No description available.

Tropical soils are often characterised by low phosphorus availability prompting the view that the productivity of many tropical forests may be phosphorus (P) rather than nitrogen (N) limited. Nevertheless, to date, no study has assessed the mechanisms by which P-deficiency might be limiting rates of photosynthesis in tropical trees. A controlled glasshouse experiment investigated the effect of P deficiency on rates of photosynthesis (A) and related leaf traits for seven Australian tropical tree species drawn from different plant functional types (pFTs) thought to differ in their photosynthesis/nutrient relationships. Measurements of gas exchange and leaf structure were combined with laboratory assays ofleaf nutrients; subsequent field campaigns were conducted in tropical Queensland (also comparing forest with savanna), Peru and French Guiana. The greenhouse results showed that the A- [N] relationship is affected by P supply, but PFT effects were not as predicted and in Queensland savanna species were found to have higher photosynthetic N use efficiency compared with forest trees - despite lower leaf [P]. In South America, an expected cross-basin gradient in P availability was' confirmed with higher [P] for the Peruvian trees, but Ama.'{ did not differ between the two Peruvian plots despite a 48% increase in mean [P]. The combined field dataset, including more than 80 species, allowed novel cross-continental comparisons of major leaf fractions of P and N - these were found to differ at each hierarchical level: country, site and species. Attempts to define a unifying photosynthetic model for tropical trees confirmed a dominant role for N, but with a critical role for P also invoked. Model performance was, however, improved by allowing for specific geographic and phylogenetic effects. A current lack of understanding as to the basis of these unexplained phytogeograhic effects on photosynthesis/nutrient relationships constitutes a major obstacle in the development of universally-applicable large-scale photosynthesis models.

No description available.

Interest in arsenic in groundwater has greatly increased in the past decade because of the increased awareness of human health effects linked to prolonged drinking of untreated ground water supplies high in arsenic content. A number of studies on arsenic bioavailability in soils have linked the presence of organic matter to high arsenic content. The question of whether arsenic interacts with organic matter chemically becomes significant. The work reported in this thesis investigates the chemistry of arsenic interaction with humic acid which comprises 50 % of soil organic matter. The thesis begins with an overview of arsenic environmental chemistry including its signifitcance, distribution, metabolism and toxicity. A literature review outlines the aqueous chemistry of arsenic specifically speciation, adsorption and mobility. The first part of the study focuses on the investigation of arsenic humic acid reactions over a range of conditions, for example changes in pH and ionic strength. Hydrolysed species of inorganic arsenic M and (111), and an organic form of arsenic (CH3)2AsOOH, were employed. Results show that the extent of reaction generally increased with pH and decreased with ionic strength. The results were interpreted firstly by assuming simple association and then by postulating ligand exchange. The derived equilibrium constants showed weak arsenic interaction with humic acid. The second part of the study examined the identification of arsenic bearing phases in a reference soil sample and contaminated soil samples. The results were processed using Chemometric Identification of Substrates and Elements Distribution (CISED). The research concluded that arsenic was mainly associated with an iron oxide phase in soils.

The aim of this work was to investigate palladium-catalysed cyclisations of bromoenynamides in the synthesis of amidodienes, which on further reaction or oxidation can lead to a diverse range of heteroaromatic systems. Building upon work within the Anderson group on the palladium-catalysed cyclisations of bromoenynes, we have been able to successfully apply a palladium-catalysed carbopalladation/Stille coupling/electrocyclisation cascade to bromoenynamides and then further develop this to incorporate a Suzuki coupling, leading to bicyclic amidodienes which can undergo selective oxidation to a range of heteroaromatics including indolines, indoles, tetrahydroquinolines and benzazepines. During the investigations into the cascade cyclisation, a reductive cyclisation was discovered which enabled access to a range of monocyclic amidodienes. These could subsequently be subjected to a series of Diels-Alder cycloadditions (thermal, Lewis acid-catalysed, arynes) and oxidations to afford a complimentary range of heteroaromatic systems. Whilst this methodology was successful with bromoenynamides, extension of its application to bromoenynhydrazides, with the hope of accessing a relatively unusual range of heteroaromatic structures including indazoles, cinnolines and diazepines, proved to be more problematic. Finally, expansion of the cascade methodology into a fully intramolecular cyclisation, enabled studies towards the synthesis of the trikentrin family of natural products to be conducted.

2 offprints in pocket / Bibliography: leaves 184-210 / xx, 217 leaves, [1] leaf of plates : ill. (some col.) ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Soil Science, 1987

