Kinetic and thermodynamic analysis of Creosote degradation process under isothermal experimental conditions.

Isothermal degradation process of commercial Creosote was analyzed by the thermogravimetric (TG) technique in a nitrogen atmosphere, at four different operating temperatures (230, 250, 270 and 290°C). The kinetic triplet [Ea , A and f(α)] and the thermodynamic parameters (ΔH (≠), ΔS (≠)and ΔG (≠)) for investigated Creosote samples were calculated. It was found that two-parameter autocatalytic Sesták-Berggren (SB) kinetic model best describes the process, but in the form of accommodation function with phenomenological character. Applying the multiplicative factor, the true value of activation energy (E (true) a ) was calculated. The experimental density distribution function of the apparent activation energy values was evaluated from isoconversional kinetic analysis. Based of the characteristic shape of distribution curve, it was concluded that the isothermal degradation of Creosote represents a complex physico-chemical process, given the chemical structure of the studied system. It is assumed that the considered process probably includes primary and secondary (autocatalytic) pyrolysis reactions, together with various decomposition reactions and radicals recombination pathways. The objective of the presented work is the proof of principle of the pyrolysis-based thermo-chemical conversion technologies for the production of value-added chemicals from the complex organic compounds, which even include chemical contaminants (such as PAHs). Also, the present work allows us that by using a unified kinetic approach we can obtain a significant physico-chemical characteristics of the tested system, which can then be used in the procedure for the separation of organics from creosote-treated woods and creosote-contaminated soils. The significance of this research is to identify the global kinetic behavior of some target contaminant compounds for pyrolysis, which are primarily PAHs.

Tritium concentration analysis in atmospheric precipitation in Serbia.

Tritium activity concentration were monitored in monthly precipitation at five locations in Serbia (Meteorological Station of Belgrade at Zeleno Brdo, Vinca Institute of Nuclear Sciences, Smederevska Palanka, Kraljevo and Nis) over 2005, using electrolytic enrichment and liquid scintillation counting. The obtained concentrations ranged from 3.36 to 127.02 TU. The activity values obtained in samples collected at Zeleno Brdo were lower or close to the minimum detectable activity (MDA), which has a value of 3.36 TU. Significantly higher tritium levels were obtained in samples collected in Vinca Institute of Nuclear Sciences compared with samples from the other investigated locations. Amount of precipitation were also recorded. A good linear correlation (r = 0.75) for Zeleno Brdo and VINS between their tritium activity was obtained. It was found that the value of the symmetrical index n (which indicates the magnitude of tritium content changes with time (months) through its second derivative) is the highest for Vinca Institute of Nuclear Sciences compared to other locations, which is in accordance with the fact that the highest concentrations of tritium were obtained in the samples from the cited place.