Different carbon nanostructures have different properties and different applications. It is needed to synthesize good quality and also on large scale. From the point of industrial applications, highly productive and low cost synthesis method is very essential. Research has been done extensively on the intrinsic and individual properties of both single walled carbon nanotubes (SWCNTs) and multiwalled carbon nanotubes (MWC-NTs) in the range of nanometer to micrometer length scale. The important question is how the properties change beyond this length scale and if they are used in group in the form of an array instead of the individual carbon nanotubes (CNTs). Some applications require large current output, large energy production etc. For such kind of applications, it becomes essential to use CNTs in large number in the form of arrays or array, instead of using large numbers of CNTs in individual level. Future nanotechnology scope requires large scale application using the very rich intrinsic properties of the CNTs and nanomaterials. Keeping these problems and challenges in front, this thesis work is devoted to the research of the large scale synthesis of mm long MWCNTs, having different morphology and studies on various physical properties of MWCNTs in the form of arrays. Synthesis of mm long aligned and buckled MWCNTs have been reported for the first time. Generally buckled CNTs were obtained by compressing the straight CNTs. Apart from this, different morphologies like, aligned straight, helical or coiled CNTs are also synthesized. Resistance of the individual CNT increases with the increase in length. Resistance versus length of an array of CNT also shows similar behaviour. The thermal conductivity of CNT array is observed to decrease with the increase of array diameter (diameter �100 µm). There are few reports of the similar behaviour with the experiments done on small diameter CNT arrays (diameter �100 nm). From these observations, it seems that in the arrays of CNT, their intrinsic individual property is preserved though the magnitudes are different. The conductance measurements done on buckled CNT array by compressing it to apply uniaxial strain, shows the conductance oscillation. This conductance oscillation seems to be originating from the band gap change due to strain when the CNTs bend during compression. Recent research focuses on the arrays of CNT as they can carry large current of the order of several milliamperes that make the arrays suitable in nanoscale electronics and in controlling macroscopic devices such as light emitting diodes and electromotors. Regarding this aspect, a part of this thesis work is devoted on the application of CNT array to field effect transistor (FET) and study of thermoelectric power generation using CNT arrays. The entire thesis is based on the works discussed above. It has been organized as follows: Chapter 1 deals with introduction about the different carbon nanostructures and different synthesis methods. A brief introduction about the different current-voltage (IV) characteristics of SWCNTs and MWCNTs, length and diameter dependence and effect of the mode of contacts, are given. Some applications of the array of CNTs like buckling effect on compression, stretching of CNT into the form of rope, and conduction change on compression are discussed. Application of CNT as FET, as a thermometer, and thermoelectric effect of CNT are discussed. The electromechanical effect of CNT is also discussed briefly. Chapter 2 deals with experimental setup for synthesis of different morphologies of carbon nanostructures. The samples are characterized using common characterization techniques like, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. A brief introduction about Raman Spectroscopy of CNT is given. Chapter 3 reports the unusual IV characteristics and breakdown of long CNT arrays. The current carrying ability and the threshold voltage as a function of array diameter are reported. The effect of the ambient like temperature and pressure are discussed. Chapter 4 deals with theoretical models to analyze the IV characteristics reported in Chapter 3. It has been shown that a set of classical equations are applicable to quantum structures and the band gap can be evaluated. Chapter 5 describes with application of CNT arrays as temperature sensors. It has been shown that CNT arrays of suitable diameters are used as temperature sensors after calibration. Chapter 6 reports the high current FET application of CNT arrays. Effects of temperature and ambient pressure are discussed. The type of the majority charge carrier is determined. Chapter 7 deals with application of CNT arrays as thermoelectric power generator to get large thermoelectric current. Effects of different array diameter are discussed. Modulation of thermoemf with gate voltage is discussed. The type of the majority charge carrier is determined. Chapter 8 reports the effect of compressive strain on buckled MWCNT arrays. Conductance is measured during the compression of the array. Quantum electromechanical conductance oscillation is observed. The structural changes are observed with SEM. Raman spectroscopic study supports the explanation of the effect. Chapter 9 provides the conclusion and overall summary of the thesis.

No description available.

