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. ^

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, ä15N 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 ä15N values ranged on a quarterly basis by 7‰, while ä13C 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.

Using Optical Properties to Quantify Fringe Mangrove Inputs to the Dissolved Organic Matter (DOM) Pool in a Subtropical Estuary

Dissolved organic carbon (DOC) concentration and dissolved organic matter (DOM) optical properties were analyzed along two estuarine river transects during the wet and dry seasons to better understand DOM dynamics and quantify mangrove inputs. A tidal study was performed to assess the impacts of tidal pumping on DOM transport. DOM in the estuaries showed non-conservative mixing indicative of mangrove-derived inputs. Similarly, fluorescence data suggest that some terrestrial humic-like components showed non-conservative behavior. An Everglades freshwater-derived fluorescent component, which is associated with soil inputs from the Northern Everglades, behaved conservatively. During the dry season, a protein-like component behaved conservatively until the mid-salinity range when non-conservative behavior due to degradation and/or loss was observed. The tidal study data suggests mangrove porewater inputs to the rivers following low tide. The differences in quantity of DOM exported by the Shark and Harney Rivers imply that geomorphology and tidal hydrology may be a dominant factor controlling the amount of DOM exported from the mangrove ecotone, where up to 21 % of the DOC is mangrove-derived. Additionally, nutrient concentrations and other temporal factors may control DOM export from the mangroves, particularly for the microbially derived fluorescent components, contributing to the seasonal differences. The wet and dry season fluxes of mangrove DOM from the Shark River is estimated as 0.27 × 109 mg C d−1 and 0.075 × 109 mg C d−1, respectively, and the Harney River is estimated as 1.9 × 109 mg C d−1 and 0.20 × 109 mg C d−1.

An aquatic risk assessment of ethion and bromacil inputs to the C-25 Canal and Indian River Lagoon

Pesticide monitoring in St. Lucie County by various local, state and federal agencies has indicated consistent residues of several pesticides, including ethion and bromacil. Although pesticides have long been known to pose a threat to non-target species and much background monitoring has been done, no pesticide aquatic risk assessment has been done in this geographical area. Several recognized United States Environmental Protection Agency (USEPA) methods of quantifying risk are employed here to include hazard quotients (HQ) and probabilistic modeling with sensitivity analysis. These methods are employed to characterize potential impacts to aquatic biota of the C-25 Canal and the Indian River Lagoon (in St. Lucie County, Florida) based on current agricultural pesticide use and drainage patterns. The model used in the analysis incorporates available physical-chemical property data, local hydrology, ecosystem information, and pesticide use practices. HQ's, probabilistic distributions, and field sample analyses resulted in high levels of concern (LOCs), which usually indicates a need for regulatory action, including restrictions on use, or cancellation. ^

Soil carbon dynamics in primary and secondary tropical forests in Colombia

Soils play a central role in the dynamics of biospheric carbon and in climate change. They contain the largest carbon stock of terrestrial ecosystems and return to the atmosphere a significant proportion of carbon fixed by photosynthesis. Soils of tropical forests are tremendously important in the carbon cycle because they receive the largest organic matter inputs, they have the largest respiration rates, and they are among the largest carbon reservoirs among world soils. This research assesses the main components of the soil carbon dynamics in primary (PF) and secondary (SF) tropical forests in Colombia. I evaluated the production, stocks, and decomposition rates of aboveground detritus as well as the stocks, growth, mortality, and decomposition of fine roots in these two forest types. Soil carbon outputs were evaluated as total soil, heterotrophic, and root respiration. The stocks of soil organic carbon down to 4 m deep in these two cover types and in degraded pastures (PAS) were also evaluated. ^ Soil inputs of organic carbon from above and belowground sources were lower in SF than in PF. Litterfall in SF was 58% and production of fine root detritus was 60% of that in PF. When production of woody detritus and palm fronds was considered, the difference between these forest types was even larger. However, outputs of mineral carbon through heterotrophic soil respiration were similar; in SF they equaled 97% of those in PF. As a result, soil carbon balance was positive in PF and negative in SF. Despite that soil carbon balances suggest that soils of SF are losing carbon, soil carbon stocks of SF were higher than of degraded pastures, suggesting that they have already started to recover soil carbon stocks lost under degraded pastures. This discrepancy can be partially explained by the effect of drier conditions on heterotrophic soil respiration as a consequence of a moderate El Niño event during the period of soil respiration measurements. The positive carbon balance in soils of PF despite the El Niño event, suggests that soils of PF accumulated about 664 Kg C ha−1 yr−1. Therefore, soil carbon dynamics mainly depended on successional status of vegetation and on climatic conditions. ^

Origin, transport and fate of organic matter in Florida Bay: A biomarker record of historical environmental changes

