Soil carbon saturation : evaluation and corroboration by long-term incubations

Although current assessments of agricultural management practices on soil organic C (SOC) dynamics are usually conducted without any explicit consideration of limits to soil C storage, it has been hypothesized that the SOC pool has an upper, or saturation limit with respect to C input levels at steady state. Agricultural management practices that increase C input levels over time produce a new equilibrium soil C content. However, multiple C input level treatments that produce no increase in SOC stocks at equilibrium show that soils have become saturated with respect to C inputs. SOC storage of added C input is a function of how far a soil is from saturation level (saturation deficit) as well as C input level. We tested experimentally if C saturation deficit and varying C input levels influenced soil C stabilization of added C-13 in soils varying in SOC content and physiochemical characteristics. We incubated for 2.5 years soil samples from seven agricultural sites that were closer to (i.e., A-horizon) or further from (i.e., C-horizon) their C saturation limit. At the initiation of the incubations, samples received low or high C input levels of 13 C-labeled wheat straw. We also tested the effect of Ca addition and residue quality on a subset of these soils. We hypothesized that the proportion of C stabilized would be greater in samples with larger C Saturation deficits (i.e., the C- versus A-horizon samples) and that the relative stabilization efficiency (i.e., Delta SCC/Delta C input) would decrease as C input level increased. We found that C saturation deficit influenced the stabilization of added residue at six out of the seven sites and C addition level affected the stabilization of added residue in four sites, corroborating both hypotheses. Increasing Ca availability or decreasing residue quality had no effect on the stabilization of added residue. The amount of new C stabilized was significantly related to C saturation deficit, supporting the hypothesis that C saturation influenced C stabilization at all our sites. Our results suggest that soils with low C contents and degraded lands may have the greatest potential and efficiency to store added C because they are further from their saturation level. (c) 2008 Elsevier Ltd. All rights reserved.

Spatial variability of soil carbon in forested and cultivated sites: Implications for change detection

The potential to sequester atmospheric carbon in agricultural and forest soils to offset greenhouse gas emissions has generated interest in measuring changes in soil carbon resulting from changes in land management. However, inherent spatial variability of soil carbon limits the precision of measurement of changes in soil carbon and hence, the ability to detect changes. We analyzed variability of soil carbon by intensively sampling sites under different land management as a step toward developing efficient soil sampling designs. Sites were tilled crop-land and a mixed deciduous forest in Tennessee, and old-growth and second-growth coniferous forest in western Washington, USA. Six soil cores within each of three microplots were taken as an initial sample and an additional six cores were taken to simulate resampling. Soil C variability was greater in Washington than in Tennessee, and greater in less disturbed than in more disturbed sites. Using this protocol, our data suggest that differences on the order of 2.0 Mg C ha(-1) could be detected by collection and analysis of cores from at least five (tilled) or two (forest) microplots in Tennessee. More spatial variability in the forested sites in Washington increased the minimum detectable difference, but these systems, consisting of low C content sandy soil with irregularly distributed pockets of organic C in buried logs, are likely to rank among the most spatially heterogeneous of systems. Our results clearly indicate that consistent intramicroplot differences at all sites will enable detection of much more modest changes if the same microplots are resampled.

Carbon pools and fluxes along an environmental gradient in northern Arizona

Carbon pools and fluxes were quantified along an environmental gradient in northern Arizona. Data are presented on vegetation, litter, and soil C pools and soil CO2 fluxes from ecosystems ranging from shrub-steppe through woodlands to coniferous forest and the ecotones in between. Carbon pool sizes and fluxes in these semiarid ecosystems vary with temperature and precipitation and are strongly influenced by canopy cover. Ecosystem respiration is approximately 50 percent greater in the more mesic, forest environment than in the dry shrub-steppe environment. Soil respiration rates within a site vary seasonally with temperature but appear to be constrained by low soil moisture during dry summer months, when approximately 75% of total annual soil respiration occurs. Total annual amount of CO2 respired across all sites is positively correlated with annual precipitation and negatively correlated with temperature. Results suggest that changes in the amount and periodicity of precipitation will have a greater effect on C pools and fluxes than will changes in temperature :in the semiarid Southwestern United States.

AC/DC electrical characteristics of epoxy-multi wall carbon nanotube nanocomposites

Expoxy nanocomposites with multiwell carbon nanotubes (mwcnts) filler up to 0.3%wt were prepared by sheer mixing and good dispersion of the MWCNTS in the epoxy was successfully achieved. The electrical behaviour was characterized by measurements of the alternating current (ac) and direct current (dc) conductives at room temperature. Typical percolation behaviour was observed at a low percolation threshold of 0.055%. Frequency independent ac conductivity was observed at low frequencies but not at high frequencies. An equivalent circuit models was used to predict the impedence response in these nanocomposites.