The objective of this research and aim of this dissertation was to determine the potential impact of the introduction of a carbon emissions tax (hereafter CET) on the South African mining industry and this has been achieved by addressing the following three areas of research: Most urgently, a literature review was required in order to obtain an understanding of why a carbon tax or alternative system was required. A detailed understanding of the functioning of these systems was invaluable to the outcome of the study. The survey conducted, confirmed the fact that global warming and related climate change brought about by human interference, constitute both global and national complications. The study confirmed that market based instruments can assist in addressing this problem and that these are generally considered to be more effective than traditional command-and-control policies. Notwithstanding this finding, in order to ensure efficacy, careful consideration should be given to the economic climate in which they are to be implemented. Secondly, a literature review was essential in order to fully comprehend the nature of the South African economy and specifically the South African mining industry’s contribution to the aforementioned problem. The importance of the industry to the economy had to be acknowledged. It was then established that the South African economy, and in particular the South African mining industry, contribute to this predicament due to their considerable dependence on coal fired power stations for the supply of electricity. The study revealed that should this industry be adversely affected by the proposed taxation, the economy as a whole would suffer. Finally, a literature review as well as quantitative examples were used to estimate the impact of CET on the South African mining industry. This outcome was achieved by evaluating the results of taxation as opposed to the objectives of the Mineral and Petroleum Resources Development Act 28 of 2002 (MPRDA). The study found that the effect on most of the objectives of the MPRDA, and especially those related to job creation, economic growth and equal access for all applicants on entering the arena of the mining industry, may well be affected adversely by the implementation of the proposed CET, as the tax was found to impact negatively on the industry’s profits. It has also been assessed that the iron ore sector will be the most affected sector and that smaller companies will be affected to a larger degree than larger companies. The modus operandi and selection of allocated beneficiaries when allocating the revenue collected from the proposed CET by the National Treasury were also found to play a significant role in whether or not the objectives of the MPRDA were positively or negatively influenced by the implementation of the tax. The outcome of the study performed on the research question confirmed that, if said effect of the proposed CET on the South African mining industry was to be compared to the objective of the MPRDA, both positive and negative implications could be identified. / MCom (South African and International Taxation), North-West University, Potchefstroom Campus, 2014

The baseline of uncertainty in aerosol radiative forcing is large and depends on aerosol characteristics (e.g. size and composition), which can vary significantly on a regional scale. Sources (natural and anthropogenic) can be directly linked to the aerosol characteristics of a region, making monitoring campaigns to determine aerosol composition in different regions very important. Limited data currently exists for atmospheric aerosol black carbon (BC) and organic carbon (OC) in South Africa. In this study, BC and OC concentrations were explored in terms of spatial and temporal patterns, mass fractions of BC and OC of the overall aerosol mass, as well as possible sources. Primary pollutants, of which BC is an example, are emitted directly from the source. Certain primary pollutants can react with other pollutants to form secondary pollutants. OC can either be a primary or secondary pollutant, e.g. formed by gas-to-particle conversion of volatile organic compounds (VOCs) in the atmosphere (nucleation and condensation of gaseous precursors). Greenhouse gases (GHG) and BC absorb terrestrial long wave radiation causing an increase of atmospheric temperature. In contrast, OC generally reflects incoming radiation, cooling the atmosphere. GHGs have a long residence time in the atmosphere (10 to 100 years), while the residence time of aerosols is usually only a week or more. The climatic effects of aerosols are therefore particularly important from a regional perspective. Aerosols are also important from an air quality perspective, especially since ultrafine particles (diameter smaller than 100nm) are small enough to go through the membranes of the respiratory tract and into the blood stream. They can then be transported to the brain. Up to 2005, DEBITS (Deposition of Biogeochemical Import Trace Species) activities in South Africa did not include aerosol measurements. In order to initiate aerosol monitoring, campaigns were launched during the 2005 to 2007 period. Additionally, OC and BC measurements for the PM10 and PM2.5 (particulate matter smaller than or equal to 10 and 2.5 μm, respectively) fractions were started in 2009. PM10 and PM2.5 samples were collected at five sampling sites in South Africa operated within the DEBITS network, i.e. Louis Trichardt, Skukuza, Vaal Triangle, Amersfoort and Botsalano, with MiniVol samplers. The selected sites are mostly located in rural areas, but with the surrounding atmosphere influenced by industries, transportation, biomass burning, etc. Winters are characterised by an increase in biomass burning (fires) and combustion for domestic use (cooking and space heating). Samples were analysed with a Thermal/Optical Carbon analyser (Desert Research Institute). OC and BC results showed that the total carbonaceous content decreased during the summer due to less biomass burning (fires). BC was the highest at the industrially influenced sites, while OC was highest at regional background sites. OC was higher than BC