A mechanistic model for carbon dioxide corrosion of mild steel in the presence of protective iron carbonate films - Part 3: Film growth model

A model of iron carbonate (FeCO3) film growth is proposed, which is an extension of the recent mechanistic model of carbon dioxide (CO2) corrosion by Nesic, et al. In the present model, the film growth occurs by precipitation of iron carbonate once saturation is exceeded. The kinetics of precipitation is dependent on temperature and local species concentrations that are calculated by solving the coupled species transport equations. Precipitation tends to build up a layer of FeCO3 on the surface of the steel and reduce the corrosion rate. On the other hand, the corrosion process induces voids under the precipitated film, thus increasing the porosity and leading to a higher corrosion rate. Depending on the environmental parameters such as temperature, pH, CO2 partial pressure, velocity, etc., the balance of the two processes can lead to a variety of outcomes. Very protective films and low corrosion rates are predicted at high pH, temperature, CO2 partial pressure, and Fe2+ ion concentration due to formation of dense protective films as expected. The model has been successfully calibrated against limited experimental data. Parametric testing of the model has been done to gain insight into the effect of various environmental parameters on iron carbonate film formation. The trends shown in the predictions agreed well with the general understanding of the CO2 corrosion process in the presence of iron carbonate films. The present model confirms that the concept of scaling tendency is a good tool for predicting the likelihood of protective iron carbonate film formation.

Genetic variation in foliar carbon isotope composition in relation to tree growth and foliar nitrogen concentration in clones of the F-1 hybrid between slash pine and Caribbean pine

The objectives of this study were: (1) to quantify the genetic variation in foliar carbon isotope composition (delta(13)C) of 122 clones of ca. 4-year-old F-1 hybrids between slash pine (Pinus elliottii Engelm var. elliottii) and Caribbean pine (Pinus caribaea var. hondurensis Barr.,et Golf.) grown at two field experimental sites with different water and nitrogen availability in southeast Queensland, Australia, in relation to tree growth and foliar nitrogen concentration (N-mass); and (2) to assess the potential of using delta(13)C measurements, in the foliage materials collected from the clone hedges at nursery and the 4-year-old tree canopies in the field, as an indirect index of tree water use efficiency for selecting elite F-1 hybrid pine clones with improved tree growth. There were significant differences in foliar delta(13)C between the nursery hedges and the 4-year-old tree canopies in the field, between the summer and winter seasons, between the two experimental sites, and between the upper outer and lower outer canopy positions sampled. This indicates that delta(13)C measurements in the foliage materials are significantly influenced by the sampling techniques and environmental conditions. Significant differences in foliar delta(13)C, at the upper outer canopy in both field experiments in summer and winter, were detected between the clones, and between the female parents of the clones. Clone means of tree height at age ca. 3 years were positively related to those of the upper outer canopy delta(13)C at both experimental sites in winter, but only for the wetter site in summer. There were positive, linear relationships between clone means of canopy delta(13)C and those of canopy N-mass, indicating that canopy photosynthetic capacity might be an important factor regulating the clonal variation in canopy delta(13)C. Significant correlations were found between clone means of canopy delta(13)C at both experimental sites in summer and winter, and between those at the upper outer and lower outer canopy positions. Mean clone delta(13)C for the nursery hedges was only positively related to mean clone stem diameter at 1.3 m height at age 3 years on the wetter site. The clone by site interaction for foliar delta(13)C at the upper outer canopy was significant only in summer. Overall, the relatively high genetic variance components for foliar delta(13)C and significant, positive correlations between clone means of foliar delta(13)C and tree growth have highlighted the potential of using foliar delta(13)C measurements for assisting in selection of the elite F-1 hybrid pine clones with improved tree growth. (C) 2002 Elsevier Science B.V. All rights reserved.