Development and deployment challenges for low emissions coal technology : the IGCC with CCS case

Carbon Capture and Storage (CCS) is a critical part of the global effort to address climate change as CCS has the potential to achieve deep cuts in CO2 emissions to atmosphere from the use of fossil fuels. In this context, pre-combustion capture through Integrated Gasification Combined Cycle (IGCC) power plants with CCS is one of the key pathways to low emissions power generation. There are, however, very significant challenges to the development, commercialization and deployment of IGCC with CCS technologies. This article examines matters of cost, the need for government support to early movers, the attribution of economic value for carbon dioxide and various other regulatory, policy, technical and infrastructural barriers to the development and subsequent deployment of this low emissions coal technology option.

Offsetting greenhouse gas emissions through biological carbon sequestration in North Eastern Australia

The Kyoto Protocol recognises trees as a sink of carbon and a valid means to offset greenhouse gas emissions and meet internationally agreed emissions targets. This study details biological carbon sequestration rates for common plantation species Araucaria cunninghamii (hoop pine), Eucalyptus cloeziana, Eucalyptus argophloia, Pinus elliottii and Pinus caribaea var hondurensis and individual land areas required in north-eastern Australia to offset greenhouse gas emissions of 1000tCO 2e. The 3PG simulation model was used to predict above and below-ground estimates of biomass carbon for a range of soil productivity conditions for six representative locations in agricultural regions of north-eastern Australia. The total area required to offset 1000tCO 2e ranges from 1ha of E. cloeziana under high productivity conditions in coastal North Queensland to 45ha of hoop pine in low productivity conditions of inland Central Queensland. These areas must remain planted for a minimum of 30years to meet the offset of 1000tCO 2e.

Characterisation of multi wall carbon nanotube–polymer composites for strain sensing applications

Carbon nanotubes (CNTs) have excellent electrical, mechanical and electromechanical properties. When CNTs are incorporated into polymers, electrically conductive composites with high electrical conductivity at very low CNT content (often below 1% wt CNT) result. Due to the change in electrical properties under mechanical load, carbon nanotube/polymer composites have attracted significant research interest especially due to their potential for application in in-situ monitoring of stress distribution and active control of strain sensing in composite structures or as strain sensors. To sucessfully develop novel devices for such applications, some of the major challenges that need to be overcome include; in-depth understanding of structure-electrical conductivity relationships, response of the composites under changing environmental conditions and piezoresistivity of different types of carbon nanotube/polymer sensing devices. In this thesis, direct current (DC) and alternating current (AC) conductivity of CNT-epoxy composites was investigated. Details of microstructure obtained by scanning electron microscopy were used to link observed electrical properties with structure using equivalent circuit modeling. The role of polymer coatings on macro and micro level electrical conductivity was investigated using atomic force microscopy. Thermal analysis and Raman spectroscopy were used to evaluate the heat flow and deformation of carbon nanotubes embedded in the epoxy, respectively, and related to temperature induced resistivity changes. A comparative assessment of piezoresistivity was conducted using randomly mixed carbon nanotube/epoxy composites, and new concept epoxy- and polyurethane-coated carbon nanotube films. The results indicate that equivalent circuit modelling is a reliable technique for estimating values of the resistance and capacitive components in linear, low aspect ratio-epoxy composites. Using this approach, the dominant role of tunneling resistance in determining the electrical conductivity was confirmed, a result further verified using conductive-atomic force microscopy analysis. Randomly mixed CNT-epoxy composites were found to be highly sensitive to mechanical strain and temperature variation compared to polymer-coated CNT films. In the vicinity of the glass transition temperature, the CNT-epoxy composites exhibited pronounced resistivity peaks. Thermal and Raman spectroscopy analyses indicated that this phenomenon can be attributed to physical aging of the epoxy matrix phase and structural rearrangement of the conductive network induced by matrix expansion. The resistivity of polymercoated CNT composites was mainly dominated by the intrinsic resistivity of CNTs and the CNT junctions, and their linear, weakly temperature sensitive response can be described by a modified Luttinger liquid model. Piezoresistivity of the polymer coated sensors was dominated by break up of the conducting carbon nanotube network and the consequent degradation of nanotube-nanotube contacts while that of the randomly mixed CNT-epoxy composites was determined by tunnelling resistance between neighbouring CNTs. This thesis has demonstrated that it is possible to use microstructure information to develop equivalent circuit models that are capable of representing the electrical conductivity of CNT/epoxy composites accurately. New designs of carbon nanotube based sensing devices, utilising carbon nanotube films as the key functional element, can be used to overcome the high temperature sensitivity of randomly mixed CNT/polymer composites without compromising on desired high strain sensitivity. This concept can be extended to develop large area intelligent CNT based coatings and targeted weak-point specific strain sensors for use in structural health monitoring.

