Spatial and temporal heterogeneity of water and nutrient pools is closely associated with the existence of different plant communities in hydrologically-controlled ecosystems such as the Everglades. These various communities differ in their flooding and fire tolerances as well as nutrient requirements. Upland plant communities are of particular ecological significance since they have high biodiversity and provide habitat to terrestrial fauna, yet comprise less than 10 % of the total area. Restoration and maintenance of such communities requires an understanding of their water and nutrient requirements. Chapter 2 compares water source utilization in hammocks and pine rocklands on the Miami Rock Ridge using stable isotopes of water. Hammocks do not flood, while adjacent pinelands may flood between 2-3 months. In the wet season, hammocks were found to use phosphorus (P) rich soilwater, a local pool of water and nutrients while pineland plants primarily relied upon groundwater, the regional pool. Access to a rich pool of P in the oligotrophic Everglades was associated with higher community-level foliar P concentration in hammocks. However in the dry season, hammocks utilized groundwater, which suggests sensitivity to extended droughts. Chapter 3 compares the hammock (upland or head) and swamp forests (lowland or tail) on tree islands in the Shark River Slough. Uplands were associated with P-rich soilwater uptake in the wet season, with regional water uptake in the dry season. Accordingly, tree island heads are rich in foliar P and thereby P-hotspots in the Everglades. Foliar nutrient concentrations can thus indicate limiting nutrient availability in the Everglades. Chapter 4 looks at how leaf phenology patterns are tied to water and nutrient pools. Leaf fall in ridge hammocks is associated with high foliar carbon isotope values over the dry season, which is not the case for tree island hammocks. However, in some species, high levels of foliar nitrogen are also associated with high foliar C13 values indicating stomatal limitation of photosynthesis. Growing season for most hammock species is the wet season coinciding with high availability of P, as reflected in high foliar P in this season. Linking water sources to foliar nutrients elucidates roles of water and nutrient pools in leading to different plant communities within an ecosystem.

Lake sediments are valuable paleoenvironmental archives that provide information on past climate and land-use change. Most lake sediment studies rely on a single core, usually recovered from the center of a lake, and do not consider spatial variability in the lake basin. My dissertation presents a spatially-explicit record of prehistoric agriculture from Laguna Zoncho, Costa Rica and evaluates spatial variability in lake sediment proxies based on a network of five sediment cores. Results extend earlier proxy analyses of a single core collected near the center of the lake, which documented prehistoric agriculture and forest clearance from 3000 to about 500 years ago, followed by strong forest recovery at the time of the Spanish Conquest. Analyses of the new suite of cores show that agricultural activities increased erosion in the watershed, which lowered organic content from 16% to 5%, and resulted in a shift in bulk sediment stable carbon isotope values from –27 ‰ to –23 ‰ VPDB due to forest clearance. Agriculture made the lake slightly more productive, shown by a decrease in carbon/nitrogen ratios from 16 to 13 and an increase in stable nitrogen ratios from 1 to 3 ‰. Basinwide trends in organic matter and stable carbon isotopes ratios show two distinct periods of agricultural decline (1150–960 and 840–650 cal yr BP) that coincide with intervals of drought detected in regional paleoclimate records. This finding suggests that climate change, not the Spanish Conquest, was the driving force of site abandonment at Laguna Zoncho, and by extension throughout the region. Inter-core variability in proxies for agricultural activity reveals that crop cultivation may have continued longer in some portions of the watershed, and highlights the influence of sediment-focusing processes on proxy signatures of agriculture in lake basins. Maize pollen concentrations in the sediment cores did not correspond to geochemical and isotopic agricultural indicators, suggesting a need for caution in using the abundance of maize pollen to infer the scale of agriculture in neotropical watersheds.

