Three strains of cyanobacteria (Anabaena PCC7120, A. variabilis and Nostoc commune), all belonging to the family Nostocaceae, were found to be capable of modulating the production and chemical composition of extracellular polysaccharides (EPS) in response to carbon and nitrogen availability as well as pH. While the carbohydrate compositions of the glycans produced by the different organisms were indicative of their recent evolutionary divergence, there were measurable differences that were dependent upon growth conditions. The EPS resulting from biofilm growth conditions was reduced in glucuronic acid levels in both Anabaena variabilis ATCC 29413 and Anabaena PCC 7120. Under planktonic conditions, the glycan from A. variabilis contained glucuronic acid when grown in nitrate-free BG-11₀ medium whereas A. PCC 7120 produced similar levels in standard BG-11 medium. This suggests that phylogeneticallyrelated cyanobacteria respond very differently to changes in their local environment. The pH of BG-11 cultures increased to 9-10 for all three strains of cyanobacteria. The increase resulted in an increase in the amount of dissolved inorganic carbon available in the medium, creating an imbalance in the carbon-nitrogen ratio, with the complete consumption of 17.65 mmol L⁻¹ nitrates raising the pH to near 10 in BG-11 medium. While increased carbon availability has been shown to induce capsulated morphologies in strains of cyanobacteria, only Nostoc commune DRH-1 exhibited this behavior, and only when grown in BG-11 medium. Carbon and nitrogen availability as well as pH modulate the monosaccharide composition of the glycan generated by cyanobacteria investigated. The different characteristics of the glycans produced can affect the survivability of the organisms and the community structure of cyanobacterial biofilms and microbial mats found in nature. As cyanobacteria are ubiquitous organism both now and in the past, they play a pivotal role in the biological and geological processes of the Earth, controlling the availability and cycling of carbon and nitrogen both actively and passively. / Master of Science in Life Sciences

The forests of south-eastern Australia, having evolved in one of the most fire-prone environments in the world, are characterized by many adaptations to recovery following burning. Thus forest ecosystems are characterized by rapid regenerative capacity, from either seed or re-sprouting, and mechanisms to recover nutrients volatilized, including an abundance of N2 fixing plants in natural assemblages. Soil physical, chemical and biological properties are directly altered during fire due to heating and oxidation of soil organic matter, and after fire due to changes in heat, light and moisture inputs. In natural ecosystems, carbon (C) and nitrogen (N) lost from soil due to fires are recovered through photosynthesis and biological N2 fixation (BNF) by regenerating vegetation and soil microbes. / This study investigated post-fire recovery of soil C and N in four structurally different sub-alpine plant communities (grassland, heathland, Snowgum and Alpine ash) of south-eastern Australia which were extensively burnt by landscape-scale fires in 2003. The amount and isotopic concentration of C and N in soils to a depth of 20 cm from Alpine ash forest were assessed five years after fire in 2008 and results were integrated with measurements taken immediately prior to burning (2002) and annually afterwards. / Because the historical data set, comprised of three soil samplings over the years 2002 to 2005, consisted of soil total C and N values which were determined as an adjunct to 13C and 15N isotopic studies, it was necessary to establish the accuracy of these IRMS-derived measurements prior to further analysis of the dataset. Two well-established and robust methods for determining soil C (total C by LECO and oxidizable C by the Walkley-Black method) were compared with the IRMS total C measurement in a one-off sampling to establish equivalence prior to assembling a time-course change in soil C from immediately pre-fire to five years post-fire. The LECO and IRMS dry combustion measurements were essentially the same (r2 >0.99), while soil oxidizable C recovery by the Walkley-Black method (wet digestion) was 68% compared to the LECO/IRMS measurements of total C. Thus the total C measurement derived from the much smaller sample size (approximately 15 mg) combusted during IRMS are equivalent to LECO measurement which require about 150 mg of sample. / Both total C and N in the soil of Alpine ash forests were significantly higher than soils from Snowgum, heathland and grassland communities. The ratio of soil NH4+ to NO3- concentration was greater for Alpine ash forest and Snow gum woodland but both N-fractions were similar for heathland and grassland soils. The abundance of soil 15N and 13C was significantly depleted in Alpine ash but both isotopes were enriched in the heathland compared to the other ecosystems. Abundance of both 15N and 13C increased with soil depth. / The natural abundance of 15N and 13C in the foliage of a subset of non-N2 fixing and N2 fixing plants was measured as a guide to estimate BNF inputs. Foliage N concentration was significantly greater in N2 fixers than non-N2 fixers while C content and 13C abundance were similar in both functional groups. Abundance of 15N was depleted in the N2 fixing species but was not significantly different from the non-N2 fixers to confidently calculate BNF inputs based on the 15N abundance in the leaves. / The total C pool in soil (to 20 cm depth) had not yet returned to the pre-fire levels in 2008 and it was estimated that such levels of C would be reached in another 6-7 years (about 12 years after the fire). The C and N of soil organic matter were significantly enriched in 15N and 13C isotopes after fire and had not returned to the pre-fire levels five years after the fire. It is concluded that the soil organic N pool can recover faster than the total C pool after the fire in the Alpine ash forests.