concentrations at all sites in both size fractions. Most OC and BC occurred in the PM2.5 fraction. OC/BC ratios reflected the setting of the different DEBITS sites, with sites in or close to anthropogenic source regions having the lowest OC/BC ratios, while background sites had the highest OC/BC ratios. The OC mass fraction percentage of the total aerosol weight varied up to 24% and the BC up to 12%. The highest OC mass fraction was found at Skukuza, which was attributed to both natural (lies within the savannah biome) and anthropogenic (dominant path of air mass movement from the anthropogenic industrial hub of South Africa) reasons. The highest mass fraction of BC was found in the Vaal Triangle, since it is situated within a well-known anthropogenic source region. Household combustion for space heating and cooking also seemed to make a significant contribution to BC at this site in the cold winter months. A relatively well-defined seasonal pattern was observed, with higher OC and BC concentrations measured from May to October, which coincides with the dry season in the interior of South Africa. Positive correlations between OC and BC concentrations with the distance back trajectories passed fires were observed, indicating that fires contribute significantly to both atmospheric OC and BC during the burning season. / MSc (Environmental Sciences), North-West University, Potchefstroom Campus, 2014

The objective of this research and aim of this dissertation was to determine the potential impact of the introduction of a carbon emissions tax (hereafter CET) on the South African mining industry and this has been achieved by addressing the following three areas of research: Most urgently, a literature review was required in order to obtain an understanding of why a carbon tax or alternative system was required. A detailed understanding of the functioning of these systems was invaluable to the outcome of the study. The survey conducted, confirmed the fact that global warming and related climate change brought about by human interference, constitute both global and national complications. The study confirmed that market based instruments can assist in addressing this problem and that these are generally considered to be more effective than traditional command-and-control policies. Notwithstanding this finding, in order to ensure efficacy, careful consideration should be given to the economic climate in which they are to be implemented. Secondly, a literature review was essential in order to fully comprehend the nature of the South African economy and specifically the South African mining industry’s contribution to the aforementioned problem. The importance of the industry to the economy had to be acknowledged. It was then established that the South African economy, and in particular the South African mining industry, contribute to this predicament due to their considerable dependence on coal fired power stations for the supply of electricity. The study revealed that should this industry be adversely affected by the proposed taxation, the economy as a whole would suffer. Finally, a literature review as well as quantitative examples were used to estimate the impact of CET on the South African mining industry. This outcome was achieved by evaluating the results of taxation as opposed to the objectives of the Mineral and Petroleum Resources Development Act 28 of 2002 (MPRDA). The study found that the effect on most of the objectives of the MPRDA, and especially those related to job creation, economic growth and equal access for all applicants on entering the arena of the mining industry, may well be affected adversely by the implementation of the proposed CET, as the tax was found to impact negatively on the industry’s profits. It has also been assessed that the iron ore sector will be the most affected sector and that smaller companies will be affected to a larger degree than larger companies. The modus operandi and selection of allocated beneficiaries when allocating the revenue collected from the proposed CET by the National Treasury were also found to play a significant role in whether or not the objectives of the MPRDA were positively or negatively influenced by the implementation of the tax. The outcome of the study performed on the research question confirmed that, if said effect of the proposed CET on the South African mining industry was to be compared to the objective of the MPRDA, both positive and negative implications could be identified. / MCom (South African and International Taxation), North-West University, Potchefstroom Campus, 2014

The baseline of uncertainty in aerosol radiative forcing is large and depends on aerosol characteristics (e.g. size and composition), which can vary significantly on a regional scale. Sources (natural and anthropogenic) can be directly linked to the aerosol characteristics of a region, making monitoring campaigns to determine aerosol composition in different regions very important. Limited data currently exists for atmospheric aerosol black carbon (BC) and organic carbon (OC) in South Africa. In this study, BC and OC concentrations were explored in terms of spatial and temporal patterns, mass fractions of BC and OC of the overall aerosol mass, as well as possible sources. Primary pollutants, of which BC is an example, are emitted directly from the source. Certain primary pollutants can react with other pollutants to form secondary pollutants. OC can either be a primary or secondary pollutant, e.g. formed by gas-to-particle conversion of volatile organic compounds (VOCs) in the atmosphere (nucleation and condensation of gaseous precursors). Greenhouse gases (GHG) and BC absorb terrestrial long wave radiation causing an increase of atmospheric temperature. In contrast, OC generally reflects incoming radiation, cooling the atmosphere. GHGs have a long residence time in the atmosphere (10 to 100 years), while the residence time of aerosols is usually only a week or more. The climatic effects of aerosols are therefore particularly important from a regional perspective. Aerosols are also important from an air quality perspective, especially since ultrafine particles (diameter smaller than 100nm) are small enough to go through the membranes of the respiratory tract and into the blood stream. They can then be transported to the brain. Up to 2005, DEBITS (Deposition of Biogeochemical Import Trace Species) activities in South Africa did not include aerosol measurements. In order to initiate aerosol monitoring, campaigns were launched during the 2005 to 2007 period. Additionally, OC and BC measurements for the PM10 and PM2.5 (particulate matter smaller than or equal to 10 and 2.5 μm, respectively) fractions were started in 2009. PM10 and PM2.5 samples were collected at five sampling sites in South Africa operated within the DEBITS network, i.e. Louis Trichardt, Skukuza, Vaal Triangle, Amersfoort and Botsalano, with MiniVol samplers. The selected sites are mostly located in rural areas, but with the surrounding atmosphere influenced by industries, transportation, biomass burning, etc. Winters are characterised by an increase in biomass burning (fires) and combustion for domestic use (cooking and space heating). Samples were analysed with a Thermal/Optical Carbon analyser (Desert Research Institute). OC and BC results showed that the total carbonaceous content decreased during the summer due to less biomass burning (fires). BC was the highest at the industrially influenced sites, while OC was highest at regional background sites. OC was higher than BC concentrations at all sites in both size fractions. Most OC and BC occurred in the PM2.5 fraction. OC/BC ratios reflected the setting of the different DEBITS sites, with sites in or close to anthropogenic source regions having the lowest OC/BC ratios, while background sites had the highest OC/BC ratios. The OC mass fraction percentage of the total aerosol weight varied up to 24% and the BC up to 12%. The highest OC mass fraction was found at Skukuza, which was attributed to both natural (lies within the savannah biome) and anthropogenic (dominant path of air mass movement from the anthropogenic industrial hub of South Africa) reasons. The highest mass fraction of BC was found in the Vaal Triangle, since it is situated within a well-known anthropogenic source region. Household combustion for space heating and cooking also seemed to make a significant contribution to BC at this site in the cold winter months. A relatively well-defined seasonal pattern was observed, with higher OC and BC concentrations measured from May to October, which coincides with the dry season in the interior of South Africa. Positive correlations between OC and BC concentrations with the distance back trajectories passed fires were observed, indicating that fires contribute significantly to both atmospheric OC and BC during the burning season. / MSc (Environmental Sciences), North-West University, Potchefstroom Campus, 2014

Northern peatlands represent a significant carbon reservoir, containing approximately a third of the terrestrial carbon pool. The stability of these carbon stores is poorly understood, and processes of accumulation and degradation appear to be finely balanced. Over the last decade, it has become increasingly clear that losses of dissolved organic carbon (DOC) from peatlands can be of considerable size and this flux appears to have increased substantially over the last 20 years. Despite its significance, the chemical composition of peatland-derived DOC remains poorly understood. This study aimed to characterise dissolved organic matter (DOM) at the molecular level using a novel combination of techniques. The study site (Cors Fochno, Wales, UK) is an ombrotrophic bog on which a number of studies into carbon cycling and hydrology have been carried out, providing a useful context for this project. The size and compositions of the DOC pool was monitored over 18 months, from three banks of piezometers, sampling from depths of 15 cm to 6 m. DOM which is representative of bog runoff was also monitored. DOC concentrations varied considerably between locations, spanning an order of magnitude (11.4 to 114 mgC l-1). Several relationships between DOC concentration and environmental and physical factors were established: DOC levels near the surface of the peatland varied with temperature, those in the runoff were most affected by recent rainfall events and the apparent DOC concentration at depth was related to the hydraulic conductivity of peat at that depth. The annual flux of DOC from the site was estimated at 113 tonnes, or 17.4 gC m-2. Only a small portion of the DOC pool could be characterised by analysis of dissolved combined amino acids (DCAA) and dissolved carbohydrates (as neutral sugars). Non-protein amino acids were most abundant in runoff samples, suggesting microbial reworking of DOM on entering drainage systems. DCAA yields decreased with depth, and the DCAA pool in deeper peat layers was characterised by more hydrophobic compounds. Interpretation of semi-quantitative results from TMAH thermochemolysis GC-MS analysis suggested oxidative degradation of organic matter near the surface of the peatland and photochemical degradation where DOM entered drainage networks, and this was supported by novel interpretation of results from ultrahigh resolution mass spectrometry analysis. The deepest porewaters were dominated by nalkanes, with notable contributions from fatty acids, suggesting a plant wax source for this DOM. The highest DOC concentrations were found at intermediate depth from a site midway between the centre of the bog and the southern boundary where hydraulic conductivities were low, and DOM from these piezometers were characterised by high contributions from a suite of phenolic compounds (with mainly para-hydroxyphenyl structures). These compounds have been linked to Sphagnum species, and are known to be functionally important to the development and maintenance of the unusual chemical environment in peatlands which slows decay rates, reduces microbial activity, and allows the sequestration of the large carbon reservoir. The findings of this study highlight the dynamic nature of peatland derived DOM, both in the size of the carbon pool and its composition which change dramatically with both season and depth.