Veins are ubiquitous features in deformed rocks. Despite observations on syntectonic veins spanning two centuries, fundamental questions remain unanswered. Their origin as fractures is largely established but it is still not known why these fractures initiate where they do and how the vein evolves once started. We studied veins from the Lower Ordovician Mazarn Formation in the Arkansas’ Ouachitas combining textural observations, stable isotopes, fluid inclusions, SEM-based cathodoluminescence and electron back-scattered diffraction to understand the initial stage of vein formation, its later evolution, the role of fluids and their environment of formation. The veins are located at boudin necks and are synchronous with cleavage formation. Texturally, veins are characterized by veinlets (thin veins between 5 and 25 μm thick) that parallel the vein-host interface and fibers (columns of quartz or calcite) perpendicular to the vein-host interface between 30 and 350 μm wide. Veinlets are localized fractures filled with quartz. The crystallographic orientation of the precipitated material in veinlets is inherited from host grains at the micron scale and replicated as fibers’ lengths grow to centimeters. The vein-forming fluid was cyclically supersaturated yet never very far from saturation. δ18O values of vein quartz and host are within 2‰ of each other suggesting that the fluid was rock-buffered. Nevertheless, δ18O and δ13C define a ‘J’ shaped trend. Although it is not possible to date any portion of this curve, the simplest explanation is that the fluid evolved from rock-buffered in a closed system to fluid-dominated in an open system. The range of pressure-temperature conditions of vein formation is between 275 and 385 °C and 1100 and 3400 bars, from fluid inclusions and quartz-calcite oxygen isotopes thermometry. By examining a vein from tip to middle, we have established a sequence of events from inception to maturity in vein growth. Vein formation starts with folding followed by flattening of resistant sandstone layers which in turn gives rise to boudinage. Boudinage formation allowed for fracture localization along boudin-necks. The vein grew by the repeated addition of veinlets in the neck region. Recrystallization later modified the fibers by obliterating some evidence of the veinlets and moving fiber walls.

Increased knowledge of stock mixing and migration patterns of Atlantic bluefin tuna (Thunnus thynnus) is required to appropriately manage and conserve declining populations. The nursery origin of giant bluefin tuna present in the Gulf of St. Lawrence was identified using stable carbon (δ13C) and oxygen (δ18O) isotopes in sagittal otoliths. Anthropogenic and natural processes are capable of impacting atmospheric and oceanic concentrations of δ13C and δ18O, affecting otolith concentrations. Therefore, inter-decadal variation of δ13C and δ18O in the otolith cores (corresponding to the first year of life) of bluefin tuna was examined prior to stock predictions and temporal variability was detected in both isotope ratios. Significant changes in both δ13C and δ18O were recorded in the otolith cores of individuals with birthdates between 1947 and 2003. Both δ13C and δ18O varied significantly as a function of year of birth, with δ13C decreasing and δ18O increasing over the time period investigated (-2.39×10-2 and 5.78×10-3 per year, respectively). The rate of change in otolith δ13C was nearly identical to the reported rates of atmospheric δ13C depletion, recently attributed to the burning of fossil fuels (referred to as the Suess effect). Observed shifts in otolith δ18O were less pronounced and likely linked to changing physicochemical conditions (i.e. salinity) in oceanic reservoirs over the time period investigated. The results show that otolith cores of bluefin tuna effectively track inter-decadal trends and record past oceanic δ13C and δ18O levels. After adjusting for inter-decadal trends, the isotopic composition of milled otolith cores of giants from three decades (1970s, 1980s, 2000s) and three regions were compared to otolith δ13C and δ18O values of yearling bluefin tuna collected from eastern and western nurseries. Maximum likelihood estimates indicated that 99% of bluefin tuna caught in the Gulf of St. Lawrence fishery originated from the western nursery, with no significant differences among the decades and regions examined. Results suggest that little to no mixing of eastern and western populations of adult bluefin tuna occurs in the Gulf of St. Lawrence, making it important for the management and conservation of the declining western population.

A number of charred surface residues, adhering to ceramic containers, were obtained from various coastal and inland sites in north-west Europe dating from the sixth to the fourth millennium cal bc. In order to investigate the use of these vessels and in particular to identify any marine products, the residues were subjected to carbon and nitrogen stable isotope analysis. Variation in carbon isotope ratios between different samples indicated that some vessels may have been used to process marine products. This analysis was corroborated by specific identification of aquatic products following structural and isotopic characterization of lipids extracted from selected samples.