De nombreux sols forestiers français sont acides et pauvres en éléments nutritifs et les forêts françaises font face aujourd'hui à des pressions extérieures croissantes. Ces nouvelles contraintes sont d'ordre nutritionnel et/ou sylvicole et/ou climatique et risquent d'impacter la durabilité des écosystèmes forestiers à faible fertilité minérale. Il est donc très important de comprendre et quantifier les processus qui régissent les cycles des éléments nutritifs dans ces écosystèmes afin de prédire au mieux leurs évolutions possibles face à de telles contraintes et ainsi aider les gestionnaires forestiers à prendre des décisions réfléchies pour assurer leur durabilité. L'objectif principal de cette thèse était de comprendre le cycle du calcium et du magnésium dans un écosystème forestier productif bien que croissant sur un sol très faiblement pourvu en Ca et Mg. Pour cela, nous avons établi dans un peuplement de hêtre âgé de 35 ans des bilans de flux « entrées-sorties » basés sur des mesures classiques de pools et flux entre 2003 et 2008. Puis une expérience de multi-traçage isotopique (2H, 15N, 26Mg et 44Ca) a ensuite été conduite: les traceurs ont été apportés à la surface du sol en avril 2010 sous forme soluble et leur progression a été suivie dans l'écosystème jusqu'en mars 2012. Les résultats ont mis en évidence le rôle primordial que joue la matière organique dans les cycles du Mg et du Ca, en leur conférant notamment un caractère très conservatif. Le 26Mg et le 44Ca apportés ont été captés dans la fine couche de litière au sol puis lentement libérés. Dans les horizons minéraux, la matière organique du sol, qui semble contribuer à la plus grande part de CEC du sol, a fortement contribué à ralentir la migration du Mg et du Ca à travers le sol. Par rapport au Mg, le calcium apporté a été plus intensément retenu dans la litière, et moins intensément lixivié à travers le sol en raison de sa plus grande affinité pour la matière organique. Malgré les flux préférentiels d'eau mis en évidence par le traçage au 2H, aucune perte par drainage de 26Mg ou 44Ca n'a été mesurée. Deux années après l'apport, il restait dans la litière 8% du 26Mg et 33% du 44Ca apportés tandis que, respectivement, 52% et 46% ont été retrouvés dans les 10 premiers cm du sol. Les traceurs, rapidement absorbés par les racines fines ont migré dans l'arbre à des vitesses très différentes: les feuilles étaient enrichies en 15N dès le mois suivant l'apport des traceurs, tandis que seuls de très faibles enrichissements en 26Mg (mais pas de 44Ca) ont été mesurés dans la canopée en 2012. Le bilan en 2012 montre les arbres ont absorbé 27% de 26Mg et 20% de 44Ca et qu'ils sont majoritairement concentrés dans les tissus de la base du tronc. L'utilisation de traceurs isotopiques a permis de mettre en évidence la lenteur de la redistribution de Mg et encore plus de Ca dans l'écosystème, d'une part de la litière vers les sols et d'autre part des racines vers les canopées. Ce comportement est attribué à l'affinité de ces ions pour les charges carboxyliques portées par la matière organique. Enfin, la dilution isotopique mesurée dans les différents compartiments de l'écosystème à l'issue de deux années a permis de calculer des bilans et ainsi de valider les pertes de Mg calculées par l'approche classique de « bilan de fertilité minérale ». En revanche, les pertes de Ca calculées par cette même approche ont été mises en défaut, démontrant la contribution d'une source externe (absorption par les feuilles, altération…) ou interne (mobilisation du stock des tissus ligneux), non prise en compte dans l'approche classique. L'ensemble de ces travaux souligne l'intérêt de l'approche « traçage isotopique » en complément des approches conventionnelles afin d'étudier la fertilité minérale des écosystèmes forestiers. / Many forest soils in France are acid and nutrient poor. French forests endure today increased external constraints which may be nutritional and/or silvicultural and/or climatic. These constraints may strongly impact the sustainability of nutrient-poor ecosystems. It is thus important to understand and quantify the processes which govern nutrient cycling in these ecosystems to better predict soil fertility changes and help forest managers make sound decisions to sustain these ecosystems.The main objective of this thesis was to study magnesium and calcium cycles in a productive forest ecosystem with low available magnesium and calcium pools in the soils. For this purpose, in a 35-year-old beech stand, we computed input-output nutrient budgets between 2003 and 2008 using conventional approaches to measure nutrient pools and fluxes. A multi-isotopic (2H, 15N, 26Mg et 44Ca) tracing experiment was then carried out in the same plot: tracers were sprayed on the forest floor in April 2010 as soluble salts, tracer transfer was then monitored in the whole ecosystem until March 2012 (litter-layer, exchangeable pools, soil solutions, above-ground biomass…).The results evidenced the predominant role of organic matter in the very conservative cycling of Mg and Ca in this nutrient-poor soil. Indeed, the applied 26Mg and 44Ca were very rapidly retained in the fine litter-layer by ion-exchange processes. In the soil profile, most of the CEC was probably due to soil organic matter which played an important role in the retention of Mg and Ca in the soil. Compared to magnesium, calcium was more strongly retained in the litter layer and transferred more slowly in the soil profile because of the higher affinity of calcium for organic CEC. Despite preferential water flow evidenced by the water tracing experiment (2H), no leaching of 26Mg or 44Ca was observed during the study period. Two years after the application of tracers, 8% of applied 26Mg and 33% of applied 44Ca was still retained in the litter layer while, respectively, 52% and 46% of applied tracers were found in the first 10cm of the soil profile. Tracers were rapidly absorbed by the fine roots but were transferred from the roots to the canopy at very different velocities: leaves were enriched in 15N one month after the application of tracers while only very small 26Mg enrichments and not 44Ca were observed in the canopy in 2012. Tracer budgets in 2012 showed that trees absorbed 27% of 26Mg and 20% of 44Caand that tracers were mainly concentrated at the base of the bole. The use of isotope tracers evidenced the slow distribution of magnesium and the slower distribution of calcium in the ecosystem, on the one hand from the litter pool to the soil profile and on the other hand from the roots to the canopy. This behavior was attributed to the affinity of the cations for organic matter functional groups such as carboxyl groups.Finally the isotopic dilution technique of the applied tracers measured in the different ecosystem compartments after two years of monitoring enabled us to validate the Mg losses computed by nutrient budgets. However, Ca depletion suggested by nutrient budgets were proven to be nil thus evidencing the contribution of an external (foliar absorption, weathering) and/or internal (mobilization of nutrients stored in ligneous tissues) sources which are currently not taken into account in conventional approaches.Overall the results of the in situ ecosystem scale multi-isotopic tracing experiment show the added value of the “isotopic tracing” approach to study nutrient pools and fluxes in forest ecosystems in addition to conventional approaches.

Thesis (M.A. (Horticulture)) --University of Limpopo, 2010 / Refer to document / University of Namibia