from the simplest hydrocarbon, methane. Solar radiation and magnetosphere electrons are the main energy sources that drive the reactions in Titan's atmosphere. Since energy from solar radiation is 200 times greater than that from magnetosphere electrons, we have investigated the products formed by the action of UV radiation (185 and 254 nm) on a mixture of gases containing nitrogen, methane, hydrogen, acetylene, ethylene, and cyanoacetylene, the basic gas mixture (BGM) that simulates aspects of Titan's atmosphere using a flow reactor [Tran, B.N., Ferris, J.P., Chera, J.J., 2003a. Icarus 162, 114-124; Tran, B.N., Joseph, J.C., Force, M., Briggs, R.G., Vuitton, V., Ferris, J.P., 2005. Icarus 177, 106-115]. The present research extends these studies by the addition of carbon monoxide and hydrogen cyanide to the BGM. Quantum yields for the loss of reactants and the formation of volatile products were determined and compared with those measured in the absence of the hydrogen cyanide and carbon monoxide. The GCMS analyses of the volatile photolysis products from the BGM, with added hydrogen cyanide, had a composition similar to that of the BGM while the photolysis products of the BGM with added carbon monoxide contained many oxygenated compounds. The infrared spectrum of the corresponding solid product revealed the absorption band of a ketone group, which was probably formed from the reaction of carbon monoxide with the free radicals generated by photolysis of acetylene and ethylene. Of particular interest was the observation that the addition of HCN to the gas mixture only resulted in a very small change in the C/N ratio and in the intensity of the CN frequency at 2210 cm⁻¹ in the infrared spectrum suggesting that little HCN is incorporated into the haze analog. The C/N ratio of the haze analogs was found to be in the 10-12 range. The UV spectra of the solid products formed when HCN or CO added to the BGM is similar to the UV absorption formed from the BGM alone. This result is consistent with absence of additional UV chromophores to the solid product when these mixtures are photolyzed. The following photoproducts, which were not starting materials in our photochemical studies, have been observed on Titan: acetonitrile, benzene, diacetylene, ethane, propene, propane, and propyne.     

Determination of predevelopment denudation rates of an agricultural watershed (Cayaguás River, Puerto Rico) using in-situ-produced Be in river-borne quartz

Accurate estimates of watershed denudation absent anthropogenic effects are required to develop strategies for mitigating accelerated physical erosion resulting from human activities, to model global geochemical cycles, and to examine interactions among climate, weathering, and uplift. We present a simple approach to estimate predevelopment denudation rates using in-situ-produced cosmogenic ¹⁰Be in fluvial sediments. Denudation processes in an agricultural watershed (Cayaguás River Basin, Puerto Rico) and a matched undisturbed watershed (Icacos River Basin) were compared using ¹⁰Be concentrations in quartz for various size fractions of bed material. The coarse fractions in both watersheds bear the imprint of long subsurface residence times. Fine material from old shallow soils contributes little, however, to the present-day sediment output of the Cayaguás. This confirms the recent and presumably anthropogenic origin of the modern high denudation rate in the Cayaguás Basin and suggests that pre-agricultural erosional conditions were comparable to those of the present-day Icacos.     

Mercury: Internal structure and thermal evolution

Astronomical observations and cosmochemical calculations suggest that the planet Mercury may be composed of materials which condensed at relatively high temperatures in the primitive solar nebula and may have a basaltic crust similar to parts of the moon. These findings, plus the long standing inference that Mercury is much richer in metallic iron than the other terrestrial planets, provide important constraints which we apply to models of the thermal evolution and density structure of the planet. The thermal history calculations include explicitly the differing thermal properties of iron and silicates and account for core segregation, melting and differentiation of heat sources, and simulated convection during melting. If the U and Th abundances of Mercury are taken from the cosmochemical model of Lewis, then the planet would have fully differentiated a metal core from the silicate mantle for all likely initial temperature distributions and heat transfer properties. Density distributions for the planet are calculated from the mean density and estimates of the present-day temperature. For the fully differentiated model, the moment of inertia C/MR² is 0.325 (J₂=0.302×10^?6). For models with lower heat source abundances, the planet may not yet have differentiated. The density profiles for such models give C/MR²=0.394 (J₂=0.487×10^?6). These results should be useful for preliminary interpretation of the Mariner 10 measurements of Mercury's gravitational field.     

From A to B,randomly: a point-to-point random trajectory generator for animal movement

For applications in animal movement, we propose a random trajectory generator (RTG) algorithm that combines the concepts of random walks, space-time prisms, and the Brownian bridge movement model and is capable of efficiently generating random trajectories between a given origin and a destination point, with the least directional bias possible. Since we provide both a planar and a spherical version of the algorithm, it is suitable for simulating trajectories ranging from the local scale up to the (inter-)continental scale, as exemplified by the movement of migrating birds. The algorithm accounts for physical limitations, including maximum speed and maximum movement time, and provides the user with either single or multiple trajectories as a result. Single trajectories generated by the RTG algorithm can be used as a null model to test hypotheses about movement stimuli, while the multiple trajectories can be used to create a probability density surface akin to Brownian bridges.     

