Thermal oxidative degradation kinetics of agricultural residues using distributed activation energy model and global kinetic model.

The study concerned the thermal oxidative degradation kinetics of agricultural residues, peanut shell (PS) and sunflower shell (SS). The thermal behaviors were evaluated via thermogravimetric analysis and the kinetic parameters were determined by using distributed activation energy model (DAEM) and global kinetic model (GKM). Results showed that thermal oxidative decomposition of two samples processed in three zones; the ignition, burnout, and comprehensive combustibility between two agricultural residues were of great difference; and the combustion performance could be improved by boosting heating rate. The activation energy ranges calculated by the DAEM for the thermal oxidative degradation of PS and SS were 88.94-145.30 kJ mol-1 and 94.86-169.18 kJ mol-1, respectively. The activation energy obtained by the GKM for the oxidative decomposition of hemicellulose and cellulose was obviously lower than that for the lignin oxidation at identical heating rate. To some degree, the determined kinetic parameters could acceptably simulate experimental data.

Evaluation of agricultural residues pyrolysis under non-isothermal conditions: Thermal behaviors, kinetics, and thermodynamics.

The thermal conversion characteristics, kinetics, and thermodynamics of agricultural residues, rape straw (RS) and wheat bran (WB), were investigated under non-isothermal conditions. TGA experiments showed that the pyrolysis characteristics of RS were quite different from those of WB. As reflected by the comprehensive devolatilization index, when the heating rate increased from 10 to 30Kmin-1, the pyrolysis performance of RS and WB were improved 5.27 and 5.96 times, respectively. The kinetic triplets of the main pyrolysis process of agricultural residues were calculated by the Starink method and the integral master-plots method. Kinetic analysis results indicated that the most potential kinetic models for the pyrolysis of RS and WB were D2 and F2.7, respectively. The thermodynamic parameters (ΔH, ΔG, and ΔS) were determined by the activated complex theory. The positive ΔH, positive ΔG, and negative ΔS at characteristic temperatures validated that the pyrolysis of agricultural residues was endothermic and non-spontaneous.

Comparative evaluation of thermal oxidative decomposition for oil-plant residues via thermogravimetric analysis: Thermal conversion characteristics, kinetics, and thermodynamics.

Thermal oxidative decomposition characteristics, kinetics, and thermodynamics of rape straw (RS), rapeseed meal (RM), camellia seed shell (CS), and camellia seed meal (CM) were evaluated via thermogravimetric analysis (TGA). TG-DTG-DSC curves demonstrated that the combustion of oil-plant residues proceeded in three stages, including dehydration, release and combustion of organic volatiles, and chars oxidation. As revealed by combustion characteristic parameters, the ignition, burnout, and comprehensive combustion performance of residues were quite distinct from each other, and were improved by increasing heating rate. The kinetic parameters were determined by Coats-Redfern approach. The results showed that the most possible combustion mechanisms were order reaction models. The existence of kinetic compensation effect was clearly observed. The thermodynamic parameters (ΔH, ΔG, ΔS) at peak temperatures were calculated through the activated complex theory. With the combustion proceeding, the variation trends of ΔH, ΔG, and ΔS for RS (RM) similar to those for CS (CM).

[Effects of long-term application of fertilizers on soil microbial biomass nitrogen and organic nitrogen components in subtropical paddy soils].

The effect of long-term fertilization on soil organic nitrogen components and microbial biomass nitrogen (B(N)) in paddy soils from two experiment sites in Hunan province were studied. Soil samples were collected from the plough layers of different fertilizer treatments. Soil B(N) was measured by the fumigation-extraction method, and soil organic N was fractionated by acid hydrolysis-distillation method according to the scheme of Bremner (1965). Results showed that the soil N increased 40 mg x kg(-1) every year at Ningxiang site (low N level) for 17 years under the application combined of fertilizers and manure, while that at Nanxian site (high N level) was 55 mg x kg(-1). Soil total nitrogen (T(N)), total hydrolysable nitrogen (THN) and microbial biomass nitrogen(B(N)) were increased by long-term combined application of chemical fertilizer and manure (NPKM). NPKM significantly increased the content of T(N), B(N), total hydrolysable nitrogen (THN), ammonia acid nitrogen (AAN), hydrolysable unidentified nitrogen (HUN) and the percentage of B(N) to T(N). Besides, NPKM increased the easily mineralizable B(N), AAN, and low decomposed HUN. There was positive correlated relationship between B(N) and THN and different THN components, and the effect of AAN and HUN on B(N) was biggest. It is obvious that NPKM increased soil fertility and enhanc the nitrogen-supplying capability of paddy soils. NPKM had the effect on increasing soil nitrogen capability of paddy soils, both easily decomposed fractions and difficultly decomposed ones.

[Seasonal characteristics of CO2 fluxes from the paddy ecosystem in subtropical region].

CO2 fluxes from paddy ecosystem in subtropical hilly region were measured continuously using eddy covariance technique. Based on data rejecting, correcting and filling, the daily and annual CO2 fluxes were calculated from the instantaneous values, respectively. The objectives were to investigate the variation of CO2 fluxes on seasonal temporal scale, analyze the relationship between CO2 fluxes and environmental factors, and to quantify the annual net ecosystem exchange (NEE) from the paddy ecosystem. Results show the values of GPP, R(eco) and NEE are higher from Jun. to Sep. and lower in the other months. The NEE from May to Sep. accounted for above 80% of the annual value and is crucial to the whole annual value. Photosynthetically active radiation (PAR) and mean daily air temperature (T(a)) were two main influential factors for controlling the seasonal trend of GPP and NEE and could be described by binary linear functions, respectively. The annual NEE in paddy ecosystem was 2 475.6 g/(m2 x a). This is showed that paddy ecosystem was a carbon sink for the atmosphere in subtropical region.

[Effects of temperature on organic carbon mineralization in paddy soils with different clay content].

An incubation test with three kinds of paddy soil (sandy loam, clay loam, and silty clay soils) in subtropical region was conducted at 10, 15, 20, 25 and 30 degrees C to examine the response of the mineralization of soil organic carbon (SOC) to temperature change. The results showed that during the period of 160 d incubation, the accumulative mineralized amount of SOC in sandy loam, clay loam, and silty clay soils at 30 degrees C was 3.5, 5.2 and 4.7 times as much as that at 10 degrees C, respectively. The mineralization rate was lower and relatively stable at lower temperatures (< or = 20 C), but was higher at the beginning of incubation and decreased and became stable as the time prolonged at higher temperatures (> or = 25 degrees C). During incubation, the temperature coefficient (Q10) of SOC mineralization in test soils fluctuated, with an average Q10 in sandy loam, clay loam, and silty clay soils being 1.92, 2.37 and 2.32, respectively. There was a positive exponential correlation between SOC mineralization constant k and temperature (P < 0.01), and the response of SOC mineralization to temperature change was in the order of clay loam soil > silty clay soil > sandy loam soil.