Application of biomarkers and compound specific stable isotopes for the assessment of hydrology as a driver of organic matter dynamics in the Everglades ecosystem

The Everglades is a sub-tropical coastal wetland characterized among others by its hydrological features and deposits of peat. Formation and preservation of organic matter in soils and sediments in this wetland ecosystem is critical for its sustainability and hydrological processes are important divers in the origin, transport and fate of organic matter. With this in mind, organic matter dynamics in the greater Florida Everglades was studied though various organic geochemistry techniques, especially biomarkers, bulk and compound specific δ13C and δD isotope analysis. The main objectives were focused on how different hydrological regimes in this ecosystem control organic matter dynamics, such as the mobilization of particulate organic matter (POM) in freshwater marshes and estuaries, and how organic geochemistry techniques can be applied to reconstruct Everglades paleo-hydrology. For this purpose organic matter in typical vegetation, floc, surface soils, soil cores, and estuarine suspended particulates were characterized in samples selected along hydrological gradients in the Water Conservation Area 3, Shark River Slough and Taylor Slough. ^ This research focused on three general themes: (1) Assessment of the environmental dynamics and source-specific particulate organic carbon export in a mangrove-dominated estuary. (2) Assessment of the origin, transport and fate of organic matter in freshwater marsh. (3) Assessment of historical changes in hydrological conditions in the Everglades (paleo-hydrology) though biomarkes and compound specific isotope analyses. This study reports the first estimate of particulate organic carbon loss from mangrove ecosystems in the Everglades, provides evidence for particulate organic matter transport with regards to the formation of ridge and slough landscapes in the Everglades, and demonstrates the applicability of the combined biomarker and compound-specific stable isotope approach as a means to generate paleohydrological data in wetlands. The data suggests that: (1) Carbon loss from mangrove estuaries is roughly split 50/50 between dissolved and particulate carbon; (2) hydrological remobilization of particulate organic matter from slough to ridge environments may play an important role in the maintenance of the Everglades freshwater landscape; and (3) Historical changes in hydrology have resulted in significant vegetation shifts from historical slough type vegetation to present ridge type vegetation. ^

Organic matter dynamics in the Florida coastal Everglades: A molecular marker and isotopic approach

Everglades National Park (ENP) is about to undergo the world's largest wetland restoration with the aim of improving the quality, timing and distribution of water flow. The changes in water flow are hypothesized to alter the nutrient fluxes and organic matter (OM) dynamics within ENP, especially in the estuarine areas. This study used a multi-proxy approach of molecular markers and stable δ 13C isotope measurements, to determine the present day OM dynamics in ENP. ^ OM dynamics in wetland soils/sediments have proved to be difficult to understand using traditional geochemical approaches. These are often inadequate to describe the multitude of OM sources (e.g. higher land plant, emergent vegetation, submerged vegetation) to the soils/sediments and the complex diagenetic processes that can alter the OM characteristics. A multi-proxy approach, however, that incorporates both molecular level and bulk parameter information is ideal to comprehend complex OM dynamics in aquatic environments. Therefore, biomass-specific molecular markers or proxies can be useful in tracing the sources and processing of OM. This approach was used to examine the OM dynamics in the two major drainage basins, Shark River Slough and Taylor River Slough, of ENP. Freshwater to marine transects were sampled in both systems for soils/sediments and suspended particulate organic matter (SPOM) to be characterized through bulk OM analyses, lipid biomarker determinations (e.g. sterols, fatty acids, hydrocarbons and triterpenoids) and compound-specific stable carbon isotope (δ 13C) determinations. ^ One key accomplishment of the research was the assessment of a molecular marker proxy (Paq) to distinguish between emergent/higher plant vegetation from submerged vegetation within ENP. This proxy proved to be quite useful at tracing OM inputs to the soils/sediments of ENP. A second key accomplishment was the development of a 3-way model using vegetation specific molecular markers. This novel, descriptive model was successfully applied to the estuarine areas of Taylor and Shark River sloughs, providing clear evidence of mixing of freshwater, estuarine and marine derived OM in these areas. In addition, diagenetic transformations of OM in these estuaries were found to be quite different between Taylor and Shark Rivers, and are likely a result of OM quality and hydrological differences. ^