Climate driven coevolution of weathering profiles and hillslope topography generates dramatic differences in critical zone architecture

Considerable debate revolves around the relative importance of rock type, tectonics, and climate in creating the architecture of the critical zone. We demonstrate the importance of climate and in particular the rate of water recharge to the subsurface, using numerical models that incorporate hydrologic flowpaths, chemical weathering, and geomorphic rules for soil production and transport. We track alterations in both solid phase (plagioclase to clay) and water chemistry along hydrologic flowpaths that include lateral flow beneath the water table. To isolate the role of recharge, we simulate dry and wet cases and prescribe identical landscape evolution rules. The weathering patterns that develop differ dramatically beneath the resulting parabolic interfluves. In the dry case, incomplete weathering is shallow and surface parallel, whereas in the wet case, intense weathering occurs to depths approximating the base of the bounding channels, well below the water table. Exploration of intermediate cases reveals that the weathering state of the subsurface is strongly governed by the ratio of the rate of advance of the weathering front itself controlled by the water input rate, and the rate of erosion of the landscape. The system transitions between these end‐member behaviours rather abruptly at a weathering front speed ‐ erosion rate ratio of approximately 1. Although there are undoubtedly direct roles for tectonics and rock type in critical zone architecture, and yet more likely feedbacks between these and climate, we show here that differences in hillslope‐scale weathering patterns can be strongly controlled by climate.     

Reply to the Discussion by Rose of Phelps et al. (2014) ‘Oceanographic and eustatic control of carbonate platform evolution and sequence stratigraphy on the Cretaceous (Valanginian–Campanian) passive margin,northern Gulf of Mexico’, Sedimentology, 61, 461–496

Discussion points raised by Rose ( 2016 ) concentrate on late Albian stratigraphic relationships between formations of the East Texas Basin and the San Marcos Arch of the Comanche Platform in the northern Gulf of Mexico. Criticisms of Phelps et al. (2014) regarding stratigraphic nomenclature, palaeogeography and regional lithostratigraphic correlations generally focus on interpretive aspects of the study or do not account for the full scope of published information. Revisions to the top Aptian–Albian Supersequence boundary by Rose are incompatible with the relative location of a subaerial unconformity, as well as deepening lithofacies trends and retrogradational stratigraphic patterns below the interpreted boundary. Rose's placement of the top Aptian–Albian Supersequence boundary precisely at the Albian–Cenomanian stage boundary also implies ca 1·4 Ma of diachroneity in second order sea‐level patterns between the northern Gulf of Mexico and other documented global sedimentary basins.     

Importance of water quality to nekton habitat use in a North Carolina Branch estuary

Nekton abundance and water quality were examined over 8 yr (1986–1993) in Isaac Creek, a small (2.5 km long), shallow (1–2 m), estuarine creek draining to Adams Creek (Neuse River system), North Carolina, United States. Water quality and nekton were sampled at 8 to 12 stations at 2–3 wk intervals from April to October (76 dates). The nekton assemblage, sampled by trawl, included 42 taxa but was dominated by 11 species (7 fish and 4 decapod crustaceans). Nekton and water quality (temperature, salinity, dissolved oxygen [DO], salinity gradient) data were grouped and analyzed by three (upper, middle, and lower) creek zones to determine if estimated abundance was correlated with water quality. Potentially stressful water quality conditions for salinity (<5 ppt), temperature (>30°C in morning), and DO (<2 mg 1⁻¹) mainly occurred in the upper and middle zones. The most frequent occurrence of potentially stressful conditions for salinity was in the spring and for dissolved oxygen and temperature in middle to late summer. The frequency of potentially stressful conditions increased during a 3-yr period following timber harvest of a large portion of the watershed. Canonical correspondence analysis (CCA) suggested little correlation between the top 11 species and water quality and indicated an assemblage with regular seasonal changes. Comparison of nekton use of the middle and upper zones of the creek for 3-yr pre- and post-harvest periods showed an increase in proportion of nekton caught in those zones, despite the higher frequency of potentially stressful water quality conditions. This observation suggests that a complex set of factors, including water quality, influence the pattern of nekton use in Isaac Creek.     

A high-resolution TEM-AEM, pH titration, and modeling study of Zn coprecipitation with ferrihydrite

Experiments of Zn²⁺ and Fe³⁺ coprecipitation as a function of pH were conducted in the laboratory at ambient temperature and pressure. X-ray diffraction patterns of the coprecipitates show two broad peaks at 0.149 and 0.258 nm, which is consistent with published patterns for pure 2-line ferrihydrite. Zn²⁺ uptake occurred at pH ≥5 while Fe³⁺ precipitation occurred between pH 3 and 4, although both Zn²⁺ and Fe³⁺ were present in the same solution during the entire range of pH titration. High-resolution transmission electron microscopy shows that the coprecipitates are 2 to 6 nm sized single crystalline particles but aggregated to 50 to 400 nm sized clusters. Analytical electron microscopy indicated that the 5% atomic Zn with respect to Fe was homogeneously distributed. No segregated phases were found in the clusters or at single crystal edges, which is consistent with published extended X-ray absorption fine structure (EXAFS) results at similar Zn/(Zn + Fe) ratios. Hence, occlusion and surface precipitation may be excluded as possible coprecipitation mechanisms. The bulk solution Zn²⁺ sorption edge was fitted to both solid solution and generalized diffuse layer surface complexation models. However, a solid solution model is inconsistent with published EXAFS results that show tetrahedral polydentate Zn²⁺ complexes sharing apices with Fe³⁺octahedra.