Modelling the evolution of organic carbon during its gas-phase tropospheric oxidation: development of an explicit model based on a self generating approach

Organic compounds emitted in the atmosphere are oxidized in complex reaction sequences that produce a myriad of intermediates. Although the cumulative importance of these organic intermediates is widely acknowledged, there is still a critical lack of information concerning the detailed composition of the highly functionalized secondary organics in the gas and condensed phases. The evaluation of their impacts on pollution episodes, climate, and the tropospheric oxidizing capacity requires modelling tools that track the identity and reactivity of organic carbon in the various phases down to the ultimate oxidation products, CO and CO2. However, a fully detailed representation of the atmospheric transformations of organic compounds involves a very large number of intermediate species, far in excess of the number that can be reasonably written manually. This paper describes (1) the development of a data processing tool to generate the explicit gas-phase oxidation schemes of acyclic hydrocarbons and their oxidation products under tropospheric conditions and (2) the protocol used to select the reaction products and the rate constants. Results are presented using the fully explicit oxidation schemes generated for two test species: n-heptane and isoprene. Comparisons with well-established mechanisms were performed to evaluate these generated schemes. Some preliminary results describing the gradual change of organic carbon during the oxidation of a given parent compound are presented

Some Structural Changes Observed in the Transformation of Wood into Charcoal1

On the basis of measurements of microtomed cubes of white oak and on resultant charcoal, dimensional changes occurring on the conversion of wood into charcoal are: tangential, -25.68%, radial, -15.45%, and longitudinal, -11.43%. Light microscopic examination of charcoal reveals residues of combustion present in cell cavities. Electron microscopic examination indicates that the original fibrillar arrangement of the cell wall has been replaced with a smooth, "amorphous-appearing" wall structure

A Note on Effects of Sewage Effluent Irrigation on Specific Gravity and Growth Rate of White and Red Oaks

A 2.5-acre forested terrace of mixed hardwoods (predominately oak) in southern Missouri was sprinkler-irrigated with treated sewage effluent. Ninety-two oak trees were sampled (increment cores) at breast height. There were 41 white oaks and 52 red oaks. Growth rate increased significantly for white oaks and specific gravity increased significantly for red oaks

Multi-model simulations of the impact of international shipping on Atmospheric Chemistry and Climate in 2000 and 2030

The global impact of shipping on atmospheric chemistry and radiative forcing, as well as the associated uncertainties, have been quantified using an ensemble of ten state-of-the-art atmospheric chemistry models and a predefined set of emission data. The analysis is performed for present-day conditions ( year 2000) and for two future ship emission scenarios. In one scenario ship emissions stabilize at 2000 levels; in the other ship emissions increase with a constant annual growth rate of 2.2% up to 2030 ( termed the "Constant Growth Scenario" (CGS)). Most other anthropogenic emissions follow the IPCC ( Intergovernmental Panel on Climate Change) SRES ( Special Report on Emission Scenarios) A2 scenario, while biomass burning and natural emissions remain at year 2000 levels. An intercomparison of the model results with observations over the Northern Hemisphere (25 degrees - 60 degrees N) oceanic regions in the lower troposphere showed that the models are capable to reproduce ozone (O-3) and nitrogen oxides (NOx= NO+ NO2) reasonably well, whereas sulphur dioxide (SO2) in the marine boundary layer is significantly underestimated. The most pronounced changes in annual mean tropospheric NO2 and sulphate columns are simulated over the Baltic and North Seas. Other significant changes occur over the North Atlantic, the Gulf of Mexico and along the main shipping lane from Europe to Asia, across the Red and Arabian Seas. Maximum contributions from shipping to annual mean near-surface O-3 are found over the North Atlantic ( 5 - 6 ppbv in 2000; up to 8 ppbv in 2030). Ship contributions to tropospheric O3 columns over the North Atlantic and Indian Oceans reach 1 DU in 2000 and up to 1.8 DU in 2030. Tropospheric O-3 forcings due to shipping are 9.8 +/- 2.0 mW/m(2) in 2000 and 13.6 +/- 2.3 mW/m(2) in 2030. Whilst increasing O-3, ship NOx simultaneously enhances hydroxyl radicals over the remote ocean, reducing the global methane lifetime by 0.13 yr in 2000, and by up to 0.17 yr in 2030, introducing a negative radiative forcing. The models show future increases in NOx and O-3 burden which scale almost linearly with increases in NOx emission totals. Increasing emissions from shipping would significantly counteract the benefits derived from reducing SO2 emissions from all other anthropogenic sources under the A2 scenario over the continents, for example in Europe. Globally, shipping contributes 3% to increases in O-3 burden between 2000 and 2030, and 4.5% to increases in sulphate under A2/CGS. However, if future ground based emissions follow a more stringent scenario, the relative importance of ship emissions will increase. Inter-model differences in the simulated O-3 contributions from ships are significantly smaller than estimated uncertainties stemming from the ship emission inventory, mainly the ship emission totals, the distribution of the emissions over the globe, and the neglect of ship plume dispersion