Tax evasion, inequality, and progressive taxes : a political economy perspective

The standard approach to tax compliance applies the economics-of-crime methodology pioneered by Becker (1968): in its first application, due to Allingham and Sandmo (1972) it models the behaviour of agents as a decision involving a choice of the extent of their income to report to tax authorities, given a certain institutional environment, represented by parameters such as the probability of detection and penalties in the event the agent is caught. While this basic framework yields important insights on tax compliance behavior, it has some critical limitations. Specifically, it indicates a level of compliance that is significantly below what is observed in the data. This thesis revisits the original framework with a view towards addressing this issue, and examining the political economy implications of tax evasion for progressivity in the tax structure. The approach followed involves building a macroeconomic, dynamic equilibrium model for the purpose of examining these issues, by using a step-wise model building procedure starting with some very simple variations of the basic Allingham and Sandmo construct, which are eventually integrated to a dynamic general equilibrium overlapping generations framework with heterogeneous agents. One of the variations involves incorporating the Allingham and Sandmo construct into a two-period model of a small open economy of the type originally attributed to Fisher (1930). A further variation of this simple construct involves allowing agents to initially decide whether to evade taxes or not. In the event they decide to evade, the agents then have to decide the extent of income or wealth they wish to under-report. We find that the ‘evade or not’ assumption has strikingly different and more realistic implications for the extent of evasion, and demonstrate that it is a more appropriate modeling strategy in the context of macroeconomic models, which are essentially dynamic in nature, and involve consumption smoothing across time and across various states of nature. Specifically, since deciding to undertake tax evasion impacts on the consumption smoothing ability of the agent by creating two states of nature in which the agent is ‘caught’ or ‘not caught’, there is a possibility that their utility under certainty, when they choose not to evade, is higher than the expected utility obtained when they choose to evade. Furthermore, the simple two-period model incorporating an ‘evade or not’ choice can be used to demonstrate some strikingly different political economy implications relative to its Allingham and Sandmo counterpart. In variations of the two models that allow for voting on the tax parameter, we find that agents typically choose to vote for a high degree of progressivity by choosing the highest available tax rate from the menu of choices available to them. There is, however, a small range of inequality levels for which agents in the ‘evade or not’ model vote for a relatively low value of the tax rate. The final steps in the model building procedure involve grafting the two-period models with a political economy choice into a dynamic overlapping generations setting with more general, non-linear tax schedules and a ‘cost-of evasion’ function that is increasing in the extent of evasion. Results based on numerical simulations of these models show further improvement in the model’s ability to match empirically plausible levels of tax evasion. In addition, the differences between the political economy implications of the ‘evade or not’ version of the model and its Allingham and Sandmo counterpart are now very striking; there is now a large range of values of the inequality parameter for which agents in the ‘evade or not’ model vote for a low degree of progressivity. This is because, in the ‘evade or not’ version of the model, low values of the tax rate encourages a large number of agents to choose the ‘not-evade’ option, so that the redistributive mechanism is more ‘efficient’ relative to the situations in which tax rates are high. Some further implications of the models of this thesis relate to whether variations in the level of inequality, and parameters such as the probability of detection and penalties for tax evasion matter for the political economy results. We find that (i) the political economy outcomes for the tax rate are quite insensitive to changes in inequality, and (ii) the voting outcomes change in non-monotonic ways in response to changes in the probability of detection and penalty rates. Specifically, the model suggests that changes in inequality should not matter, although the political outcome for the tax rate for a given level of inequality is conditional on whether there is a large or small or large extent of evasion in the economy. We conclude that further theoretical research into macroeconomic models of tax evasion is required to identify the structural relationships underpinning the link between inequality and redistribution in the presence of tax evasion. The models of this thesis provide a necessary first step in that direction.

Poorly graphitized carbon as a new cosmothermometer for primitive extraterrestrial materials

The presence of carbon in primitive extraterrestrial materials has long been considered a useful indicator of prevailing geochemical conditions early in the formation of the Solar System. A recent addition to the suite of primitive materials available for study by cosmochemists includes particles collected from the stratosphere called chondritic porous (CP) aggregates1. Carbon-rich CP aggregates are less abundant in stratospheric collections and contain many low-temperature phases (such as layer silicates) as minor components2,3. We describe here the nature of the most abundant carbon phase in a carbon-rich CP aggregate (sample no. W7029* A) collected from the stratosphere as part of the Johnson Space Center (JSC) Cosmic Dust Program4. By comparison with experimental and terrestrial studies of poorly graphitized carbon (PGC), we show that the graphitization temperature, or the degree of ordering in the PGC, may provide a useful cosmothermometer for primitive extraterrestrial materials.