A comparison of the cycling performance of cyclists and triathletes

The aim of this study was to compare the cycling performance of cyclists and triathletes. Each week for 3 weeks, and on different days, 25 highly trained male cyclists and 18 highly trained male triathletes performed: (1) an incremental exercise test on a cycle ergometer for the determination of peak oxygen consumption ((V) over dot O-2peak), peak power output and the first and second ventilatory thresholds, followed 15 min later by a sprint to volitional fatigue at 150% of peak power output; (2) a cycle to exhaustion test at the (V) over dot O-2peak power output; and (3) a 40-km cycle time-trial. There were no differences in (V) over dot O-2peak, peak power output, time to volitional fatigue at 150% of peak power output or time to exhaustion at (V) over dot O-2peak power output between the two groups. However, the cyclists had a significantly faster time to complete the 40-km time-trial (56:18 +/- 2:31 min:s; mean +/- s) than the triathletes (58:57 +/- 3:06 min:s; P < 0.01), which could be partially explained (r = 0.34-0.51; P < 0.05) by a significantly higher first (3.32 +/- 0.36 vs 3.08 +/- 0.36 l . min(-1)) and second ventilatory threshold (4.05 +/- 0.36 vs 3.81 +/- 0.29 l . min(-1); both P < 0.05) in the cyclists compared with the triathletes. In conclusion, cyclists may be able to perform better than triathletes in cycling time-trial events because they have higher first and second ventilatory thresholds.

Physiological responses to repeated bouts of high-intensity ultraendurance cycling - a field study case report

The present study aimed to 1) examine the relationship between laboratory-based measures and high-intensity ultraendurance (HIU) performance during an intermittent 24-h relay ultraendurance mountain bike race (similar to20 min cycling, similar to60min recovery), and 2) examine physiological and performance based changes throughout the HIU event. Prior to the HIU event, four highly-trained male cyclists (age = 24.0 +/- 2.1 yr; mass = 75.0 +/- 2.7 kg; (V)over dot O-2peak = 70 +/- 3 ml.kg(-1).min(-1)) performed 1) a progressive exercise test to determine peak Volume of oxygen uptake ((V)over dot O-2peak), peak power output (PPO), and ventilatory threshold (T-vent), 2) time-to-fatigue tests at 100% (TF100) and 150% of PPO (TF150), and 3) a laboratory simulated 40-km time trial (TT40). Blood lactate (Lac(-)), haematocrit and haemoglobin were measured at 6-h intervals throughout the HIU event, while heart rate (HR) was recorded continuously. Intermittent HIU performance, performance HR, recovery HR, and Lac declined (P < 0.05), while plasma volume expanded (P < 0.05) during the HIU event. TF100 was related to the decline in lap time (r = -0.96; P < 0.05), and a trend (P = 0.081) was found between TF150 and average intermittent HIU speed (r = 0.92). However, other measures (V)over dot O-2peak, PPO, T-vent, and TT40) were not related to HIU performance. Measures of high-intensity endurance performance (TF100, TF150) were better predictors of intermittent HIU performance than traditional laboratory-based measures of aerobic capacity.

Nitrogen cycling in degraded Leucaena leucocephala-Brachiaria decumbens pastures on an acid infertile soil in south-east Queensland, Australia

A grazing trial was conducted to quantify N cycling in degraded Leucaena leucocephala (leucaena)-Brachiaria decumbens (signal grass) pastures grown on an acid, infertile, podzolic soil in south-east Queensland. Nitrogen accumulation and cycling in leucaena-signal grass pastures were evaluated for 9 weeks until all of the leucaena on offer (mean 600 kg edible dry matter (EDM)/ha, 28% of total pasture EDM) was consumed. Nitrogen pools in the grass, leucaena, soil, cattle liveweight, faeces and urine were estimated. The podzolic soil (pH 4.8-5.9) was found to be deficient in P, Ca and K. Leucaena leaf tissues contained deficient levels of N, P and Ca. Grass tissues were deficient in N and P. Grazing was found to cycle 65% of N on offer in pasture herbage. However, due to the effect of the plant nutrient imbalances described above, biological N fixation by leucaena contributed only 15 kg/ha N to the pasture system over the 9-month regrowth period, of which 13 kg/ha N was cycled. Cattle retained 1.8 kg/ha N (8% of total N consumed) in body tissue and the remainder was excreted in dung and urine in approximately equal proportions. Mineral soil N concentrations did not change significantly (-3.5 kg/ha N) over the trial period. The ramifications of grazing and fertiliser management strategies, and implications for pasture rundown and sustainability are discussed.

