Fixed N (nitrate, nitrite, and ammonium) is a limiting nutrient for photosynthesis in the surface ocean. The rates and relative importance of N cycling processes, however, are temporally and spatially complex, which hamper their direct measurement and quantification. The South Atlantic subtropical front separates the Atlantic Ocean and the subantarctic, an area which can elucidate information about water masses both entering and leaving the basin. Through the GEOTRACES programme, an oceanographic section across 40°S in the South Atlantic is used to investigate biogeochemical cycling of nitrogen and carbon in this region. Hydrographic data, in combination with the isotopic composition of nitrate (NO3-), particulate organic carbon and particulate nitrogen (δ15NNO3, δ18ONO3, δ13CPOC, δ15NPN), is used to provide integrative measurements for temporally and spatially variable processes of the marine N-cycle and C-cycle. A thorough examination of the stable isotope cycling of particulate and dissolved N across the subtropical front is used to quantify the supply of fixed N to the mixed layer. The relative importance of nitrate from the subsurface, N2 fixation, terrestrial input and atmospheric deposition in supplying production is determined. Typically, 30-50% of the export flux in the subtropical water masses is sourced from N2 fixers and up to 75% within the Brazil Current. This finding suggests that diazotrophs may be abundant in the South West Atlantic providing a source of new N to this region. To assess the basin scale N-cycling processes, the deep water masses were analysed to reveal the origin and history of NO3-. Intermediate waters formed in the subantarctic are enriched in δ15NNO3 and δ18ONO3 from partial utilisation by algae. This enrichment in δ15NNO3 is not present in the subtropical North Atlantic or the return flow of the North Atlantic Deep Water (NADW), which decreases from ~5.9‰ in the newly formed intermediate waters to ~4.8‰ in the NADW at 40°S. The modification of isotopic signatures through the subtropical Atlantic can be calculated as an incorporation of 26-36 Tg N yr-1 of newly fixed N from an isotopic source of -1‰ (N2 fixation). The extent of N addition is higher than estimated rates of N loss within the Atlantic and surpasses the amount of N deficit supplied to the basin. Fixed N inputs and losses through the global ocean are investigated by the assessment of remineralised nitrate added to the ocean interior. A lower δ15N is observed in Atlantic remineralised nitrate in comparison to the Pacific. The relative importance of N2 fixation and pelagic denitrification within each ocean basin is quantified and through this approach, N2 fixation rates are estimated at 92-116 Tg N yr-1 in the Pacific and 24-32 Tg N yr-1 in the Indian Ocean. Combining Atlantic N2 fixation of ~32 Tg N yr-1 with Indo-Pacific, global N2 fixation rates can be estimated at 142-184 Tg N yr-1. The high inputs in the Pacific suggest that excess P is the dominant control on the success of N2 fixers. However, estimates of new N addition to the Atlantic indicate other mechanisms such as the recycling efficiency of P and supply of Fe to the surface ocean increase N2 fixation rates above this threshold. The organic matter supplied to sediments is principally derived from phytoplankton across the subtropical front. High organic content is associated with the productive Brazil-Malvinas Confluence region where a diverse supply of nutrients sustains elevated biomass. The Rio Plata outflow is characterised with high δ15NNO3 and δ15NPN, suggesting denitrification processes occur in the estuary. A low δ13C source associated with high Al concentrations is identified on the western slope, indicating a supply of terrestrial derived C to the deep ocean. The fractionation of C uptake by phytoplankton is assessed in subtropical and subantarctic waters. In the subantarctic, CO2[aq] and growth rates determine the extent of C isotope fractionation. In this region, low species diversity and a small range in cell size enable the fractionation from CO2[aq] and growth rate to be expressed in phytoplankton. In subtropical water masses a larger range of cell size is the principal determinant of C fractionation. Increased surface area to volume is the main mechanism for increasing C uptake, arguing against the use of δ13CPOC as a palaeoproxy. The low δ13CPOC and δ15NPN observed in the subtropics (from C fractionation and N2 fixation) contrast the heavier signatures in the subantarctic. These observations are propagated to the sediments, wherein organic matter shifts are determined by changes in the subtropical front over time. The results of this study have greatly improved knowledge of N and C cycling within the South Atlantic, providing new insight into the cycling of these two important elements in the surface and deep ocean, on a regional and global scale.