Thesis (MSc)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: The research was conducted in the Kwa-Zulu Natal midlands, South Africa. The vertical distribution of soil organic carbon (SOC) stocks were successfully predicted by stochastic exponential models developed for the three main land uses in the area, which are farmlands, forestry plantations and grasslands. These models, in combination with regular surface sampling, may be used for monitoring SOC dynamics in the area and mapping SOC stocks. Bulk density measurements are needed in combination with SOC content (%wt) to calculate such SOC stocks. Considering the disadvantages of bulk density sampling and measurement, an effort was made to determine if one of the commonly-used existing stochastic models could be used to successfully predict bulk densities for soils with known texture and SOC content to replace direct measurements, taking into account that different managements might affect final results. Statistica software was used to correlate the Saxton & Rawls model predictions and associated regressions with measured values for the study area. A clear distribution trend was achieved using Statistica and the correlations were fair with r2 values close to 0.5 for individual regressions and substantially higher for area averages. However, considering the depth-stratified averages and correcting for the effects of particle density changes for soils with high soil organic matter, high correlations for 2 of the 3 studied land uses were achieved (r2 values of 0.99 and 0.81 in forests and grasslands respectively). Therefore, although Saxton and Rawls (2006) predictions of bulk density may be used, it is preferable to conduct direct bulk density determinations. The proposed models to calculate the vertical distribution of SOC would substantially reduce the cost of soil carbon inventories to 1m soil depth in the study area by limiting observations to the soil surface. Triplicate 5cm-deep soil core samples would be collected at the soil surface per observation point for determination of ρb (bulk density) and Corg (organic carbon). On average, the accuracy of the normalized depth-distribution model is rather high for grasslands and forests/forest plantations (R2 = 0.98), but somewhat lower for cultivated lands (R2 = 0.96) due to mixing of the plough layer to cultivation depth. Carbon stocks to 1m depth were calculated as an integral of the normalized exponential distribution, multiplied by the value of Corg observed at the soil surface and expressed on volume basis as carbon density (Cv, kg∙m-3). The resulting stock assessment was compared to the observed values using piece-integration for sampled depth increments to give SOC stocks on an area basis (kg∙m-2). The estimated prediction error on average was 1.2 (9%) and 3.7 kg∙m-2 (21.6%) in grasslands and forests respectively, while for cultivated lands the error was 1.3 kg.m-2 (9.5%). Further improvement to reduce these errors may be achieved by introducing the soil type as variable and grouping the functions by soil type rather than land uses. The results of this work were presented at the seminar of the department of Soil Science, Stellenbosch University (Ros et al., 2014), the combined congress of the South African Soil Science, Horticulture and Agronomy societies (Rozanov et al., 2015), the First Global Soil Map conference, France (Wiese et al., 2013), the 20th International Congress of Soil Science, Korea (Wiese et al. 2014) and were submitted for publication in Geoderma special issue dedicated to digital soil mapping of soil organic carbon following the presentation at the 20th ICSS, Korea (Wiese et al., 2014). / AFRIKAANSE OPSOMMING: Hierdie navorsing is in die Kwa-Zulu Natalse middellande van Suid-Afrika