Sequestration of carbon by soil

Soil carbon is a major component of the terrestrial carbon cycle. The soils of the world contain more carbon than the combined total amounts occurring in vegetation and the atmosphere. Consequently, soils are a major reservoir of carbon and an important sink. Because of the relatively long period of time that carbon spends within the soil and is thereby withheld from the atmosphere, it is often referred to as being sequestered. Increasing the capacity of soils to sequester C provides a partial, medium-term countermeasure to help ameliorate the increasing CO2 levels in the atmosphere arising from fossil fuel burning and land clearing. Such action will also help to alleviate the environmental impacts arising from increasing levels of atmospheric CO2. The C sequestration potential of any soil depends on its capacity to store resistant plant components in the medium term and to protect and accumulate the humic substances (HS) formed from the transformations or organic materials in the soil environment. The sequestration potential of a soil depends on the vegetation it supports, its mineralogical composition, the depth of the solum, soil drainage, the availability of water and air, and the temperature of the soil environment. The sequestration potential also depends on the chemical characteristics of the soil organic matter and its ability to resist microbial decomposition. When accurate information for these features is incorporated in model systems, the potentials of different soils to sequester C can be reliably predicted. It is encouraging to know that improved soil and crop management systems now allow field yields to be maintained and soil C reserves to be increased, even for soils with depleted levels of soil C. Estimates of the soil C sequestration potential are discussed. Inevitably HS are the major components of the additionally sequestered C. It will be important to know more about the compositions and associations of these substances in the soil if we are able to predict reasonably accurately the ability of any soil type to sequester C in different cropping and soil management systems.

Control of dimethylsulfoxide reductase expression in Rhodobacter capsulatus: the role of carbon metabolites and the response regulators DorR and RegA

Regulation of the expression of dimethylsulfoxide (DMSO) reductase was investigated in the purple phototrophic bacterium Rhodobacter capsulatus. Under phototrophic, anaerobic conditions with malate as carbon source, DMSO caused an approximately 150-fold induction of DMSO reductase activity. The response regulator DorR was required for DMSO-dependent induction and also appeared to slightly repress DMSO reductase expression in the absence of substrate. Likewise, when pyruvate replaced malate as carbon source there was an induction of DMSO reductase activity in cells grown at low light intensity (16 W m(-2)) and again this induction was dependent on DorR. The level of DMSO reductase activity in aerobically grown cells was elevated when pyruvate replaced malate as carbon source. One possible explanation for this is that acetyl phosphate, produced from pyruvate, may activate expression of DMSO reductase by direct phosphorylation of DorR, leading to low levels of induction of dor gene expression in the absence of DMSO. A mutant lacking the global response regulator of photosynthesis gene expression, RegA, exhibited high levels of DMSO reductase in the absence of DMSO, when grown phototrophically with malate as carbon source. This suggests that phosphorylated RegA acts as a repressor of dor operon expression under these conditions. It has been proposed elsewhere that RegA-dependent expression is negatively regulated by the cytochrome cbb(3) oxidase. A cco mutant lacking cytochrome cbb(3) exhibited significantly higher levels of Phi[dorA::lacZ] activity in the presence of DMSO compared to wild-type cells and this is consistent with the above model. Pyruvate restored DMSO reductase expression in the regA mutant to the same pattern as found in wild-type cells. These data suggest that R. capsulatus contains a regulator of DMSO respiration that is distinct from DorR and RegA, is activated in the presence of pyruvate, and acts as a negative regulator of DMSO reductase expression.

Accurate orientation relationship between ferrite and austenite in low carbon martensite and granular bainite

Convergent beam Kikuchi diffraction was used to accurately determine the orientation relationships (ORs) between austenite and martensite, and between austenite and granular bainite in two Fe-Ni-Mn-C alloys. Both martensite and granular bainite have the same crystallographic characteristics with the OR: (111)(A)parallel to(101)(F), [1 (1) over bar0](A) 2.5degrees +/- 2degrees from [1 (1) over bar(1) over bar](B).

