Carbon and nitrogen stable isotopic patterns in South Florida coastal ecosystems: Modern and paleoceanographic perspectives

Long term management plans for restoration of natural flow conditions through the Everglades increase the importance of understanding potential nutrient impacts of increased freshwater delivery on coastal biogeochemistry. The present study sought to increase understanding of the coastal marine system of South Florida under modern conditions and through the anthropogenic changes in the last century, on scales ranging from individual nutrient cycle processes to seasonal patterns in organic material (OM) under varying hydrodynamic regime, to century scale analysis of sedimentary records. In all applications, carbon and nitrogen stable isotopic compositions of OM were examined as natural recorders of change and nutrient cycling in the coastal system. ^ High spatial and temporal variability in stable isotopic compositions were observed on all time scales. During a transient phytoplankton bloom, δ 15N values suggested nitrogen fixation as a nutrient source supporting enhanced productivity. Seasonally, particulate organic material (POM) from ten sites along the Florida Reef Tract and in Florida Bay demonstrated variable fluctuations dependent on hydrodynamic setting. Three separate intra-annual patterns were observed, yet statistical differences were observed between groupings of Florida Bay and Atlantic Ocean sites. The POM δ 15N values ranged on a quarterly basis by 7‰, while δ 13C varied by 22‰. From a sediment history perspective, four cores collected from Florida Bay further demonstrated the spatial and temporal variability of the system in isotopic composition of bulk OM over time. Source inputs of OM varied with location, with terrestrial inputs dominating proximal to Everglades freshwater discharge, seagrasses dominating in open estuary cores, and a marine mixture of phytoplankton and seagrass in a core from the boundary zone between Florida Bay and the Gulf of Mexico. Significant shifts in OM geochemistry were observed coincident with anthropogenic events of the 20th century, including railroad and road construction in the Florida Keys and Everglades, and also the extensive drainage changes in Everglades hydrology. The sediment record also preserved evidence of the major hurricanes of the last century, with excursions in geochemical composition coincident with Category 4-5 storms. ^

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. ^

Relative significance of pelagic, benthic and allochthonous organic matter to microbial carbon cycling in a phosphorus-depleted subtropical estuary (Florida Bay)

Heterotrophic bacteria are important decomposers and transformers of primary production and provide an important link between detritus and the aquatic food web. In seagrass ecosystems, much of seagrass primary production is unavailable through direct grazing and must undergo microbial reworking before seagrass production can enter the aquatic food web. The goal of my dissertation research is to understand better the role heterotrophic bacteria play in carbon cycling in seagrass estuaries. My dissertation research focuses on Florida Bay, a seagrass estuary that has experienced recent changes in carbon source availability, which may have altered ecosystem function. My dissertation research investigates the importance of seagrass, algal and/or cyanobacterial, and allochthonous-derived organic matter to heterotrophic bacteria in Florida Bay and helps establish the carbon base of the estuarine food web. ^ A three tiered approach to the study of heterotrophic bacterial carbon cycling and trophic influences in Florida Bay was used: (1) Spatiotemporal observations of environmental parameters (hydrology, nutrients, extracellular enzymes, and microbial abundance, biomass, and production); (2) Microbial grazing experiments under different levels of top-down and bottom-up influence; and (3) Bulk and compound-specific (bacteria-biomarker fatty acid analysis) stable carbon isotope analysis. ^ In Florida Bay, spatiotemporal patterns in microbial extracellular enzyme (also called ectoenzyme) activities indicate that microorganisms hydrolyzed selectively fractions of the estuarine organic matter pool. The microbial community hydrolyzed organic acids, peptides, and phosphate esters and did not use storage and structural carbohydrates. Organic matter use by heterotrophic bacterioplankton in Florida Bay was co-regulated by bottom-up (resource availability) and top-down (grazer mediated) processes. A bacterial carbon budget based on bacterial, epiphytic, and seagrass production indicates that heterotrophic bacterial carbon cycles are supported primarily through epiphytic production with mixing from seagrass production. Stable carbon isotope analysis of bacteria biomarkers and carbon sources in Florida Bay corroborate the results of the bacterial carbon budget. These results support previous studies of aquatic consumers in Florida Bay, indicating that epiphytic/benthic algal and/or cyanobacterial production with mixing from seagrass-derived organic matter is the carbon base of the seagrass estuarine food web. ^

Quantitative diatom-based reconstruction of paleoenvironmental conditions in Florida Bay and Biscayne Bay, U.S.A.

The spatial and temporal distribution of modern diatom assemblages in surface sediments, on the most dominant macrophytes, and in the water column at 96 locations in Florida Bay, Biscayne Bay and adjacent regions were examined in order to develop paleoenvironmental prediction models for this region. Analyses of these distributions revealed distinct temporal and spatial differences in assemblages among the locations. The differences among diatom assemblages living on subaquatic vegetation and sediments, and in the water column were significant. Because concentrations of salts, total phosphorus (WTP), total nitrogen (WTN) and total organic carbon (WTOC) are partly controlled by water management in this region, diatom-based models were produced to assess these variables. Discriminant function analyses showed that diatoms can also be successfully used to reconstruct changes in the abundance of diatom assemblages typical for different habitats and life habits. ^ To interpret paleoenvironmental changes, changes in salinity, WTN, WTP and WTOC were inferred from diatoms preserved in sediment cores collected along environmental gradients in Florida Bay (4 cores) and from nearshore and offshore locations in Biscayne Bay (3 cores). The reconstructions showed that water quality conditions in these estuaries have been fluctuating for thousands of years due to natural processes and sea-level changes, but almost synchronized shifts in diatom assemblages occurred in the mid-1960’s at all coring locations (except Ninemile Bank and Bob Allen Bank in Florida Bay). These alterations correspond to the major construction of numerous water management structures on the mainland. Additionally, all the coring sites (except Card Sound Bank, Biscayne Bay and Trout Cove, Florida Bay) showed decreasing salinity and fluctuations in nutrient levels in the last two decades that correspond to increased rainfall in the 1990’s and increased freshwater discharge to the bays, a result of increased freshwater deliveries to the Everglades by South Florida Water Management District in the 1980’s and 1990’s. Reconstructions of the abundance of diatom assemblages typical for different habitats and life habits revealed multiple sources of diatoms to the coring locations and that epiphytic assemblages in both bays increased in abundance since the early 1990’s. ^