gedoen. Die vertikale verspreiding van grondorganiese koolstof (GOK) is suksesvol voorspel deur middel van stogastiese eksponensiële modelle wat vir die drie hoof landsgebruike ontwikkel is. In kombinasie met roetine monsterneming by die grondoppervlak kan hierdie modelle suksesvol aangewend word vir die monitering van GOK dinamika in die studiegebied, sowel as kartering van GOK voorraad. Bulkdigtheidsmetings word tesame met GOK inhoud (%massa) benodig om die GOK voorraad te bereken. Weens die nadele van monsterneming vir bulkdigtheidsbepalings is ‘n poging aangewend om te bepaal of een van die mees algemeen gebruikte bestaande stogastiese modelle (Saxton & Rawls 2006) gebruik kan word om die bulkdigtheid van gronde suksesvol vanaf tekstuur en GOK inhoud te voorspel en sodoende direkte metings te vervang. Statistica sagteware is gebruik om die voorspellings met behulp van die Saxton & Rawls modelle en gevolglike regressies met gemete waardes vanuit die studiegebied te korreleer en ‘n duidelike verspreidingstendens is hierdeur opgelewer. Die korrelasies vir individuele regressies was redelik met r2 waardes naby 0.5 en merkwaardig hoër waardes vir area gemiddeldes. Hoë korrelasies is egter behaal vir 2 van die 3 bestudeerde landsgebruike (r2 waardes van 0.99 en 0.81 in bosbou en grasveld onderskeidelik) wanneer die gemiddelde dieptestratifikasies gebruik en gekorrigeer word vir die verandering in deeltjiedigtheid vir gronde met hoë grondorganiese material. Alhoewel die Saxton and Rawls (2006) voorspellings van bulkdigtheid gebruik kan word, behoort bulkdigtheidsbepalings egter verkieslik direk gedoen te word. Die voorgestelde modelle vir die bepaling van vertikale GOK verspreiding tot 1m gronddiepte sou die koste van grondkoolstof opnames in die studiegebied dramaties verlaag deur grondmetings tot die grondoppervlak te beperk. Grondmonsters sal in triplikaat per waarnemingspunt met 5cm diep silinders op die grondoppervlak geneem word vir ρb (bulkdigtheid) and Corg (organiese koolstof) bepalings. Die gemiddelde akkuraatheid van die genormaliseerde diepteverspreidingsmodel is hoog vir grasveld en woude/bosbou plantasies (R2 = 0.98), maar ietwat laer vir bewerkte landerye (R2 = 0.96) as gevolg van die vermenging van die ploeglaag tot op die diepte van bewerking. Koolstof voorraad tot 1m gronddiepte is bepaal deur middel van die integraal van die genormaliseerde eksponensiele verspreiding, vermenigvuldig met die waarde van Corg op die grondoppervlak en op ‘n volume basis uitgedruk as koolstofdigtheid (Cv, kg∙m-3). Die gevolglike voorraadopname is met gemete waardes vergelyk deur middel van ‘n stuksgewyse integrasie van die gemonsterde diepteinkremente om GOK voorraad per area (kg∙m-2) te lewer. Die gemiddelde geskatte fout van voorspelling was 1.2 (9%) en 3.7 kg∙m-2 (21.6%) in grasveld and plantasies onderskeidelik en 1.3 kg.m-2 (9.5%) in bewerkte landerye. Verdere verbetering van die modelle en ‘n verlaging in hierdie foute kan verkry word deur die grondtipe inligting as veranderlike in te bring en die funksies volgens grondtipe eerder as landsgebruik te groepeer. Resultate van hierdie werk is reeds aangebied tydens ‘n seminar by die department Grondkunde, Stellenbosch Universiteit (Ros Mesa et al., 2014), die gesamentlike kongres vir die Suid-Afrikaanse Verenigings vir Grondkunde, Hortologie, Onkruidwetenskap en Gewasproduksie (Rozanov et al. 2015), die Eerste Global Soil Map konferensie, Frankryk (Wiese et al, 2013), die 20ste Internasionale Grondkunde Kongres, Korea (Wiese et al. 2014) en is ingehandig vir publikasie in ‘n spesiale uitgawe van Geoderma wat, na aanleiding van die aanbieding by die 20ste Internasionale Grondkunde Kongres, Korea (Wiese et al., 2014), fokus op digitale grondkartering van grondorganiese koolstof.