This dissertation explores the electrochemical behavior of enzymes and their cofactors at carbon nanotube (CNT) and nitrogen-doped carbon nanotube (N-CNT) electrodes. Two common types of oxidoreductases are considered: flavin adenine dinucleotide (FAD)-dependent oxidases and nicotinamide adenine dinucleotide-dependent (NAD⁺)-dehydrogenases. Chapter 1 presents the oxygen reduction reaction (ORR) at N-CNT electrodes as a way to electrochemically measure enzymatic turnover at the electrode surface. The unique peroxide pathway at N-CNT electrodes, which catalytically disproportionates hydrogen peroxide (H₂O₂) back into oxygen, provides an increased ORR current directly proportional to the rate of enzymatic turnover for H₂O₂ producing enzymes, even in an oxygen saturated solution. Biosensing of L-lactate using the increased ORR current is demonstrated using L-lactate oxidase. Chapter 2 explores the surface bound electrochemical signal of FAD when FAD-dependent enzyme or free FAD is allowed to spontaneously adsorb onto the CNT/N-CNT surface. Specifically, the origin of the enzymatically generated FAD signal and the rate constant of the electron transfer are elucidated. Chapter 3 continues the discussion of the cofactor FAD by demonstrating its use as an informative surface specific redox probe for graphitic carbon surfaces. Primarily, FAD can be used to determine the electroactive surface area and the relative hydrophobicity/hydrophilicity of graphitic surfaces. Chapter 4 changes gears to NAD⁺-dependent dehydrogenases by investigating the electrocatalytic oxidation of NADH at N-CNTs in comparison with conventional carbon electrodes or nondoped CNTs. Biosensing of glucose through the oxidation of NADH is demonstrated using glucose dehydrogenase adsorbed onto the N-CNT surface. Chapter 5 continues the discussion of NAD⁺-dependent dehydrogenases by addressing the reaction kinetics of NADH oxidation at N-CNTs as a tool to measure the enzymatic reduction of NAD⁺.

Bryophytes form an important component of northern vegetation communities. Mosses efficiently capture aerially deposited nutrients, restricting nutrient availability to the soil. Given that key ecosystem processes of northern ecosystems are nutrient-limited, understanding nutrient cycling of the moss layer is key to understanding ecosystem nutrient and C cycling in these systems. However, the role of the moss layer in regulating ecosystem-scale nutrient and C cycling, while potentially significant, is largely unknown. The aim of this thesis is to investigate the effect of the relative availability of N and P on aspects of bryophyte nutrient uptake, retention and C acquisition. The hypothesis investigated is that the availability of one nutrient will influence the demand for the other and thereby moss nutrient acquisition and retention mechanisms. To test this hypothesis, various aspects of moss nutrient cycling in response to the relative availability of N and P were investigated. As the C cycle is tightly linked to the N and P cycles, the hypothesis extended to include bryophyte C assimilation and decomposition processes of an arctic tundra. Bryophyte nutrient demand was chiefly governed by the tissue N:P ratio. Consequently, nutrient uptake, both from aerially deposited nutrients and through moss-cyanobacteria N2 fixation, and nutrient losses after a simulated rainfall event were mostly in response to the relative availability of N and P rather than the availability of one nutrient alone. This thesis provides novel evidence that ectohydric mosses have the ability to internally translocate nutrients. In conjunction with efficient nutrient capture, this trait makes mosses strong nutrient sinks which are likely to exert considerable control over ecosystem nutrient cycling. The relative availability of N and P played a role in C uptake of mosses. Through the production of recalcitrant litter and their insulating effect on soil microclimate mosses exerted an influence over ecosystem C cycling.