Thesis (Ph. D.)--University of Washington, 2002. / Vita. Includes bibliographical references (leaves 148-163).

Carbon-carbon and carbon-nitrogen bond forming events are essential in chemistry. Although numerous stoichiometric/catalytic methods provided elegant and powerful solutions enabling those processes, the use of scarce/toxic reagents and harsh conditions is still ubiquitous in this field. As a result, extensive research has been conducted in the development of environmentally benign and inexpensive reagents for such transformations, however, general solutions remain a challenge. In this context, one of the focuses of our lab is to enable those processes in a more practical and sustainable fashion by using hypervalent iodine reagents. In this dissertation we demonstrate the synthetic applications of λ3-iodane reagents towards the formation of challenging carbon-carbon and carbon-nitrogen bonds in a complementary way to the methods already reported. Chapter 1 of this dissertation outlines the general electronic structure, geometry, synthesis and reactivity of λ3-iodanes as serves and background regarding these reagents. Chapter 2 highlights the applications of λ3-iodanes to access high-oxidation state transition metals until the year of 2017. This literature review provides detailed information about how λ3-iodanes can be applied to access 1st, 2nd and 3rd row high-oxidation complexes, as well as mechanistic details and synthetic utility of high-valent transition metals. Chapter 3 demonstrates our efforts to generate selective carbon-nitrogen and carbon-carbon products from a high-valent nickel complex. This led to important information of this mechanism adopted by the reaction and how the choice of oxidant can impact 1e- versus 2e- oxidative pathways on “hard” nickel pincer scaffolds. Chapter 4 describes our efforts towards the selective formation of α-C(sp2)-C(sp2) bonds at the α-position of enones via a reductive Iodonium-Claisen rearrangement. We demonstrate the utility of β-pyridinium silyl enol ethers as a platform for direct α-arylation, and how the 2-iodo-aryl-α-arylated enones can be used to access diverse heterocyclic structures. Chapter 5 demonstrates our initial efforts towards the selective C2 or C3 carbon-nitrogen bond formation on indoles. By exposing different indoles to (bis)cationic nitrogen-ligated HVI (N-HVI) reagents we found that selective C2 or C3 C-H indole-pyridinium salts can be formed in good to excellent yield. Although, this project is not finished yet, we anticipate the indole-pyridinium salts generated could serve as platform for accessing diverse piperidines, pyridones and primary amines through straightforward procedures. The combined chapters of this dissertation highlight the applications of λ3-iodanes towards transition metals and emphasize the applications of these reagents to enable challenging C–C and C–N bond formation events. More importantly, this dissertation serves as a guide for future development of the hypervalent iodine field. / Chemistry

Diss. (sammanfattning) Umeå : Umeå universitet, 2008. / Härtill 3 uppsatser.