Nanoporous Graphitic-C3N4@Carbon Metal-Free Electrocatalysts for Highly Efficient Oxygen Reduction

Based on theoretical prediction, a g-C3N4@carbon metal-free oxygen reduction reaction (ORR) electrocatalyst was designed and synthesized by uniform incorporation of g-C3N4 into a mesoporous carbon to enhance the electron transfer efficiency of g-C3N4. The resulting g-C3N4@carbon composite exhibited competitive catalytic activity (11.3 mA cm–2 kinetic-limiting current density at −0.6 V) and superior methanol tolerance compared to a commercial Pt/C catalyst. Furthermore, it demonstrated significantly higher catalytic efficiency (nearly 100% of four-electron ORR process selectivity) than a Pt/C catalyst. The proposed synthesis route is facile and low-cost, providing a feasible method for the development of highly efficient electrocatalysts.

Recent advances in catalytic/biocatalytic conversion of greenhouse methane and carbon dioxide to methanol and other oxygenates

Methane gas has been identified as the most destructive greenhouse gas (Liu et al., 2004). It was reported that the global warming potential of methane per molecule relative to CO2 is approximately 23 on a 100-year timescale or 62 over a 20-year period (IPCC, 2001). Methane has high C-H bond energy of about 439 kJ/mol and other higher alkanes (or saturated hydrocarbons) also have a very strong C-C and C-H bonds, thus making their molecules to have no empty orbitals of low energy or filled orbitals of high energy that could readily participate in chemical reactions as is the case with unsaturated hydrocarbons such as olefins and alkynes (Crabtree, 1994; Labinger & Bercaw, 2002)...

Modelling carbon membranes for gas and isotope separation

Molecular modelling has become a useful and widely applied tool to investigate separation and diffusion behavior of gas molecules through nano-porous low dimensional carbon materials, including quasi-1D carbon nanotubes and 2D graphene-like carbon allotropes. These simulations provide detailed, molecular level information about the carbon framework structure as well as dynamics and mechanistic insights, i.e. size sieving, quantum sieving, and chemical affinity sieving. In this perspective, we revisit recent advances in this field and summarize separation mechanisms for multicomponent systems from kinetic and equilibrium molecular simulations, elucidating also anomalous diffusion effects induced by the confining pore structure and outlining perspectives for future directions in this field.

Enhanced hydrogen separation by vertically-aligned carbon nanotube membranes with zeolite imidazolate frameworks as a selective layer

Vertically-aligned carbon nanotube (VACNT) membranes show very high permeation fluxes due to the inherent smooth and frictionless nature of the interior of the nanotubes. However, the hydrogen selectivities are all in the Knudsen range and are quite low. In this study we grew molecular sieve zeolite imidazolate frameworks (ZIFs) via secondary seeded growth on the VACNT membranes as a gas selective layer. The ZIF layer has a thickness of 5–6 μm and shows good contact with the VACNT membrane surface. The VACNT supported ZIF membrane shows much higher H2 selectivity than Ar (7.0); O2 (13.6); N2 (15.1) and CH4 (9.8). We conclude that tailoring metal–organic frameworks on the membrane surface can be an effective route to improve the gas separation performance of the VACNT membrane.

Vertically-aligned carbon nanotube membranes for hydrogen separation

Vertically-aligned carbon nanotube membranes have been fabricated and characterized and the corresponding gas permeability and hydrogen separation were measured. The carbon nanotube diameter and areal density were adjusted by varying the catalyst vapour concentration (Fe/C ratio) in the mixed precursor. The permeances are one to two magnitudes higher than the Knudsen prediction, while the gas selectivities are still in the Knudsen range. The diameter and areal density effects were studied and compared, the temperature dependence of permeation is also discussed. The results confirm the existence of non-Knudsen transport and that surface adsorption diffusion may affect the total permeance at relative low temperature. The permeance of aligned carbon nanotube membranes can be improved by increasing areal density and operating at an optimum temperature.

Adsorption of carbon dioxide and nitrogen on single-layer aluminum nitride nanostructures studied by density functional theory

The adsorption of carbon dioxide and nitrogen molecules on aluminum nitride (AlN) nanostructures has been explored using first-principle computational methods. Optimized configurations corresponding to physisorption and, subsequentially, chemisorption of CO2 are identified, in contrast to N2, for which only a physisorption structure is found. Transition-state searches imply a low energy barrier between the physisorption and chemisorption states for CO2 such that the latter is accessible and thermodynamically favored at room temperature. The effective binding energy of the optimized chemisorption structure is apparently larger than those for other CO2 adsorptive materials, suggesting the potential for application of aluminum nitride nanostructures for carbon dioxide capture and storage.