Carbon dioxide release from fossil-fuel burning is significant enough that we may soon experience perceptible changes in climate with important human consequences. Man's activities involving deforestation and agriculture have undoubtedly also affected atmospheric CO₂, although quantitative, and even qualitative, net effects of these processes are incompletely understood relative to fossil-fuel production. An accurate reconstruction of past ¹³C/¹²C ratios of atmospheric CO₂ may provide key constraints on the historical activity of the biosphere as CO₂ source or sink. Tree rings appear to be a repository of this information but there is much noise in the collection of previous reconstructions, presumably associated with site selection, radial variability, choice of representative wood chemical constituent, and subtle effects of climate on fractionation. This study attempts to avoid these pitfalls and develop a 50-yr δ¹³C(ATM) record from juniper trees (genus Juniperus), in fact, by taking advantage of the influence of climate on fractionation. Trees were harvested from suitable sites in close proximity to weather stations with monthly records of temperature and precipitation. Ring material was then separated from each of the sections in 5-yr intervals from 1930 to 1979 around their full circumference, and cellulose was extracted from the wood. After measuring δ¹³C of the cellulose by standard mass-spectrometric techniques, a variety of δ¹³C vs. climate functions were examined for each interval. The most useful relationships for at most 7 of the 10 sites were δ¹³C with December temperature or precipitation, because the coefficients were nearly constant from one interval to the next (averaging -0.27%₀ °C⁻¹ for temperature and -0.04%₀ mm⁻¹ for precipitation) and the intercepts differed. Local pollution effects are believed responsible for the three anomalous sites. The separation of these regression lines of different intervals is interpreted as the response of the trees to the changing δ¹³C of atmospheric CO₂ so that δ¹³C(ATM) curves are constructed from this spacing. The shape of the best-fit reconstruction suggests the biosphere has acted as CO₂ source to about 1965 and may now be a net sink. Although these conclusions are limited by certain assumptions and statistical restrictions, evidence from the recent scientific literature tends to support the increasing role of the biosphere as an important carbon sink.

The interaction between carbon dioxide (CO2) and N-compounds such as 1,8-diazobicyclo[5.4.0]undec-7-ene (DBU) has been extensively studied in the Jessop Lab. Carbon disulfide (CS2) is the sulfur congener of CO2, although it exhibits different reactivity with N-containing compounds. This thesis presents the search for zwitterionic CO2-switchable polarity solvents, new and general reactivity of CS2 with amidines and guanidines, and attempts at using CO2 as a carbonyl source in the synthesis of nitrogen containing compounds. In the second chapter, the reactions of CO2 with various diamines are described. Spectroscopic methods and X-ray crystallography determined the structure of a solid zwitterionic carbamate salt of CO2 and N,N’-dimethyl-1,3-propanediamine. The polarity of the liquid zwitterionic carbamate salt formed with N,N,N’-trimethyl-1,3-propanediamine was measured using UV-Vis and the solvatochromic dye Nile red; its polarity was comparable to previous switchable polarity systems. The CO2 gravimetric uptake of the liquid zwitterionic carbamate salt was 28%, far greater than other solvents for the capture and release of CO2. In the third chapter, it was found that a variety of products can be accessed depending on the structure of the N-base (cyclic or acyclic) upon reaction of the base with CS2 at room temperature. The reaction of CS2 with cyclic amidines produced a cyclic trithioanhydride structure, forming a new C-C bond at a sp2-carbon beta to the imino nitrogen centre. When an amidine was acyclic it led to cleavage and formation of isothiocyanates in near quantitative yields. When a N-base had a N-H bond, CS2 can insert, forming a dimer in the presence of dichloromethane. In the fourth chapter, preliminary investigations are ascribed for synthesis of α-amino acids, amides, and ureas. Carboxylation of ketimines was detected, although the formed carboxylates from a variety of ketimines readily decomposed. Isomerization products of two ketimines were generated with DBU and CO2. Lewis acid catalysts were implemented towards the amidation of benzoylacetic acid and synthesis of ureas. Amidation of benzoylacetic acid did not occur in the presence of Lewis acid catalysts and CO2. Formation of a cyclic tetraalkylurea was afforded in low yields by the use of a diamine, CO2 and Lewis acid catalysts. / Thesis (Ph.D, Chemistry) -- Queen's University, 2013-12-01 19:16:55.257