Glucose is the most important fetal nutrient and the production of this substrate increases in the pregnant woman. In the last trimester the increased insulin resistance directs energy substrates to the fetus. Fetal growth is sometimes disturbed, often without an obvious explanation. After birth the newborn infant must produce its own glucose, primarily for the brain. Fatty acids from lipolysis are also important energy substrates. Hypoglycaemia can be a problem, occurring frequently in preterm infants and infants born small for gestational age (SGA). In addition, SGA infants are at risk of developing the metabolic syndrome in adulthood. Neonatal medication can influence energy metabolism. One such medication is theophylline, administered in preterm infants to prevent apnoea. We investigated energy substrate production in women with normal and IUGR pregnancies, in preterm neonates, before and after theophylline treatment and in newborn SGA infants, using stable isotope-labelled compounds and gas chromatography-mass spectrometry. We found that late pregnancy was associated with an almost twofold increase in the rate of lipolysis. This provides substrates for maternal energy metabolism, which may spare glucose for the fetus. Even though glucose production was comparable in the two groups of pregnant women, those with IUGR had a lower rate of lipolysis. A reduced supply of energy substrates could be one factor underlying IUGR. In spite of the insulin resistance of late pregnancy, insulin still had a regulatory role in energy substrate production in the women with normal pregnancies, but not in those with IUGR. Although infants born preterm and/or SGA have limited energy stores, we demonstrated that they are capable of both lipolysis and glucose production. Theophylline had no adverse effects on energy substrate production. Data on insulin and IGFBP-1 in the SGA infants indicate that in such infants insulin sensitivity is increased peripherally but reduced in the liver.

The main aim of this thesis was to contribute with detailed information of regional environmental change during the Holocene through studies of speleothems and their growth environments from two caves, Korallgrottan and Labyrintgrottan in northwestern Sweden, and a cellar vault in Uppsala. This was done through studies of stable isotopes and luminescence properties in the speleothems in combination with a detailed monitoring study in Korallgrottan. The monitoring study suggests that stalagmites fed by stalactites with slow and stable drip rates from deep inside the cave may be suitable as palaeoclimate archives. Similarities between oxygen isotope signals of contemporary samples from Labyrintgrottan and Korallgrottan emphasize the potential of speleothems from Labyrintgrottan to also provide high resolution regional palaeoclimate information. Except for a number of cold events stalagmite δ18O records from northern Scandinavia indicate that temperatures were warmer than today between 9500 and 6000 years ago. During this period the interval between 7800 and 6000 years ago seems to have been the warmest. The area above Labyrintgrottan was most likely covered by much denser vegetation than today at the time of stalagmite growth (9500-7500 years ago) and was, unlike today, probably situated below the local tree-limit between 9000 and 8000 years ago. The δ18O record of a stalagmite from Korallgrottan covering the last 4000 years agrees with the concept of a warmer period, the so called Medieval Warm Period, centred around AD1000 and a colder period, the so called Little Ice Age, somewhere between AD1000 and today. Studies of luminescence properties in fast growing speleothems from Uppsala indicate that the variations in luminescence intensity are annual and that the annual lamiae of the luminescent record represent a flush of organic material.

This thesis describes a multi-parameter biogeochemical investigation in a shallow hyper-eutrophic freshwater coastal lake, Zeekoevlei, in South Africa. The predominance of autochthonous algal-derived organic matter in lake sediments is indicated by low C/N, high H/C ratios and δ13Corganic values. Seepage from a nearby waste water treatment plant, rapid urbanization, raw sewage input and heavily fertilized farming in the catchments have caused enhanced productivity and is reflected by the changes in TOC concentrations, δ15N values, terrestrial to aquatic (n-alkane) ratio (TAR) and low carbon preference index (CPI) values. Eutrophic conditions were initiated in the lake with the start of recreational activities in early 1900s. Construction of dams and pondweed eradication in mid-1900s caused the transformation of the lake towards a hyper-eutrophic water body. Moreover, the aquatic macrophyte n-alkane proxy (Paq) values indicate the slow takeover by floating macrophytes after the eradication of submerged pondweeds in 1951. Low δ15N values and appearance of zeaxanthin indicate initiation of cyanobacterial bloom in the lake following pondweed eradication. Furthermore, the lake experienced intense cyanobacterial bloom after 1983 dredging. Although, cyanobacterial domination has decreased in recent years, hyper-eutrophic condition persists in the lake. Chemical weathering process supplies major fraction of trace metals, whereas fertilizers, agricultural wastes, sewage effluents and road runoff constitute the anthropogenic fraction. Low industrialization in the catchments causes low metal pollution in waters. In addition, high pH and metal scavenging by planktons result low dissolved trace metal concentrations. Adsorption by CaCO3 and planktonic assimilation control trace metal and phosphorus (P) sedimentation. Lake sediments have low P retention capacity and P is released from surface sediments by wind-induced resuspension.