Gender differences in audit committees

Issues related to the composition of audit committees have attracted significant interest from legislators and regulators in recent years. In my dissertation, I examine one overlooked component of audit committee composition – namely, the presence of female directors on the audit committee. I empirically test to see if there are any differences in the functioning of audit committee when there is at least one female director on the audit committee. My dissertation examines three issues: audit committee diligence, audit pricing and earnings management. ^ The absence of females on corporate boards has become the focus of legislators in some countries. Prior research, in a variety of contexts, suggests that women are in general more conservative in their judgments and decisions. The first part of my dissertation empirically shows that the presence of at least one female director on the audit committee makes the audit committee have more meetings. The second essay empirically examines if there is a positive association between audit fees and the presence of female directors in the audit committee. I posit that having a female director on the audit committee will result in higher audit fees. I find no significant evidence to show that audit fees are higher when there is a female director on the audit committee. The third part of my dissertation empirically examines if there an association between the presence of a female director on the audit committee and earnings management. I find no significant evidence to show that the presence of female directors on the audit committee constrains earnings management. Overall, the results suggest that having a female on the audit committee changes the form – if not the substance – of audit committee functioning. ^

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.

The role of dissolved organic matter bioavailability in promoting phytoplankton blooms in Florida Bay

The clear, shallow, oligotrophic waters of Florida Bay are characterized by low phytoplankton biomass, yet periodic cyanobacteria and diatom blooms do occur. We hypothesized that allochthonous dissolved organic matter (DOM) was providing a subsidy to the system in the form of bound nutrients. Water from four bay sites was incubated under natural light and dark conditions with enrichments of either DOM ( > 1 kD, 2×DOM) or inorganic nutrients (N+P). Samples were analyzed for bacterial numbers, bacterial production, phytoplankton biomass, phytoplankton community structure, and production, nutrients, and alkaline phosphatase (AP) activity. The influence of 2×DOM enrichment on phytoplankton biomass developed slowly during the incubations and was relatively small compared to nutrient additions. Inorganic nutrient additions resulted in an ephemeral bloom characterized initially as cyanobacterial and brown algae but which changed to dinoflagellate and/or brown algae by day six. The DIN:TP ratio decreased 10-fold in the N+P treatments as the system progressed towards N limitation. This ratio did not change significantly for 2×DOM treatments. In addition, these experiments indicated that both autotrophic and heterotrophic microbial populations in Florida Bay may fluctuate in their limitation by organic and inorganic nutrient availability. Both N+P and 2×DOM enrichments revealed significant and positive response in bioavailability of dissolved organic carbon (BDOC). Potential BDOC ranged from 1.1 to 35.5%, with the most labile forms occurring in Whipray Basin. BDOC at all sites was stimulated by the 2×DOM addition. Except for Duck Key, BDOC at all sites was also stimulated by the addition of N+P. BDOC was lower in the dry season than in the wet season (5.56% vs. 16.86%). This may be explained by the distinct chemical characteristics of the DOM produced at different times of year. Thus, both the heterotrophic and autotrophic microbial communities in Florida Bay are modulated by bioavailability of DOM. This has ramifications for the fate of DOM from the Everglades inputs, implicating DOM bioavailability as a contributing factor in regulating the onset, persistence, and composition of phytoplankton blooms.

A Content Analysis of Sustainability Dimensions in Annual Reports

This study examines the triple bottom line of sustainability, in the context of both profit-oriented and non-profit oriented organizations. Sustainability is a compound result of interaction between economic, environmental, and social dimensions. Sustainability cannot be achieved without balance between all three dimensions, which has implications for measuring sustainability and prioritizing goals. This study demonstrates a method for measuring organizational sustainability achievement in these three dimensions of sustainability. Content analysis of the annual reports of corporations from the United States, Continental Europe (and Scandinavia), and Asia reveals that the economic dimension remains the preeminent aspect, and corporations still have a long way to go to reach comprehensive sustainability by maintaining a balance between the three dimensions of sustainability. The analysis also shows a high level of isomorphism in the sustainability practices of corporations, suggesting that even the most sustainable corporations are taking a somewhat passive role in prioritizing sustainability goals. A list of 25 terms for each dimension of sustainability (economic, environmental, and social) has been developed which can be used by corporations to develop and communicate their sustainability practices most effectively to the maximum number of their stakeholders. In contrast, botanical gardens demonstrate more balance among the three dimensions of sustainability.