O presente trabalho avaliou o efeito da relação \'C\'/\'N\' na produção biológica de hidrogênio a partir de água residuária sintética a base de sacarose. Reatores de leito fixo e fluxo ascendente, com polietileno de baixa densidade reciclado para adesão da biomassa, foram operados a 25°C e com um tempo de detenção hidráulica (TDH) de 2 horas. Analisaram-se diferentes relações \'C\'/\'N\' (40, 90, 140 e 190), usando a sacarose e a uréia como fontes de carbono e nitrogênio, respectivamente. Os valores médios de produtividade de \'H IND.2\' foram de 0,6 mol-\'H IND.2\'/mol-sac, 1,3 mol-\'H IND.2\'/mol-sac, 2,2 mol-\'H IND.2\'/mol-sac e 1,7 mol-\'H IND.2\'/mol-sac quando operados os reatores com relações \'C\'/\'N\' iguais a 40, 90, 140 e 190, respectivamente. Encontrou-se um valor ótimo para \'C\'/\'N\' de 137, que resultaria em produtividade de \'H IND.2\' de 3,5 mol-\'H IND.2\'/mol-sac, valor igual ao alcançado na relação \'C\'/\'N\' de 140. O biogás produzido foi composto de \'H IND.2\' e \'CO IND.2\', com valores médios porcentuais para o \'H IND.2\' de 53%, 49%, 61% e 52% para as relações \'C\'/\'N\' de 40, 90, 140 e 190, respectivamente. Os principais produtos intermediários produzidos durante a produção de \'H IND.2\' foram similares em todas as relações \'C\'/\'N\', sendo principalmente detectados ácido acético, ácido butírico e etanol. Sob excesso de nitrogênio, o crescimento da biomassa foi maior com efeitos negativos sobre a produção de hidrogênio, enquanto carência de nitrogênio permitiu o controle do crescimento da biomassa e resultou em maiores produtividades de hidrogênio. Durante os experimentos observou-se queda na produção do biogás provavelmente por atuação de bactérias hidrogênio-oxidantes. / This study evaluated the effect of the carbon/nitrogen (\'C\'/\'N\') ratio on the hydrogen production from a sucrose-based synthetic wastewater. Up-flow fixed-bed anaerobic reactors with recycled low-density polyethylene for biomass attachment, were operated at 25ºC and with a 2 hours time of hydraulic detention. Several \'C\'/\'N\' relationship were studied (40, 90, 140 and 190), using sucrose and urea as carbon and nitrogen sources, respectively. The average value of the hydrogen productivity were 0,6 mol-\'H IND.2\'/mol-suc, 1,3 mol-\'H IND.2\'/mol-suc, 2,7 mol-\'H IND.2\'/mol-suc e 1,7 mol-\'H IND.2\'/mol-suc they were reached when the reactors were operated with \'C\'/\'N\' of 40, 90, 140 and 190, respectively. It was found an optimal value for \'C\'/\'N\' of 137, which would result in productivity of 3,5 mol-\'H IND.2\'/mol-suc, an amount equal to that achieved in the \'C\'/\'N\' relationship of 140. Biogas produced was composed of \'H IND.2\' and \'CO IND.2\', with average \'H IND.2\' content 53%, 49%, 61% and 52% for \'C\'/\'N\' of 40, 90, 140 e 190, respectively. The mainly intermediary products during \'H IND.2\' fermentation were similar for all the \'C\'/\'N\' ratios, being specially detected acetic acid, butyric acid and ethanol. Under excess of nitrogen the biomass growth is higher with negative effects on hydrogen production while deprivation of nitrogen permits the control of biomass growth and results in higher hydrogen productivity. During the experiments it was been observed decline in the biogas production, probably because of the action of the hydrogen-oxidizing bacteria.