Exact zero-point energy shift in the e⊗(n E)e\otimes (n~E), t⊗(n H)t\otimes (n~H) many modes dynamic Jahn-Teller systems at strong coupling

We find the exact semiclassical (strong coupling) zero-point energy shifts applicable to the $e\otimes (n E)$ and $t\otimes (n H)$ dynamic Jahn-Teller problems, for an arbitrary number $n$ of discrete vibrational modes simultaneously coupled to one single electronic level. We also obtain an analytical formula for the frequency of the resulting normal modes, which has an attractive and apparently general Slater-Koster form. The limits of validity of this approach are assessed by comparison with O'Brien's previous effective-mode approach, and with accurate numerical diagonalizations. Numerical values obtained for $t\otimes (n H)$ with $n =8$ and coupling constants appropriate to C$_{60}^-$ are used for this purpose, and are discussed in the context of fullerene.Comment: 20 pages, 4 ps figure

Organic chemistry of NH₃ and HCN induced by an atmospheric abnormal glow discharge in N₂-CH₄ mixtures

The formation of the chemical products produced in an atmospheric glow discharge fed by a N2-CH4 gas mixture has been studied using Fourier Transform InfraRed (FTIR) and Optical Emission Spectrometry (OES). The measurements were carried out in a flowing regime at ambient temperature and pressure with CH4 concentrations ranging from 0.5% to 2%. In the recorded emission spectra the lines of the second positive system CN system and the first negative system of N2 were found to be the most intensive but atomic Hα, Hβ, and C (247 nm) lines were also observed. FTIR-measurements revealed HCN and NH3 to be the major products of the plasma with traces of C2H2. These same molecules have been detected in Titan's atmosphere and the present experiments may provide some novel insights into the chemical and physical mechanisms prevalent in Titan's atmosphere with these smaller species believed to be the precursors of heavier organic species in Titan's atmosphere and on its surface

Possibility of long-range order in clean mesoscopic cylinders

A microscopic Hamiltonian of the magnetostatic interaction is discussed. This long-range interaction can play an important role in mesoscopic systems leading to an ordered ground state. The self-consistent mean field approximation of the magnetostatic interaction is performed to give an effective Hamiltonian from which the spontaneous, self-sustaining currents can be obtained. To go beyond the mean field approximation the mean square fluctuation of the total momentum is calculated and its influence on self-sustaining currents in mesoscopic cylinders with quasi-1D and quasi-2D conduction is considered. Then, by the use of the microscopic Hamiltonian of the magnetostatic interaction for a set of stacked rings, the problem of long-range order is discussed. The temperature $T^{*}$ below which the system is in an ordered state is determined.Comment: 14 pages, REVTeX, 5 figures, in print in Phys. Rev.

Magnetic Response in a Zigzag Carbon Nanotube

Magnetic response of interacting electrons in a zigzag carbon nanotube threaded by a magnetic flux is investigated within a Hartree-Fock mean field approach. Following the description of energy spectra for both non-interacting and interacting cases we analyze the behavior of persistent current in individual branches of a nanotube. Our present investigation leads to a possibility of getting a filling-dependent metal-insulator transition in a zigzag carbon nanotube.Comment: 9 pages, 14 figure