Gender Differences in Audit Committees

Issues related to the composition of audit committees have attracted significant interest from legislators and regulators in recent years. In my dissertation, I examine one overlooked component of audit committee composition – namely, the presence of female directors on the audit committee. I empirically test to see if there are any differences in the functioning of audit committee when there is at least one female director on the audit committee. My dissertation examines three issues: audit committee diligence, audit pricing and earnings management. The absence of females on corporate boards has become the focus of legislators in some countries. Prior research, in a variety of contexts, suggests that women are in general more conservative in their judgments and decisions. The first part of my dissertation empirically shows that the presence of at least one female director on the audit committee makes the audit committee have more meetings. The second essay empirically examines if there is a positive association between audit fees and the presence of female directors in the audit committee. I posit that having a female director on the audit committee will result in higher audit fees. I find no significant evidence to show that audit fees are higher when there is a female director on the audit committee. The third part of my dissertation empirically examines if there an association between the presence of a female director on the audit committee and earnings management. I find no significant evidence to show that the presence of female directors on the audit committee constrains earnings management. Overall, the results suggest that having a female on the audit committee changes the form – if not the substance – of audit committee functioning.

Chemical characterization of soil organic matter in an oligotrophic, subtropical, freshwater wetland system: Sources, diagenesis and preservation

Freshwater wetland soils of the Everglades were studied in order to assess present environmental conditions and paleo-environmental changes using organic geochemistry techniques. Organic matter in dominant vegetation, peat and marl soils was characterized by geochemical means. Samples were selected along nutrient and hydrology gradients with the objective to determine the historical sources of organic matter as well as the extent of its preservation. Effective molecular proxies were developed to differentiate the relative input of organic matter from different biological sources to wetland soils. Thus historical vegetation shifts and hydroperiods were reconstructed using those proxies. The data show good correlations with historical water management practices starting at the turn of the century and during the mid 1900's. Overall, significant shortening of hydroperiods during this period was observed. The soil organic matter (SOM) preservation was assessed through elemental analysis and molecular characterizations of bulk 13C stable isotopes, solid state 13C NMR spectroscopy, UV-Vis spectroscopy, and tetramethyl ammonium hydroxide (TMAH) thermochemolysis-GC/MS. The relationship of the environmental conditions and degradation status of the soil organic matter (SOM) among the sites suggested that both high nutrient levels and long hydroperiod favor organic matter degradation in the soils. This is probably the result of an increase in the microbial activity in the soils which have higher nutrient levels, while longer hydroperiods may enhance physical/chemical degradation processes. The most significant transformations of biomass litter in this environment are controlled by very early physical/chemical processes and once the OM is incorporated into surface soils, the diagenetic change, even over extended periods of time is comparatively minimal, and SOM is relatively well preserved regardless of hydroperiod or nutrient levels. SOM accumulated in peat soils is more prone to continued degradation than the SOM in the marl soils. The latter is presumably stabilized early on through direct air exposure (oxidation) and thus, it is more refractory to further diagenetic transformations such as humification and aromatization reactions.

Comparative study of dissolved organic matter from groundwater and surface water in the Florida coastal Everglades using multi-dimensional spectrofluorometry combined with multivariate statistics

