Rivers and streams are increasingly recognised as important components in the global carbon cycle, and act as net sources of CO2 and CH4 to the atmosphere. However, the origins and controls over the fate of these greenhouse gases are still poorly constrained. This thesis firstly explores the production of CO2 and CH4 in the sediment of several rivers over a geological gradient (chalk, sand and clay), to investigate the magnitude and controls on production. It was found that, whilst there are some general patterns due to geology, variables such as organic carbon content are much better predictors of production of CO2 and CH4 and these can vary widely within a single reach. The response of production to temperature was found to be very constant across rivers and in both summer and winter, suggesting a uniform increase in production of both CO2 and CH4 with projected future climate change. However, production of CH4 was much more responsive to temperature change than was CO2, meaning a greater proportion of carbon is mineralized as CH4 under warmer conditions and indicating a positive feedback with global warming. In addition, the amount of CO2 and CH4 out-gassed from the rivers to the atmosphere was measured. It was found that the amount out-gassed could not be explained by local sediment respiration alone: CO2 out-gassing was consistently higher (and CH4 consistently lower) than that produced by the riverbed. Instead, CO2 out-gassing was under hydrological control, and was correlated with rainfall. The source of this was ingress from the surrounding catchment, with higher out-gassing during periods of high rainfall. This strong hydrological controls on CO2 emissions were however modulated by biological processes, as lower emissions were measured during the day than night; and the difference could be accounted for by local in-stream GPP.

Fluorescent carbon dots are a new class of carbon nanomaterials that have emerged recently, and have created a lot of interest as a potential competitor to classical semiconductor quantum dots. Carbon dots possess low toxicity, biocompatibility, easy and low-cost synthesis, and good optical properties. They show huge potential as novel and versatile nanomaterials for a wide range of applications such as bioimaging, drug delivery, chemical sensing, photocatalysis, and as sensitizers for photovoltaic solar cells. The main motivation for this research was the need to produce non-toxic, low-cost nanomaterials with good optical and electrical properties for the use in the fabrication of sustainable, inexpensive nanostructured solar cells with good efficiency. The main aims and objectives of this PhD research were: to synthesize fluorescent carbon dots from biomass-derived precursors by using the hydrothermal synthesis method, to understand and explain structural and optical properties of the as-synthesized carbon dots, and to use the carbon dots as sensitizers for nanostructured solar cells. Carbon dots (CDs) were synthesized using hydrothermal synthesis method from polysaccharides (chitosan and chitin), monosaccharide (D-glucose), amino acids (L-arginine and L-cysteine), and from real food waste in the form of lobster shells. Carbon dots were thoroughly characterized to obtain the information about their structural and optical properties. The as-synthesized carbon dots showed polydispersity and quasi-spherical morphology, with particle sizes ranging from 5-17 nm. Carbon dots showed predominantly amorphous nature, and the functional groups from the starting precursors were successfully incorporated into the as-synthesized carbon dots. Diluted solutions of carbon dots were transparent under daylight and showed blue-green photoluminescence emission under UV excitation. All carbon dots showed excitation-dependent photoluminescence emission which was more pronounced for excitation wavelengths larger than 320 nm. Chitosan CDs, L-cysteine CDs and lobster CDs also showed excitation-independent emission for excitation wavelength in the range of 200 - 320 nm. The highest fluorescence quantum yield of (43.3 ± 2.1) % was calculated for L-arginine CDs. It was concluded that the origin of light emission in carbon dots must be governed by the interplay between the absorption due to the carbon cores and the surface functional groups. Considering the application of the as-synthesized carbon dots, two types of solar cells were fabricated. Carbon dots were used as sensitizers for ZnO-nanorod-based and for TiO2-based nanostructured solar cells. Three types of carbon dots (chitosan CDs, chitin CDs and D-glucose CDs) were used as sensitizers for ZnO-nanorod-based solar cells. ZnO nanorods were successfully coated with carbon dots, and the chitosan-CDs-sensitized solar cells showed the efficiency of 0.061 %. When using layer-by-layer coating method, solar cells with combination of chitosan- and chitin-CDs as sensitizers showed the efficiency of 0.077 %. All six types of carbon dots (chitosan CDs, chitin CDs, D-glucose CDs, L-arginine CDs, L-cysteine CDs, and lobster CDs) were used as sensitizers for TiO2-based nanostructured solar cells. TiO2-based solar cells sensitized with carbon dots showed much higher efficiency compared to the ZnO-nanorod-based solar cells. L-arginine-CDs sensitized TiO2-based solar cells showed the highest efficiency of (0.362 ± 0.007) %, which was the best efficiency of all fabricated solar cells. By surveying a range of biomass-derived carbon dots, and demonstrating a clear link between functionalisation and solar cell performance, this PhD research project provides a guide to direct future development of low-cost, biomass-derived sensitizers for nanostructured solar cells.