Integrated control of nitrate recirculation and external carbon addition in a predenitrification system

The integrated control of nitrate recirculation and external carbon addition in a predenitrification biological wastewater treatment system is studied. The proposed control structure consists of four feedback control loops, which manipulate the nitrate recirculation and the carbon dosage flows in a highly coordinated manner such that the consumption of external carbon is minimised while the nitrate discharge limits (based on both grab and composite samples) are met. The control system requires the measurement of the nitrate concentrations at the end of both the anoxic and the aerobic zones. Distinct from ordinary control systems, which typically minimise the variation in the controlled variables, the proposed control system essentially maximises the diurnal variation of the effluent nitrate concentration and through this maximises the use of influent COD for denitrification, thus minimising the requirement for external carbon source. Simulation studies using a commonly accepted simulation benchmark show that the controlled system consistently achieves the designated effluent quality with minimum costs.

Surface diffusion of strongly adsorbing vapors in activated carbon by a differential permeation method

Conventional methods to determine surface diffusion of adsorbed molecules are proven to be inadequate for strongly adsorbing vapors on activated carbon. Knudsen diffusion permeability (B-k) for strongly adsorbing vapors cannot be directly estimated from that of inert gases such as helium. In this paper three models are considered to elucidate the mechanism of surface diffusion in activated carbon. The transport mechanism in all three models is a combination of Knudsen diffusion, viscous flow and surface diffusion. The collision reflection factor f (which is the fraction of molecules undergoing collision to the solid surface over reflection from the surface) of the Knudsen diffusivity is assumed to be a function of loading. It was found to be 1.79 in the limit of zero loading, and decreases as loading increases. The surface diffusion permeability increases sharply at very low pressures and then starts to decrease after it has reached a maximum (B(mum)s) at a threshold pressure. The initial rapid increase in the total permeability is mainly attributed to surface diffusion. Interestingly the B(mum)s for all adsorbates appear at the same volumetric adsorbed phase concentration, suggesting that the volume of adsorbed molecules may play an important role in the surface diffusion mechanism in activated carbon. (C) 2003 Elsevier Ltd. All rights reserved.

Solubility of selected esters in supercritical carbon dioxide

The solubility of ethyl propionate, ethyl butyrate, and ethyl isovalerate in supercritical carbon dioxide was measured at temperature ranging from 308.15 to 333.15 K and pressure ranging from 85 to 195 bar. At the same temperature, the solubility of these compounds increases with pressure. The crossover pressure region was also observed in this study. The experimental data were correlated by the semi-empirical Chrastil equation and Peng-Robinson equation of state (EOS) using several mixing rules. The Peng-Robinson EOS gives better solubility prediction than the empirical Chrastil equation. (C) 2002 Elsevier Science B.V. All rights reserved.

Analysis of multicomponent adsorption kinetics on activated carbon

An integrated mathematical model for the kinetics of multicomponent adsorption on microporous carbon was developed. Transport in this bidisperse solid is represented by balance equations in the macropore and micropore phases, in which gas-phase diffusion dominates the mass transfer in the macropores, with the phenomenological diffusivities represented by the generalized Maxwell-Stefan (GMS) formulation. Viscous flow also contributes to the macropore fluxes and is included in the MS expressions. Diffusion of the adsorbed phase controls the mass transfer in the micro ore phase, p which is also described in a similar way by the MS method. The adsorption isotherms are represented by a new heterogeneous modified vacancy solution theory formulation of adsorption, which has proved to be a robust method for adsorption on activated carbons. The model is applied to the coadsorption and codesorption of C2H6 and C3H8 on Ajax and Norit carbon, as well as the displacement on Ajax carbon. The effect of the viscous flow in the macropore phase is not significant for the cases studied. The model accurately predicts the overshoot behavior and rollup of C2H6 during coadsorption. The prediction for the heavier compound C3H8 is always satisfactory, though at higher C3H8 mole fraction, the overshoot extent of C2H6 is overpredicted, possibly due to neglect of heat effects.