The bioaccumulation of organic contaminants in aquatic ecosystems has been a key focus in environmental toxicology over the last decades. Bioaccumulation is a key concept in ecological risk assessments since it controls the internal dose of potential environmental contaminants. Information on the bioaccumulation of contaminants is used by regulatory authorities in the development of water quality standards, categorizing substances that are potential hazards and quantifying the risk of chemicals to human health. A basis for identifying priority chemicals has been the use of the octanol-water partition coefficient (KOW) as a criterion to estimate bioaccumulation potential. However, recognizing that the bioaccumulation process is not controlled by the hydrophobicity of a chemical alone, this thesis proposes a set of tools, incorporating chemical properties, environmental characteristics and physiological properties of organisms, to study the bioaccumulation of contaminants in aquatic ecosystems.  In striving to achieve this objective, a tool based on an equilibrium lipid partitioning approach was used in Paper I to evaluate monitoring data for bioaccumulation of organic contaminants. In Papers II and III, mechanistic based modelling tools were developed to describe bioaccumulation of hydrophobic compounds in aquatic food webs. In Paper IV, the bioaccumulation of organic compounds in aquatic food chains was studied using stable isotopes of nitrogen. The mechanistic fate and food web models developed in this thesis provide regulators and chemical manufacturers with a means of communicating scientific information to the general public and readily applicable mechanistic fate and food web models that are easily modified for evaluative assessments purposes.

This thesis describes the development and the use of quantitative deuterium Nuclear Magnetic Resonance spectroscopy (NMR) as a tool in two areas of environmental research: the study of long term climate-plant interactions and the source tracking of persistent organic pollutant. Long-term interactions between plants and climate will influence climate change during this century and beyond, but cannot be studied in manipulative experiments. We propose that long tree rings series can serve as records for tracking such interactions during past centuries. The abundance of the stable hydrogen isotope deuterium (D) is influenced by physical and biochemical isotope fractionations. Because the overlapping effects of these fractionations are not understood, studies of the D abundance of tree rings led to conflicting results. We hypothesized that both types of fractionations can be separated if the D abundance of individual C-H groups of metabolites can be measured, that is if individual D isotopomers are quantified. The first paper describes a technique for quantification of D isotopomers in tree-ring cellulose by NMR. The technique showed that the D isotopomers distribution (DID) was non-random. Therefore, the abundance of each isotopomer potentially contains individual information which suggests an explanation for the conflicting results obtained by measuring the overall D abundance (dD). In the second paper, this technique was used to study hydrogen isotope exchange during cellulose synthesis in tree rings. This revealed that some C-H positions exchange strongly with xylem water, while others do not. This means that the exchanging C-H positions should acquire the D abundance of source water, which is determined by physical fractionations, while non-exchanging C-H positions of tree-ring cellulose should retain biochemical fractionations from the leaf level. Therefore, the abundance of the corresponding D isotopomers should contain information about climate and physiology. When analysing tree-ring series, the DIDs should reflect information about temperature, transpiration and regulation of photosynthesis. In the third paper, we showed that CO2 concentration during photosynthesis determines a specific abundance ratio of D isotopomers. This dependence was found in metabolites of annual plants, and in tree-ring cellulose. This result shows that D isotopomers of tree-ring series may be used to detect long-term CO2 fertilisation effects. This information is essential to forecast adaptations of plants to increasing CO2 concentrations on time scales of centuries. In the fourth paper, the source of persistent organic pollutants in the environment was tracked using DID measurements. The dD values of two compounds of related structures were not enough to show indisputably that they did not originate from the same source. However, the DIDs of the common part between the two compounds proved that they did not originate from the same source. These results underline the superior discriminatory power of DIDs, compared to dD measurements. The versatility of DID measurements makes them a precious tool in addressing questions that can not be answered by dD measurements. / Betson, Tatiana R