Relationship between stress-induced martensitic transformation and impact toughness in low carbon austenitic steels

The effect of test temperature, which controls the stability of austenite, on the impact toughness of a low carbon Fe-Ni-Mn-C austenitic steel and 304 stainless steel, has been investigated. Under impact conditions, stress-induced martensitic transformation occurred, in a region near the fracture surface, at test temperatures below 80degreesC for the Fe-Ni-Mn-C steel and below -25degreesC for 304 stainless steel. The former shows significant transformation toughening and the highest impact toughness was obtained at 10degreesC, which corresponds to the maximum amount of martensite formed by stress-induced transformation above the Ms temperature. The stress-induced martensitic transformation contributes negatively to the impact toughness in the 304 stainless steel. Increasing the amount of stress-induced transformation to martensite, lowered the impact toughness. The experimental results can be well explained by the Antolovich theory through the analysis of metallography and fractography. The different effect of stress-induced transformation on the impact toughness in Fe-Ni-Mn-C steel and 304 stainless steel has been further understood by applying the crystallographic model for stress-induced martensitic transformation to these two steels. (C) 2002 Kluwer Academic Publishers.

Molecular orbital theory calculations of the H2O-carbon reaction

Carbon gasification with steam to produce H-2 and CO is an important reaction widely used in industry for hydrogen generation. Although the literature is vast, the. mechanism for the formation of H-2 is still unclear. In particular, little has, been done to investigate the potential of molecular orbital theory to distinguish different mechanism possibilities. In this work, we used molecular orbital theory to demonstrate a favorable energetic pathway where H2O is first physically adsorbed on the virgin graphite surface with negligible change in molecular structure. Chemisorption occurs via O approaching the carbon edge site with one H atom stretching away from the O in the transition state. This is followed by a local minimum. state in which the stretching H is further disconnected from the O atoms and the remaining OH group is still on the carbon edge site. The disconnected H then pivot around the OH group to bond with the H of the OH group and forms H-2. The O atom remaining on the carbon edge site is subsequently desorbed as CO. The reverse occurs when H-2 reacts with the surface oxygen to produce H2O.

Effects of the solute ionization on the adsorption of aromatic compounds from dilute aqueous solutions by activated carbon

Adsorption of four dissociating aromatic compounds and one nondissociating compound on a commercial activated carbon is investigated systematically. All adsorption experiments were carried out in pH-controlled aqueous solutions. The adsorption isotherms are fitted to the binary homogeneous Langmuir model, where the concentrations of the molecular and the ionic species in the liquid phase are expressed in terms of the sum of the two and the degree of solute ionization. Examination of the relationships between the solution pH, the degree of ionization of the solutes, and the model parameters is found to give new insights into the adsorption process. Furthermore, this is used to correlate the variation of the monolayer capacity with the solution pH.

Comparison of adsorption capacity of p-Cresol & p-Nitrophenol by activated carbon in single and double solute

Adsorption of p-Cresol and p-Nitrophenol by untreated activated carbon in single and multisolute solutions was carried out at 301 K and at controlled pH conditions. In acidic conditions, well below the pK(a) of both solutes, it was observed that the adsorbate solubility and the electron density of aromatic rings influenced the extent of adsorption by affecting the extent of London dispersion forces. The fitted parameters obtained from single-solute Langmuir equation show that Q(max) and the adsorption affinity of carbon for the compound with low pK(a) decrease more significantly. In higher solution pH conditions, on the other hand, it was found that electrostatic forces played a significant role on the extent of adsorption. The presence of another compound decreases Q(max) and the adsorption affinity of carbon for the principal compound. The effect of pH, on the carbon surface and on the solute molecules, must be considered. Adsorption of the solute at higher pH values was found to be dependent on the concentration of anionic form of the solute. The isotherm data were fitted to the Langmuir isotherm equation for both single and double solute solutions.