Dissolved organic matter (DOM) in groundwater and surface water samples from the Florida coastal Everglades were studied using excitation–emission matrix fluorescence modeled through parallel factor analysis (EEM-PARAFAC). DOM in both surface and groundwater from the eastern Everglades S332 basin reflected a terrestrial-derived fingerprint through dominantly higher abundances of humic-like PARAFAC components. In contrast, surface water DOM from northeastern Florida Bay featured a microbial-derived DOM signature based on the higher abundance of microbial humic-like and protein-like components consistent with its marine source. Surprisingly, groundwater DOM from northeastern Florida Bay reflected a terrestrial-derived source except for samples from central Florida Bay well, which mirrored a combination of terrestrial and marine end-member origin. Furthermore, surface water and groundwater displayed effects of different degradation pathways such as photodegradation and biodegradation as exemplified by two PARAFAC components seemingly indicative of such degradation processes. Finally, Principal Component Analysis of the EEM-PARAFAC data was able to distinguish and classify most of the samples according to DOM origins and degradation processes experienced, except for a small overlap of S332 surface water and groundwater, implying rather active surface-to-ground water interaction in some sites particularly during the rainy season. This study highlights that EEM-PARAFAC could be used successfully to trace and differentiate DOM from diverse sources across both horizontal and vertical flow profiles, and as such could be a convenient and useful tool for the better understanding of hydrological interactions and carbon biogeochemical cycling.

The effects of manipulation of sedimentary iron and organic matter on sediment biogeochemistry and seagrasses in a subtropical carbonate environment

The microbial metabolism of organic matter (OM) in seagrass beds can create sulfidic conditions detrimental to seagrass growth; iron (Fe) potentially has ameliorating effects through titration of the sulfides and the precipitation of iron-sulfide minerals into the sediment. In this study, the biogeochemical effects of Fe availability and its interplay with sulfur and OM on sulfide toxicity, phosphorous (P) availability, seagrass growth and community structure were tested. The availability of Fe and OM was manipulated in a 2 × 2 factorial experiment arranged in a Latin square, with four replicates per treatment. The treatments included the addition of Fe, the addition of OM, the addition of both Fe and OM as well as no addition. The experiment was conducted in an oligotrophic, iron-deficient seagrass bed. Fe had an 84.5% retention efficiency in the sediments with the concentration of Fe increasing in the seagrass leaves over the course of the experiment. Porewater chemistry was significantly altered with a dramatic decrease in sulfide levels in Fe addition plots while sulfide levels increased in the OM addition treatments. Phosphorus increased in seagrass leaves collected in the Fe addition plots. Decreased sulfide stress was evidenced by heavier δ34S in leaves and rhizomes from plots to which Fe was added. The OM addition negatively affected seagrass growth but increased P availability; the reduced sulfide stress in Fe added plots resulted in elevated productivity. Fe availability may be an important determinant of the impact that OM has on seagrass vitality in carbonate sediments vegetated with seagrasses.

The impact of the Miami Cuban exile's political culture on the 1996 fiscal crisis of the city of Miami

The purpose of this study was to determine if the political culture of the Miami Cuban exile community was a significant factor in creating the environment that led to the 1996 fiscal crisis of the City of Miami. The study performed an ethnographic case study that utilized a triangulation strategy which included both qualitative and quantitative methods. Focus groups were conducted to ascertain qualitative and quantitative data as to differences among ethnic and generational groups regarding notions of governance, public administration practices, and overall political values and core beliefs. Quantitative data was obtained through a five year and seven month review of newspaper articles from two periodicals based in Miami-Dade County. A review was also conducted of secondary data in audit and management reports, blue ribbon commission studies, Certified Public Manager (CPM) enrollment, and legal case decisions to examine the administrative practices of the City of Miami leading up to and subsequent to its fiscal crisis. The study found that a political subculture of caudillismo was present in Cuban exile core areas of Miami that appears to have had an influence on the administrative practices and notions of governance that led to the fiscal crisis. The author concludes that an imported foreign political culture has imposed itself as a subculture in core areas of the exile community and that the operationalization of this subculture has manifested itself in non-mainstream notions of governance and public administration practices. ^