It has been found that the composites of carbon nanotubes (CNTs) and epoxy resin could greatly enhance damping ability while the stiffness is kept at a very high level. In this research, carbon nanotube enhanced epoxy resin is fabricated. The dynamic properties of the nanotube composites are evaluated. A testing apparatus for obtaining composite dynamic properties is set up and measurement procedures are given. Multiple groups of specimens are made for investigations. In particular, the loss factors together with dynamic stiffness are measured for the specimens with different CNT weight ratio. Experimental results show that CNT additive can provide the composite with several times higher damping as compared with pure epoxy. The composite is much stiffer than viscoelastic material (VEM) while the damping is comparable when strain is above certain level. In order to further study the damping mechanism of the CNT composite, models are developed. Composite unit cell models containing single CNT segments are built by using finite element method (FEM). Models with varying CNT orientations are considered in order to describe the behaviors of the randomly oriented CNTs inside the epoxy matrix. Composite loss factors are calculated based on the average ratio of the unit cell energy loss to the unit cell energy input. Calculated loss factors under different strain levels are compared to experimental results. With the validated model, parametric study is thereafter performed. Parameters such as CNT dimensions and CNT alignment orientation are studied. Those factors lead to higher composite damping capacity are identified. / by Dai, Ruoli. / "September 2007." / Adviser: Wei-Hsin Liao. / Source: Dissertation Abstracts International, Volume: 69-08, Section: B, page: 4978. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2007. / Includes bibliographical references (p. 93-97). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307.

Submitted by LAÍS GALVÃO CAETANO null (laisgalvao@iq.unesp.br) on 2017-02-06T13:41:04Z No. of bitstreams: 1 Dissertação Mestrado Laís Galvão Caetano.pdf: 2178003 bytes, checksum: 2239574ffc48afbca6a43b06084d326b (MD5) / Approved for entry into archive by LUIZA DE MENEZES ROMANETTO (luizamenezes@reitoria.unesp.br) on 2017-02-09T17:06:10Z (GMT) No. of bitstreams: 1 caetano_lg_me_arafo.pdf: 2178003 bytes, checksum: 2239574ffc48afbca6a43b06084d326b (MD5) / Made available in DSpace on 2017-02-09T17:06:10Z (GMT). No. of bitstreams: 1 caetano_lg_me_arafo.pdf: 2178003 bytes, checksum: 2239574ffc48afbca6a43b06084d326b (MD5) Previous issue date: 2016-12-21 / A fibroína da seda extraída dos casulos do bicho-da-sêda é um co-polímero particularmente atraente para aplicações em dispositivos fotônicos e opticoeletrônicos devido a sua transparência óptica, biocompatibilidade e propriedades mecânicas. Esta tese apresenta a obtenção de suspensões e filmes iridescentes-luminescentes de fibroína contendo nanopartículas luminescentes de carbono (“carbon dots”) obtidos a partir de carvão vegetal. As nanopartículas luminescentes de carbono apresentam biocompatibilidade, baixa toxicidade, propriedades de fotoluminescência interessantes e possibilidade de modificação da superfície. Redes de difração foram produzidas nestes filmes utilizando como molde um DVD comercial. Os materiais obtidos foram caracterizados por um conjunto de técnicas de análise: Microscopia de Força Atômica (AFM), Microscopia Eletrônica de Varredura (MEV), Microscopia Eletrônica de Transmissão (MET), Espectroscopia de absorção na região do UVVis, Espectrofotometria de absorção molecular na região do infravermelho com transformada de Fourier (FTIR) e Luminescência. Medidas de luminescência mostram que os carbon dots emitem múltiplas cores entre toda a região do visível. Planos cristalinos foram observados nas imagens de MET das nanopartículas, no qual foram asssociadas a estrutura do grafite. Pela análise de UV-Vis dos carbon dots observou-se que a absorção óptica decai gradualmente à medida em que ocorre deslocamento para o vermelho e para os filmes de fibroína observou-se um ombro referente a transição eletrônica da tirosina (aminoácido de sua composição). A partir dos espectros de FTIR observou-se que não houve mudança na estrutura da fibroína após a adição dos carbon dots. As imagens de AFM e MEV comprovam a presença dos micropadrões periódicos na superfície dos filmes. Os resultados mostraram que os filmes de fibroína contendo carbono dots tem um grande potencial para a biomedicina, principalmente devido os seus parâmetros de luminescência se extenderem em toda a região do visível e por apresentar uma matriz sustentável, com excelentes propriedades ópticas e mecânicas. / Silk fibroin extracted from silkworm cocoons is a particularly attractive copolymer for applications in photonics and optoelectronics devices due its optical transparency, biocompatibility and high mechanical strength. This thesis presents the preparation of suspensions and iridescent-luminescent films of silk fibroin containing luminescent carbon nanoparticles (carbon dots) obtained from vegetal coal. Luminescent carbon nanoparticles present high biocompatibility, low toxicity, interesting photoluminescence properties and possibility of surface modification. Diffraction gratings were produced in these films using a commercial DVD as a template. The materials obtained were characterized by a set of analysis techniques: Atomic-Force Microscopy (AFM), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), UV-Visible Spectroscopy, Fourier transform infrared spectroscopy (FTIR), and Luminescence. Luminescence measurements show that carbon dots emit light at the entire visible region. Crystalline planes were observed in the TEM images of the nanoparticles, where upon the graphite structure was associated. By analyzing the UV-Vis spectra of the carbon dots it was observed that the optical absorption gradually decreases as the red shift occurs. In the UV-Vis spectra of the silk fibroin films it was observed a shoulder referring to the electronic transition of the tyrosine (amino acid of its composition). From the FTIR spectra it was observed that there was no change in the silk fibroin structure after addition of the carbon dots. The AFM and SEM images confirm the presence of the periodic micro-patterns on the surface of the films. The results showed that the silk fibroin films containing carbon dots have a great potential for biomedicine, mainly due to its luminescence parameters extending throughout the visible region and due to a sustainable platform with excellent optical and mechanical properties.

