Fluorescence Characteristics of Size-Fractionated Dissolved Organic Matter: Implications for a Molecular Assembly Based Structure?

Surface freshwater samples from Everglades National Park, Florida, were used to investigate the size distributions of natural dissolved organic matter (DOM) and associated fluorescence characteristics along the molecular weight continuum. Samples were fractionated using size exclusion chromatography (SEC) and characterized by spectroscopic means, in particular Excitation-Emission Matrix fluorescence modeled with parallel factor analysis (EEM-PARAFAC). Most of the eight components obtained from PARAFAC modeling were broadly distributed across the DOM molecular weight range, and the optical properties of the eight size fractions for all samples studied were quite consistent among each other. Humic-like components presented a similar distribution in all the samples, with enrichment in the middle molecular weight range. Some variability in the relative distribution of the different humic-like components was observed among the different size fractions and among samples. The protein like fluorescence, although also generally present in all fractions, was more variable but generally enriched in the highest and lowest molecular weight fractions. These observations are in agreement with the hypothesis of a supramolecular structure for DOM, and suggest that DOM fluorescence characteristics may be controlled by molecular assemblies with similar optical properties, distributed along the molecular weight continuum. This study highlights the importance of studying the molecular structure of DOM on a molecular size distribution perspective, which may have important implications in understanding the environmental dynamics such materials.

Essays on city size distribution and real estate bubbles

This is a dissertation about urban systems; within this broad subject I tackle three issues, one that focuses on an observed inter-city relationship and two that focus on an intra-city phenomenon. In Chapter II I adapt a model of random emergence of economic opportunities from the firm growth literature to the urban dynamics situation and present several predictions for urban system dynamics. One of these predictions is that the older the city the larger and more diversified it is going to be on average, which I proceed to verify empirically using two distinct datasets. In Chapter III I analyze the Residential Real Estate Bubble that took place in Miami-Dade County from 1999 to 2006. I adopt a Spatial-Economic model developed for the Paris Bubble episode of 1984–1993 and formulate an innovative test of the results in terms of speculative intensity on the basis of proxies of investor activity available in my dataset. My results support the idea that the best or more expensive areas are also where the greatest speculative activity takes place and where the rapid increase in prices begins. The most significant departure from previous studies that emerges in my results is the absence of a wider gap between high priced areas and low priced areas in the peak year. I develop a measure of dispersion in value among areas and contrast the Miami-Dade and Paris episodes. In Chapter IV I analyze the impact on tax equity of a Florida tax-limiting legislation known as Save Our Homes. I first compare homesteaded and non-homesteaded properties, and second, look within the subset of homesteaded properties. I find that non-homesteaded properties increase their share of taxes paid relative to homesteaded properties during an up market, but that this is reversed during a down market. For the subset of homesteaded properties I find that the impact on tax equity of SOH will depend on differential growth rates among higher and lower valued homes, but during times of rapid home price appreciation, in a scenario of no differential growth rates in property values, SOH increases progressivity relative to the prior system.

Characterization, sources, and transformations of dissolved organic matter (DOM) in Florida coastal Everglades (FCE)

Dissolved organic matter (DOM) is one of the largest carbon reservoirs on this planet and is present in aquatic environments as a highly complex mixture of organic compounds. The Florida coastal Everglades (FCE) is one of the largest wetlands in the world. DOM in this system is an important biogeochemical component as most of the nitrogen (N) and phosphorous (P) are in organic forms. Achieving a better understanding of DOM dynamics in large coastal wetlands is critical, and a particularly important issue in the context of Everglades restoration. In this work, the environmental dynamics of surface water DOM on spatial and temporal scales was investigated. In addition, photo- and bio-reactivity of this DOM was determined, surface-to-groundwater exchange of DOM was investigated, and the size distribution of freshwater DOM in Everglades was assessed. The data show that DOM dynamics in this ecosystem are controlled by both hydrological and ecological drivers and are clearly different on spatial scales and variable seasonally. The DOM reactivity data, modeled with a multi-pool first order degradation kinetics model, found that fluorescent DOM in FCE is generally photo-reactive and bio-refractory. Yet the sequential degradation proved a “priming effect” of sunlight on the bacterial uptake and reworking of this subtropical wetland DOM. Interestingly, specific PARAFAC components were found to have different photo- and bio-degradation rates, suggesting a highly heterogeneous nature of fluorophores associated with the DOM. Surface-to-groundwater exchange of DOM was observed in different regions of the system, and compositional differences were associated with source and photo-reactivity. Lastly, the high degree of heterogeneity of DOM associated fluorophores suggested based on the degradation studies was confirmed through the EEM-PARAFAC analysis of DOM along a molecular size continuum, suggesting that the fluorescence characteristics of DOM are highly controlled by different size fractions and as such can exhibit significant differences in reactivity.