No description available.

Peatland ecosystems only cover 2-3 % of the Earth‟s surface but they represent significant carbon stores, holding approximately one third of the global soil carbon (C). The major peat forming genera Sphagnum appears to be highly sensitive to increased N availability. Many studies have shown decreased productivity of Sphagnum which could lead to a decrease in the amount of C stored, especially as many studies also show an increase in the decomposition rate with higher N deposition. However, the overall effects of N on CO2 fluxes of Sphagnum remain unclear. The present study aimed to look at the effects of increased N on Sphagnum productivity, decomposition and CO2 fluxes after long-term N additions (> 5 years) using a field experiment at Whim Moss in southern Scotland where N deposition has been manipulated employing a very realistic application coupled to rainfall since 2002. The experiment also has treatments with PK addition to test the effects of removing P and/or K-limitation. Measurements of plant tissue nutrient concentrations, visual assessments of Sphagnum viability, and pore water analysis were also carried out. Nitrogen additions increased tissue N, and decreased Sphagnum shoot extension and productivity. Simultaneous P and K additions alleviated the effects of N on tissue N concentrations and growth, although this was only significant for shoot extension. Visual assessments correlated well with tissue chemistry and productivity; the decline in health was associated with high %N and reduced productivity. Interestingly, in the present study increased N decreased the mass loss and again when PK was added with N decomposition rates were more similar to the control. With respect to the carbon balance of the site and the sustainability of peatlands the results suggest that the negative effect of N on C assimilation may be partially offset by the reduced decomposition rates. The CO2 measurements showed a large loss of C as CO2 from all the Sphagnum plots which was exacerbated by adding N especially when the air temperature increased. The positive temperature response of ecosystem respiration with N additions suggests that in high N deposition areas climate change and subsequent temperature rises will increase C losses from bogs.

Este trabalho tem como objetivo aplicar a teoria de modelos mistos ao estudo do teor de nitrogênio e carbono no solo, em diversas profundidades. Devido a grande quantidade de matéria orgânica no solo, o teor de nitrogênio e carbono apresentam alta variabilidade nas primeiras profundidades, além de apresentar um comportamento não linear. Assim, fez-se necessário utilizar a abordagem de modelos não lineares mistos a dados longitudinais. A utilização desta abordagem proporciona um modelo que permite modelar dados não lineares, com heterogeneidade de variâncias, fornecendo uma curva para cada amostra. / This paper has as an objective to apply the theory of mixed models to the content of nitrogen and carbon in the soil at various depths. Due to the large amount of organic material in the soil, the content of nitrogen and carbon present high variability in the depths of soil surface, and present a nonlinear behavior. Thus, it was necessary to use the approach of nonlinear mixed models to longitudinal data analysis. The use of this approach provides a model that allows to model nonlinear data with heterogeneity of variances by providing a curve for each sample.

One of the most important parameters affecting hydrogen production in photofermentation process is the type of carbon and nitrogen sources. For this reason in this research, the effect of different nitrogen sources (5mM ammonium chloride and 2mM glutamate) and acetate concentrations (40

Carbon nanotubes (CNTs) are a relatively new allotrope of carbon that possess very unique and exciting physical characteristics. However, much is still unknown regarding their physical structure and chemical reactivity. The focus of this dissertation is to utilize the chemical modification of these filamentous carbon structures as a probe to investigate the structure and reactivity of carbon nanotubes. Also discussed is the ability of CNTs, once chemically modified, to interact with specific polymer matrices and how the addition of modified and unmodified CNTs affects the physical properties of these matrices.

Diss. (sammanfattning). Uppsala : Sveriges lantbruksuniv. / Härtill 5 uppsatser.

Thesis (M.S.)--West Virginia University, 1999. / Title from document title page. Document formatted into pages; contains xii, 120 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 102-107).