Audit committee director turnover

Actions by both private sector organizations and legislators in recent years have highlighted the importance of the audit committee of the board of directors of corporations in the financial reporting process. For example, the Sarbanes Oxley Act of 2002 has multiple sections that deal with the composition and functioning of audit committees. My dissertation examines multiple issues related to the composition of audit committees. In the first two parts of my dissertation, I examine the stock market reactions to disclosures of audit committee appointments and departures in the 8-Ks filed with the SEC during 2008 and 2009. I find that there is a positive stock market reaction to the appointment of audit committee directors who are financial experts. The second essay investigates the cumulative abnormal return to departure of audit committee directors. I find that when an accounting expert leaves the audit committee, the market reaction is significantly negative. These results are consistent with regulators’ concerns related to having directors with audit, accounting and other financial expertise on corporate audit committees. The third essay of my dissertation examines the changes in audit committee composition in the last decade. I find that while the increase in audit committee size is relatively modest, there has been a significant increase in the number of audit committee experts and the frequency of audit committee meetings over the past decade; interestingly, such increase in the number of meetings has persisted even after the media focus on the auditing profession, in the immediate aftermath of the Enron and Andersen failures, have waned. My results show that audit committee composition and its role continues to evolve with regulatory and other corporate governance related changes.

Spatial, geomorphological, and seasonal variability of CDOM in estuaries of the Florida Coastal Everglades

This paper demonstrates the usefulness of fluorescence techniques for long-term monitoring and assessment of the dynamics (sources, transport and fate) of chromophoric dissolved organic matter (CDOM) in highly compartmentalized estuarine regions with non-point water sources. Water samples were collected monthly from a total of 73 sampling stations in the Florida Coastal Everglades (FCE) estuaries during 2001 and 2002. Spatial and seasonal variability of CDOM characteristics were investigated for geomorphologically distinct sub-regions within Florida Bay (FB), the Ten Thousand Islands (TTI), and Whitewater Bay (WWB). These variations were observed in both quantity and quality of CDOM. TOC concentrations in the FCE estuaries were generally higher during the wet season (June–October), reflecting high freshwater loadings from the Everglades in TTI, and a high primary productivity of marine biomass in FB. Fluorescence parameters suggested that the CDOM in FB is mainly of marine/microbial origin, while for TTI and WWB a terrestrial origin from Everglades marsh plants and mangroves was evident. Variations in CDOM quality seemed mainly controlled by tidal exchange/mixing of Everglades freshwater with Florida Shelf waters, tidally controlled releases of CDOM from fringe mangroves, primary productivity of marine vegetation in FB and diagenetic processes such as photodegradation (particularly for WWB). The source and dynamics of CDOM in these subtropical estuaries is complex and found to be influenced by many factors including hydrology, geomorphology, vegetation cover, landuse and biogeochemical processes. Simple, easy to measure, high sample throughput fluorescence parameters for surface waters can add valuable information on CDOM dynamics to long-term water quality studies which can not be obtained from quantitative determinations alone.

An empirical analysis of the global audit market: International Financial Reporting Standards-related changes and differences within the Big 4 global networks

Ongoing debates within the professional and academic communities have raised a number of questions specific to the international audit market. This dissertation consists of three related essays that address such issues. First, I examine whether the propensity to switch between auditors of different sizes (i.e., Big 4 versus non-Big 4) changes as adoption of International Financial Reporting Standards (IFRS) becomes a more common phenomenon, arguing that smaller auditors have an opportunity to invest in necessary skills and training needed to enter this market. Findings suggest that clients are relatively less (more) likely to switch to (away from) a Big 4 auditor if the client's adoption of IFRS occurs in more recent years. ^ In the second essay, I draw on these inferences and test whether the change in audit fees in the year of IFRS adoption changes over time. As the market becomes less concentrated, larger auditors becomes less able to demand a premium for their services. Consistent with my arguments, results suggest that the change in audit service fees declines over time, although this effect seems concentrated among the Big 4. I also find that this effect is partially attributable to a differential effect of the auditors' experience in pricing audit services related to IFRS based on the period in which adoption occurs. The results of these two essays offer important implications to policy debates on the costs and benefits of IFRS adoption. ^ In the third essay, I differentiate Big 4 auditors into three classifications—Parent firms, Brand Name affiliates, and Local affiliates—and test for differences in audit fee premiums (relative to non-Big 4 auditors) and audit quality. Results suggest that there is significant heterogeneity between the three classifications based on both of these characteristics, which is an important consideration for future research. Overall, this dissertation provides additional insights into a variety of aspects of the global audit market.^