Role of oxygen in the nitrous oxide/carbon reaction

An investigation of the role of oxygen in the nitrous oxide/carbon reaction was carried out on various carbon samples (both graphitic and nongraphitic) over a range of temperatures and partial pressures. Previous work reported that oxygen strongly inhibited the nitrous oxide/carbon reaction. Large ratios of O-2/N2O were used in all previous work. In this work, the O-2/N2O ratio was kept below 1, and we found that oxygen did not inhibit the rate of the C + N2O reaction. Instead, the rate of the reaction in the presence of oxygen was essentially that predicted by the two independent reactions, nitrous oxide/carbon and oxygen/carbon, occurring simultaneously. A simple theoretical explanation is given for the observations, both past and present, on the basis of competitive chemisorption of nitrous oxide and oxygen on active sites.

Close packed transitions in slit-shaped pores: Density functional theory study of methane adsorption capacity in carbon

An important feature of improving lattice gas models and classical isotherms is the incorporation of a pore size dependent capacity, which has hitherto been overlooked. In this paper, we develop a model for predicting the temperature dependent variation in capacity with pore size. The model is based on the analysis of a lattice gas model using a density functional theory approach at the close packed limit. Fluid-fluid and solid-fluid interactions are modeled by the Lennard-Jones 12-6 potential and Steele's 10-4-3, potential respectively. The capacity of methane in a slit-shaped carbon pore is calculated from the characteristic parameters of the unit cell, which are extracted by minimizing the grand potential of the unit cell. The capacities predicted by the proposed model are in good agreement with those obtained from grand canonical Monte Carlo simulation, for pores that can accommodate up to three adsorbed layers. Single particle and pair distributions exhibit characteristic features that correspond to the sequence of buckling and rhombic transitions that occur as the slit pore width is increased. The model provides a useful tool to model continuous variation in the microstructure of an adsorbed phase, namely buckling and rhombic transitions, with increasing pore width. (C) 2002 American Institute of Physics.

Use of liquid phase adsorption for characterizing pore network connectivity in activated carbon

A simple percolation theory-based method for determination of the pore network connectivity using liquid phase adsorption isotherm data combined with a density functional theory (DFT)-based pore size distribution is presented in this article. The liquid phase adsorption experiments have been performed using eight different esters as adsorbates and microporous-mesoporous activated carbons Filtrasorb-400, Norit ROW 0.8 and Norit ROX 0.8 as adsorbents. The density functional theory (DFT)-based pore size distributions of the carbons were obtained using DFT analysis of argon adsorption data. The mean micropore network coordination numbers, Z, of the carbons were determined based on DR characteristic plots and fitted saturation capacities using percolation theory. Based on this method, the critical molecular sizes of the model compounds used in this study were also obtained. The incorporation of percolation concepts in the prediction of multicomponent adsorption equilibria is also investigated, and found to improve the performance of the ideal adsorbed solution theory (IAST) model for the large molecules utilized in this study. (C) 2002 Elsevier Science B.V. All rights reserved.

On the validity of thermogravimetric determination of carbon gasification kinetics

Thermogravimetric analysis has been widely applied in kinetic studies of carbon gasification, with the associated temporal weight change profiles being used to extract kinetic information and to validate gasification models. However the weight change profiles are not always governed by the intrinsic gasification activity because of the effect of chemisorption and its dynamics. In the present work we theoretically determine the criteria under which weight change profiles can be used to determine intrinsic kinetics for CO2 and O2 gasification by examining the region in which the chemisorption dynamics can be assumed pseudo-steady. It is found that the validity of the pseudo-steady assumption depends on the experimental conditions as well as on the initial surface area of carbon. Based on known mechanisms and rate constants an active surface area region is identified within which the steady state assumption is valid and the effect of chemisorption dynamics is negligible. The size of the permissible region is sensitive to the reaction temperature and gas pressure. The results indicate that in some cases the thermogravimetric data should be used with caution in kinetic studies. A large amount of literature on thermogravimetric analyzer determined char gasification kinetics is examined and the importance of chemisorption dynamics for the data assessed.