The effects of carbon dioxide fertilization on the ecology of tropical seagrass communities

Increasing atmospheric CO2 concentrations associated with climate change will likely influence a wide variety of ecosystems. Terrestrial research has examined the effects of increasing CO2 concentrations on the functionality of plant systems; with studies ranging in scale from the short-term responses of individual leaves, to long-term ecological responses of complete forests. While terrestrial plants have received much attention, studies on the responses of marine plants (seagrasses) to increased CO 2(aq) concentrations remain relatively sparse, with most research limited to small-scale, ex situ experimentation. Furthermore, few studies have attempted to address similarities between terrestrial and seagrass responses to increases in CO2(aq). The goals of this dissertation are to expand the scope of marine climate change research, and examine how the tropical seagrass, Thalassia testudinum responds to increasing CO 2(aq)concentrations over multiple spatial and temporal scales. ^ Manipulative laboratory and field experimentation reveal that, similar to terrestrial plants, seagrasses strongly respond to increases in CO 2(aq) concentrations. Using a novel field technique, in situ field manipulations show that over short time scales, seagrasses respond to elevated CO2(aq) by increasing leaf photosynthetic rates and the production of soluble carbohydrates. Declines in leaf nutrient (nitrogen and phosphorus) content were additionally detected, paralleling responses from terrestrial systems. Over long time scales, seagrasses increase total above- and belowground biomass with elevated CO2(aq), suggesting that, similar to terrestrial research, pervasive increases in atmospheric and oceanic CO2(aq) concentrations stand to influence the productivity and functionality of these systems. Furthermore, field experiments reveal that seagrass epiphytes, which comprise an important component of seagrass ecosystems, additionally respond to increased CO2(aq) with strong declines in calcified taxa and increases in fleshy taxa. ^ Together, this work demonstrates that increasing CO2(aq) concentrations will alter the functionality of seagrass ecosystems by increasing plant productivity and shifting the composition of the epiphyte community. These results have implications for future rates of carbon storage and sediment production within these widely distributed systems.^

Lower Aptian Comparative Stratigraphy of the Basco-Cantabrian Region (Spain) and Eastern Cordillera (Colombia): implications for local factors in the depositional record of Oceanic Anoxic Event 1a (OAE-1a)

An important episode of carbon sequestration, Oceanic Anoxic Event 1a (OAE-1a), characterizes the Lower Aptian worldwide, and is mostly known from deeper-water settings. The present work of two Lower Aptian deposits, Madotz (N Spain) and Curití Quarry (Colombia), is a multiproxy study that includes fossil assemblages, microfacies, X-ray diffraction bulk and clay mineralogy, elemental analyses (major, minor, trace elements), Rock-Eval pyrolysis, biomarkers, inorganic and organic carbon content, and stable carbon isotopes. The results provide baseline evidence of the local and global controlling environmental factors influencing OAE-1a in shallow-water settings. The data also improve our general understanding of the conditions under which organic-carbon-rich deposits accumulate. The sequence at Madotz includes four intervals (Unit 1; Subunits 2a, 2b and 2c) that overlap the times prior to, during and after the occurrence of OAE-1a. The Lower Unit 1(3m thick) is essentially siliciclastic, and Subunit 2a (20m) contains Urgonian carbonate facies that document abruptly changing platform conditions prior to OAE-1a. Subunit 2b (24.4 m) is a mixed carbonate-siliciclastic facies with orbitolinid-rich levels that coincides with OAE-1a δ13C stages C4-C6, and is coeval with the upper part of the Deshayesites forbesi ammonite zone. Levels with pyrite and the highest TOC values (0.4-0.97%), interpreted as accumulating under suboxic conditions, and are restricted to δ13C stages C4 and C5. The best development of the suboxic facies is at the level representing the peak of the transgression. Subunit 2c, within δ13C stage C7, shows a return of the Urgonian facies. The 23.35-m section at Curití includes a 6.3-m interval at the base of the Paja Formation dominated by organic-rich marlstones and shales lacking benthic fossils and bioturbation, with TOC values as high as 8.84%. The interval overlies a level containing reworked and phosphatized assemblages of middle Barremian to lowest Aptian ammonites. The range of values and the overall pattern of the δ13Corg (-22.05‰ to -20.47‰) in the 6.3m-interval is comparable with Lower Aptian δ13C stage C7. Thus, conditions of oxygen depletion at this site also occurred after Oceanic Anoxic Event-1a, which developed between carbon isotope stages C3 and C6. Both sites, Madotz and Curití, attest to the importance of terrigenous and nutrient fluxes in increasing OM productivity that led to episodic oxygen deficiency.

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.