Telogenetic epikarst carbon sourcing and transport processes and the associated hydrogeochemical responses are often complex and dynamic. Among the processes involved in epikarst development is a highly variable storage and flow relationship that is often influenced by the type, rate, and amount of dissolution kinetics involved. Diffusion rates of CO2 in the epikarst zone may drive hydrogeochemical changes that influence carbonate dissolution processes and conduit formation. Most epikarst examinations of these defining factors ignore regional-scale investigations in favor of characterizing more localized processes. This study aims to address that discrepancy through a comparative analysis of two telogenetic epikarst systems under various land uses to delineate regional epikarst behavior characteristics and mechanisms that influence carbon flux and dissolution processes in south-central Kentucky. High-resolution hydrogeochemical and discharge data from multiple data loggers and collected water samples serve to provide a more holistic picture of the processes at work within these epikarst aquifers, which are estimated to contribute significantly to carbonate rock dissolution processes and storage of recharging groundwater reservoirs on the scale of regional aquifer rates. Data indicate that, in agricultural settings, long-term variability is governed by seasonal availability of CO2, while in urban environments extensive impermeable surfaces trap CO2 in the soil, governing increased dissolution and conduit development in a heterogonous sense, which is often observed in eogenetic karst development, as opposed to bedding plane derived hydraulic conductivity usually observed in telogenetic settings. These results suggest unique, site-specific responses, despite regional geologic similarities. Further, the results suggest the necessity for additional comparative analyses between agricultural settings and urban landscapes, as well as a focus on carbon sourcing in urban environments, where increased urban sprawl could influence karst development