Kinetics of adsorption on activated carbon: application of heterogeneous vacancy solution theory

The kinetics of single component adsorption on activated carbon is investigated here using a heterogeneous vacancy solution theory (VST) of adsorption. The adsorption isotherm is developed to account for the adsorbate non-ideality due to the size difference between the adsorbate molecule and the vacant site, while incorporating adsorbent heterogeneity through a pore-width-related potential energy. The transport process in the bidisperse carbon considers coupled mass transfer in both macropore and micropore phases simultaneously. Adsorbate diffusion in the micropore network is modeled through effective medium theory, thus considering pore network connectivity in the adsorbent, with the activation energy for adsorbate diffusion related to the adsorption energy, represented by the Steele 10-4-3 potential for carbons. Experimental data of five hydrocarbons, CO2 and SO2 on Ajax carbon at multiple temperatures, as well as three hydrocarbons on Norit carbon at three temperatures are first fitted by the heterogeneous VST model to obtain the isotherm parameters, followed by application of the kinetic model to uptake data on carbon particles of different sizes and geometry at various temperatures. For the hydrocarbons studied, the model can successfully correlate the experimental data for both adsorption equilibrium and kinetics. However, there is some deviation in the fit of the desorption kinetics for polar compounds such as CO2 and SO2, due to the inadequacy of the L-J potential model in this case. The significance of viscous transport in the micropores is also considered here and found to be negligible, consistent with recent molecular simulation studies. (C) 2002 Elsevier Science Ltd. All rights reserved.

Vacancy solution theory for binary adsorption equilibria in heterogeneous carbon

A heterogeneous modified vacancy solution model of adsorption developed is evaluated. The new model considers the adsorption process through a mass-action law and is thermodynamically consistent, while maintaining the simplicity in calculation of multicomponent adsorption equilibria, as in the original vacancy solution theory. It incorporates the adsorbent heterogeneity through a pore-width-related potential energy, represented by Steele's 10-4-3 potential expression. The experimental data of various hydrocarbons, CO2 and SO2 on four different activated carbons - Ajax, Norit, Nuxit, and BPL - at multiple temperatures over a wide range of pressures were studied by the heterogeneous modified VST model to obtain the isotherm parameters and micropore-size distribution of carbons. The model successfully correlates the single-component adsorption equilibrium data for all compounds studied on various carbons. The fitting results for the vacancy occupancy parameter are consistent with the pressure change on different carbons, and the effect of pore heterogeneity is important in adsorption at elevated pressure. It predicts binary adsorption equilibria better than the IAST scheme, reflecting the significance of molecular size nonideality.

Dinoflagellate symbiosis: strategies and adaptations for the aquisition and fixation of inorganic carbon

Dinoflagellates exist in symbiosis with a number of marine invertebrates including giant clams, which are the largest of these symbiotic organisms. The dinoflagellates (Symbiodinium sp.) live intercellularly within tubules in the mantle of the host clam. The transport of inorganic carbon (Ci) from seawater to Symbiodinium (=zooxanthellae) is an essential function of hosts that derive the majority of their respiratory energy from the photosynthate exported by the zooxanthellae. Immunolocalisation studies show that the host has adapted its physiology to acquire, rather than remove CO2, from the haemolymph and clam tissues. Two carbonic anhydrase (CA) isoforms (32 and 70 kDa) play an essential part in this process. These have been localised to the mantle and gill tissues where they catalyse the interconversion of HCO3- to CO2, which then diffuses into the host tissues. The zooxanthellae exhibit a number of strategies to maximise Ci acquisition and utilisation. This is necessary as they express a form II Rubisco that has poor discrimination between CO2 and O-2. Evidence is presented for a carbon concentrating mechanism (CCM) to overcome. this disadvantage. The CCM incorporates the presence of a light-activated CA activity, a capacity to take up both HCO3- and CO2, an ability to accumulate an elevated concentration of Ci within the algal cell, and localisation of Rubisco to the pyrenoid. These algae also express both external and intracellular CAs, with the intracellular isoforms being localised to the thylakoid lumen and pyrenoid. These results have been incorporated into a model that explains the transport of Ci from seawater through the clam to the zooxanthellae.