The western Antarctic Peninsula (WAP) is a hotspot of climatic and oceanographic change, with a 6°C rise in winter atmospheric temperatures and >1°C warming of the surface ocean since the 1950s. These trends are having a profound impact on the physical environment at the WAP, with widespread glacial retreat, a 40% decline in sea ice coverage and intensification of deep water upwelling. The main objective of this study is to assess the response of phytoplankton productivity to these changes, and implications for the marine carbon and nitrogen cycles in the WAP coastal zone. An extensive suite of biogeochemical and physical oceanographic data was collected over five austral summer growing seasons in northern Marguerite Bay between 2004 and 2010. Concentrations and isotopic compositions ( 15N, 13C, 14C) of dissolved nitrate, dissolved inorganic carbon species, particulate nitrogen, organic carbon and chlorophyll a are used in the context of a substantial ancillary dataset to investigate nutrient supply, phytoplankton productivity and nutrient uptake, export flux and the fate of organic material, and the factors underpinning pronounced seasonal and interannual variability. High-resolution biogeochemical time-series data for surface and underlying seawater, sea ice brine, sediment trap material and coretop sediments allow detailed examination of carbon and nitrogen cycle processes under contrasting oceanographic conditions and the interaction between these marine processes and air-sea exchange of climate-relevant CO2. This study shows that the WAP marine environment is currently a summertime sink for atmospheric CO2 in most years due to high productivity and biological carbon uptake sufficient to offset the CO2 supply from circumpolar deep waters, which act as a persistent source of heat, nutrients and CO2 across the shelf. For the first time, CO2 sink/source behaviour is parameterised in terms of nitrate utilisation, by exploiting the relationship between CO2 and nitrate concentrations, and deriving the nitrate depletion at which surface ocean CO2 is undersaturated relative to atmosphere and carbon sink behaviour is achieved. This could have vast utility in examining CO2 sink/source dynamics over greater spatial and temporal scales than by direct CO2 measurements, of which availability is more limited. This study documents abrupt changes in phytoplankton productivity, nitrate utilisation and biological CO2 uptake during a period of rapid sea ice decline. In fact, nitrate utilisation, particulate organic matter production and biological CO2 uptake all decrease by at least 50 % between a sea ice-influenced, high productivity season and one of low sea ice and low productivity. The key driver of interannual variability in production and export of organic material is found to be upper ocean stratification and its regulation of light availability to phytoplankton. Productivity, CO2 uptake and export are maximal when stratification is sufficient to provide a stable well-lit surface environment for phytoplankton growth, but with some degree of mixing to promote export of suspended organic matter. Strong stratification causes intense initial production, but retention of suspended organic particles in the surface ocean induces a self-shading effect, and overall productivity, CO2 uptake and export fluxes are low. When stratification is weak, mixing of phytoplankton over a larger depth range exposes cells to a wider range of light levels and reduces photosynthetic efficiency, thus total productivity and CO2 uptake. A conceptual model is developed here, which attempts to describe the mechanism by which sea ice dynamics exert the principal control on stratification and therefore productivity and CO2 uptake at the WAP, with potential application to other regions of the Antarctic continental shelf. Although meteoric waters (glacial melt and precipitation) are more prevalent in surface waters throughout the study, sea ice meltwater variability is driven by large and rapid spring/early summer pulses, which stabilise the upper ocean and initiate phytoplankton growth. The timing and magnitude of these sea ice melt pulses then exert the key control on stratification and seasonal productivity. In a low sea ice year of this study, the sea ice trigger mechanism was absent and productivity was low. This strongly suggests that ongoing sea ice decline at the WAP and greater frequency of such low sea ice years is likely to drive a dramatic reduction in productivity and export, which would substantially reduce the capacity of the summertime CO2 sink in this region. Ongoing warming and ecosystem change are thus likely to have severe impacts on net CO2 sink/source behaviour at the WAP over the annual cycle, and the role of the Southern Ocean in regulating atmospheric CO2 and global climate. Finally, factors influencing the stable isotopic signature of particulate organic carbon ( 13CPOC), a common paleo-proxy, are assessed. 13CPOC is greatly influenced by seasonal shifts in diatom assemblages and isotopically heavy sea ice material, so cannot be used as a robust proxy for ambient CO2 in the coastal Southern Ocean.

Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniversitet, 2004. / Härtill 4 uppsatser.

Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniv., 2007. / Härtill 4 uppsatser.

Thesis (Ph.D.) -- University of Texas Southwestern Medical Center at Dallas, 2006. / Partial embargo. Vita. Bibliography: 128-131.