Black carbon, a proxy for woodsmoke was measured indoors and outdoors for an occupied residence in Cambria, CA during the winter months of 2009. The purpose was to investigate the infiltration parameters: air exchange rate, deposition rate, and penetration factor. The second part of this study investigated the light absorption properties of organic carbon from residential wood combustion, the dominant fraction of woodsmoke. To assess woodsmoke variation, a study conducted parallel to the one presented in this thesis (Ward, 2009), a grid array of personal emission monitors (PEMS) and aethalometers were placed in a small area, approximately one square kilometer, within a community in Cambria, California between the months of November 2008 and March 2009. In this study, PEMS were used to collect particles on filters, which were analyzed for tracers for woodsmoke, including levoglucosan, elemental carbon, and organic carbon. Aethalometers measured black carbon, an indicator of carbon combustion. Additional PEMS and aethalometers were placed inside one residential home to better understand infiltration of woodsmoke. To model the infiltration of woodsmoke, the Lawrence Berkeley National Laboratory Air Infiltration Model was used. The home of interest was chosen such that indoor sources of particulate matter (PM) were minimal. This insures that all PM measured indoors was from outdoor sources, namely household chimneys. While indoor sources such as indoor fires and resuspension of particles were of concern, homes were chosen to minimize these sources. To investigate the infiltration parameters, four different solution techniques were used. Two of the solution techniques used SOLVER, a Microsoft Excel program, to minimize the sum of squared differences between calculated indoor concentrations and measured indoor concentrations, with all three parameters (air exchange rate, penetration, and deposition) as independent variables. The other two solution techniques used the Air Exchange Rate (AER) model from Lawrence Berkeley National Laboratory (LBNL) (Sherman & Grimsrud, 1980) and then used SOLVER to calculate deposition rate and penetration factor. Solution techniques 1 and 3, which used SOLVER to find all three parameters, had average penetration factors of 0.94 and 0.97 respectively, while solution techniques 2 and 4, which used the LBNL AER model had average penetration factors of 0.85 and 0.78 respectively. The deposition rates for solution techniques 1,2,3, and 4 were 0.10, 0.07, 0.08, and 0.04 hr-1 respectively. The air exchange rates varied throughout the study and ranged from 0.1 to 0.7 hr-1. The average indoor/outdoor ratio was also found to be 0.75. The aerosols derived from the study samples were found to have light absorption properties that were heavily spectrally dependent, which is consistent with expectations for wood combustion aerosols. Conversely, traffic derived aerosols are not found to be heavily spectrally dependent and follow the power law relationship of λ-1 whereas our samples followed λ-1.7 across all wavelengths and λ-2.25 for wavelengths less than 600 nm. The reason for the difference in spectral dependence is the presence of light absorbing organic carbon in wood smoke that is not found in diesel aerosols. The optical absorbances were also calculated for our samples and average values were found to be 3 and 1 m2/g for 370 and 450 nm wavelengths respectively.

No description available.

Soil carbon (C) is important because even small changes in soil C can affect atmospheric concentrations of CO₂, which in turn can influence global climate. Adequate soil carbon is also required to maintain soil quality, which is important to if agricultural production is to be sustained. The soil carbon balance of New Zealand's pastoral soils is poorly understood, with recent research showing that soils under dairy pasture have lost large amounts of C during the past few decades. The main objective of this research was to determine an annual farm scale C budget for an intensively grazed dairy farm, with a second objective being to determine the amount of CO₂-C lost following cultivation for pasture renewal, and soil pugging by dairy cattle. A third objective was to investigate the environmental controls of CO₂ exchange in a dairy farm pasture system. Net ecosystem exchange (NEE) of CO₂ was measured using an eddy covariance (EC) system from 15 December 2007 to 14 December 2008. Closed chamber techniques were used to measure CO₂ emissions from three cultivated paddocks and three adjacent pasture paddocks between 26 January 2008 and 5 March 2008. CO₂ emissions were also measured using chambers from pugged and control plots between 25 June and 5 August. Coincidentally this research was carried out in a year with a severe summer/autumn drought and a wetter than usual winter. Annual NEE measured with the eddy covariance system was -1,843 kg C ha⁻¹ (a C gain by the land surface). Accounting for C in supplement import, milk export, pasture export and losses in methane, the dairy pasture system was a net sink of -880±500 kg C ha⁻¹. This C sequestration occurred despite severe drought during the study, which was in contrast to other studies of grasslands during drought. Cultivation under dry conditions did not increase cumulative CO₂-C emissions compared to adjacent pasture paddocks. However, when C inputs to pasture paddocks via photosynthesis were included in calculations, net C loss from the cultivated paddocks (during the 39 day study) was estimated to be 622 kg C ha⁻¹ more than the pasture paddocks. CO₂ emissions were lower from pugged plots compared to control plots, probably caused by decreased microbial and root respiration due to wetter soil conditions, and lowered root respiration as a result of lower pasture production. Volumetric soil moisture content (soil moisture) had a dominant effect on CO₂ exchange at a range of temporal scales. Respiration and photosynthesis were both reduced when soil moisture was below 43% (~the lower limit of readily available water) and photosynthesis virtually ceased when soil moisture declined below 24% (~wilting point). Soil moisture also influenced the relationship between temperature and respiration and photosynthetic flux density (PPFD) and NEE. These results suggest that management related soil disturbances of occasional cultivation for pasture renewal and soil pugging, are unlikely to cause large losses of soil C. Further, a severe drought also did not cause CO₂-C losses from the land surface to the atmosphere on an annual scale, in contrast to previous studies.

Thesis (Ph. D. in Chemistry)--Vanderbilt University, Dec. 2007. / Title from title screen. Includes bibliographical references.

Graduation date: 1995