Chemical characteristics of dissolved organic matter in an oligotrophic subtropical wetland/estuarine ecosystem

Fluorescence properties of whole water samples and molecular characteristics of ultrafiltrated dissolved organic matter (UDOM > 1,000 D) such as lignin phenol and neutral sugar compositions and 13C nuclear magnetic resonance (NMR) spectra were determined along a freshwater to marine gradient in Everglades National Park. Furthermore, UDOM samples were categorized by hierarchical cluster analysis based on their pyrolysis gas chromatography/mass spectrometry products. Fluorescence properties suggest that autochthonous DOM leached/exuded from biomass is quantitatively important in this system. 13C NMR spectra showed that UDOM from the oligotrophic Taylor Slough (TS) and Florida Bay (FB) ecosystems has low aromatic C (13% ± 3% for TS; 2% ± 2% for FB) and very high O-alkyl C (54% ± 4% for TS; 75% ± 4% for FB) concentrations. High O-alkyl C concentrations in FB suggest seagrass/phytoplankton communities as dominant sources of UDOM. The amount of neutral sugars was not appreciably different between the TS and FB sites (115 ± 12 mg C g C-1 UDOM) but their concentrations suggest a low level of diagenesis and high production rates of this material in this oligotrophic environment. Total yield of lignin phenols (vanillyl + syringyl phenols) in TS was low (0.20–0.39 mg 100 mg C-1 UDOM) compared with other riverine environments and even lower in FB (0.04–0.07 mg 100 mg C-1 UDOM) and could be a result of photodegradation and/or dilution by other utochthonous DOM. The high O-alkyl and low aromatic nature of this UDOM suggests significant biogenic inputs (as compared with soils) and limited bioavailability in this ecosystem.

Effects of In Situ CO2 Enrichment on the Structural and Chemical Characteristics of the Seagrass Thalassia Testudinum

Seagrasses commonly display carbon-limited photosynthetic rates. Thus, increases in atmospheric pCO2, and consequentially oceanic CO2(aq) concentrations, may prove beneficial. While addressed in mesocosms, these hypotheses have not been tested in the field with manipulative experimentation. This study examines the effects of in situ CO2(aq) enrichment on the structural and chemical characteristics of the tropical seagrass, Thalassia testudinum. CO2(aq) availability was manipulated for 6 months in clear, open-top chambers within a shallow seagrass meadow in the Florida Keys (USA), reproducing forecasts for the year 2100. Structural characteristics (leaf area, leaf growth, shoot mass, and shoot density) were unresponsive to CO2(aq) enrichment. However, leaf nitrogen and phosphorus content declined on average by 11 and 21 %, respectively. Belowground, non-structural carbohydrates increased by 29 %. These results indicate that increased CO2(aq) availability may primarily alter the chemical composition of seagrasses, influencing both the nutrient status and resilience of these systems.

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.

Application of excitation emission matrix fluorescence monitoring in the assessment of spatial and seasonal drivers of dissolved organic matter composition: Sources and physical disturbance controls

The environmental dynamics of dissolved organic matter (DOM) were characterized for a shallow, subtropical, seagrass-dominated estuarine bay, namely Florida Bay, USA. Large spatial and seasonal variations in DOM quantity and quality were assessed using dissolved organic C (DOC) measurements and spectrophotometric properties including excitation emission matrix (EEM) fluorescence with parallel factor analysis (PARAFAC). Surface water samples were collected monthly for 2 years across the bay. DOM characteristics were statistically different across the bay, and the bay was spatially characterized into four basins based on chemical characteristics of DOM as determined by EEM-PARAFAC. Differences between zones were explained based on hydrology, geomorphology, and primary productivity of the local seagrass community. In addition, potential disturbance effects from a very active hurricane season were identified. Although the overall seasonal patterns of DOM variations were not significantly affected on a bay-wide scale by this disturbance, enhanced freshwater delivery and associated P and DOM inputs (both quantity and quality) were suggested as potential drivers for the appearance of algal blooms in high impact areas. The application of EEM-PARAFAC proved to be ideally suited for studies requiring high sample throughput methods to assess spatial and temporal ecological drivers and to determine disturbance-induced impacts in aquatic ecosystems.

The relationship between alkaloid-based chemical defenses and diet in dendrobatid poison frogs

Chemical defenses are common among organisms and represent some of the most complex adaptations for avoiding predation, yet our understanding of the ecological nature of these systems remains incomplete. Poison frogs are a group of chemically defended organisms that are dependent entirely on diet for chemical defense. In this study, I identified the dietary arthropods responsible for chemical defense in poison frogs, described spatial and temporal patterns in alkaloid composition of poison frogs, and established links between patterns of variation in alkaloid defense and arthropod diet in poison frogs. Identifying dietary sources and studying patterns of variation in alkaloid composition is fundamental to understanding the ecology and evolution of chemical defense in poison frogs. ^ The dendrobatid poison frog Oophaga pumilio shares many alkaloids in common with other poison frogs and is known to vary in alkaloid composition throughout its geographic range. I designed my dissertation to take advantage of these characteristics and use O. pumilio as a model species for the study of chemical defense in poison frogs. Here, I identified siphonotid millipedes as a source for spiropyrrolizidine alkaloids, formicine ants as a source for pumiliotoxin alkaloids, and oribatid mites as dietary sources for the majority of alkaloids found in poison frogs. I found that alkaloid composition varied spatially and temporally, on both small and large scales, within and among populations of O. pumilio. Alkaloid variation between populations was related to geographic distance, and closer populations tended to have alkaloid compositions more similar to each other than to distant populations. ^ The findings of my study suggest that oribatid mites are the most important dietary source of alkaloids in poison frogs. However, overall alkaloid defense in poison frogs is based on a combination of dietary arthropods, including mites, ants, millipedes, and beetles. Variation in chemical defenses of poison frogs is due to (1) spatial and temporal differences in the presence of alkaloids in certain arthropods and (2) differences in the availability of certain alkaloid-containing arthropods, which are likely the result of differences as well as successional changes in forest structure among locations and through time. ^

The effect of weathering processes on the vertical turbulent dispersion characteristics of crude oil spilled on the sea

Since the Exxon Valdez accident in 1987, renewed interest has come forth to better understand and predict the fate and transport of crude oil lost to marine environments. The short-term fate of an Arabian Crude oil was simulated in laboratory experiments using artificial seawater. The time-dependent changes in the rheological and chemical properties of the oil under the influence of natural weathering processes were characterized, including dispersion behavior of the oil under simulated ocean turbulence. Methodology included monitoring the changes in the chemical composition of the oil by Gas Chromatography/Mass Spectrometry (GCMS), toxicity evaluations for the oil dispersions by Microtox analysis, and quantification of dispersed soluble aromatics by fluorescence spectrometry. Results for this oil show a sharp initial increase in viscosity, due to evaporative losses of lower molecular weight hydrocarbons, with the formation of stable water-in-oil emulsions occurring within one week. Toxicity evaluations indicate a decreased EC-50 value (higher toxicity) occurring after the oil has weathered eight hours, with maximum toxicity being observed after weathering seven days. Particle charge distributions, determined by electrophoretic techniques using a Coulter DELSA 440, reveal that an unstable oil dispersion exists within the size range of 1.5 to 2.5 um, with recombination processes being observed between sequential laser runs of a single sample.