The Everglades are undergoing the world largest wetland restoration project with the aim of returning this system to hydrological conditions in place prior to anthropogenic modifications. Therefore, it is essential to know what these pristine conditions were. In this work, molecular marker (biomarker) distributions and carbon stable isotopic signatures in sediment samples were employed to assess historical environmental changes in Florida Bay over approximately the last 4000 years. Two biomarkers of terrestrial plants, particularly for mangroves (taraxerol and C29 n-alkane), combined with two seagrass proxies (the Paq and the C25/C 27 n-alkan-2-one ratio) revealed a sedimentary environmental shift from freshwater marshes to mangrove swamps and then to seagrass dominated marine ecosystems, likely as a result of sea-level rise in Florida Bay since the Holocene. The maximum values for the Paq and the C 25/C27 n-alkan-2-ones occurred during the 20th century, suggesting that the greatest abundance of seagrass cover is a recent rather than a historical, long-term phenomenon. The greater oscillation in frequency and amplitude for the biomarkers after 1900 potentially reflects an ecosystem under increasing anthropogenic stress. Several algal biomarkers such as C20 highly branched isoprenoids (HBIs), C 25 HBIs and dinosterol indicative of cyanobacteria, diatom and dinoflagellate organic matter inputs respectively, increased dramatically in the latter part of the 20th century and were attributed to recent anthropogenic changes in Florida Bay. ^ The highlight of this work is the development of HBIs as paleo-proxies. As biomarkers of diatoms, the C25 HBIs in the core from the central bay displayed the highest concentration at mid depth, reflecting strong historical inputs of diatom-derived sedimentary OM during that period. In fact, the depth profile of C25 HBIs coincided quite well with historical variations in diatom abundance and variations in diatom species composition in central Florida Bay based on the results of fossil diatom species analysis by microscopy. This study provides evidence that some C25 HBIs can be applied as biomarkers for certain diatom inputs in paleoenvironmental studies. The sources of C20 and C30 HBIs and their potential applicability as paleo-proxies were also investigated and their sources assessed based on their δ13C distributions. ^

The importance of marine subsidies for terrestrial consumers in coastal Peru

The Peruvian coast is one the best examples of cross-ecosystem food web exchanges, in which resources from one of the richest marine ecosystems subsidize consumers in one of the driest deserts on Earth. Marine subsidies are resources that originate in the marine ecosystem, and that contribute to increase the density of consumers in the recipient ecosystem. I examined the effects of marine subsidies on animal populations in the Peruvian coastal desert. ^ I combined several approaches to study the linkages between marine resources and terrestrial consumers, such as surveying the spatial distribution and estimating the relative abundance of terrestrial consumers, studying the diet of geckos and lizards through stomach content analyses, and examining the desert food web with carbon and nitrogen stable isotope analyses. ^ I found that the distribution and diet of desert consumers were tightly coupled to the availability of marine subsidies. I revealed linkages along two pathways of nutrient fluxes: tidal action that washes ashore macroalgae and cadavers of marine organisms, and animal transport in places where pinnipeds and seabirds congregate for reproduction. In the first pathway, intertidal algivivores made marine resources available to terrestrial consumers by moving between the intertidal and supratidal zone. The relative contribution of terrestrial and algal carbon sources varied among terrestrial consumers, because scorpions assimilated a lower proportion of energy from macroalgae than did geckos and solifuges. In the second pathway, I found that pinniped colonies influenced the diet of desert consumers, and contributed to support large populations of lizards and geckos. By combining field observations, and stomach and stable isotope analyses, I constructed a simplified food web for a large sea lion colony, showing the number of trophic levels that originate from pinniped-derived nutrients. ^ My study demonstrates the enormous importance of marine resources for the diet of desert consumers. The near absence of rainfall along the Peruvian coast promotes an extreme dependence of terrestrial consumers on marine resources, and causes permanent food web effects that are affected by temporal variability in marine productivity, rather then temporal patterns of desert plant growth. ^

Biogeochemical factors affecting the fate and transport of mercury in the terrestrial environment at Oak Ridge, Tennessee

Mercury (Hg) contamination problem in the United Sates has been an important issue due to its potential threat to human and ecological health. This thesis presents a study of two Hg-contaminated sites along the East Fork Poplar Creek (EFPC) at Oak Ridge. The top soils from the terrestrial areas, along with the soils from three vertical soil horizons at the EFPC bank were sampled and analyzed for total-Hg (THg), methyl-Hg, total-organic-carbon (TOC), and pH. The stream bank soils were also analyzed for the stable-Hg-isotopes (198Hg, 199Hg, 200Hg, 201Hg, and 202Hg). Furthermore, some of the soil samples (n=7) from the same study sites were investigated for phytoavailability of mercury as measured by degree of Hg translocation in aboveground biomass of Impatiens walleriana plants grown in the soils.^ The results showed a significant difference (p<0.001) in THg concentrations for the forest soils (42.40±4.98 mg/kg) and the grassland soils (8.71±2.30 mg/kg). The higher THg and methyl-Hg concentrations were commensurate with the higher TOC content in the soils (p<0.001). Also, the THg concentrations for the upstream site was higher (129.08±34.14 mg/kg) than the downstream site (24.31±3.47 mg/kg). The two sites also differed in their stable Hg isotope compositions (p<0.001 for δ199Hg). The stable isotope analysis indicated the increased level of mass dependent isotopic fractionation with increasing depths along the EFPC bank. The difference between the two study sites was also prominent in case of the Hg uptake by the plants, with higher Hg uptake from the upstream soils compared to that from the downstream soils. A significant correlation, r=0.93 p<0.01, was observed between the Hg uptake and the soil-THg concentrations. THg was higher in the leaves (1161.87±310.01 μg/kg) than in the flowers (206.13±55.23 μg/kg) or the stems (634.54±403.35μg/kg). ^ The level of Hg contamination increased with decreasing distance from the point source and was highly influenced by plants/microbes, soil-organic-content, and Hg-speciation. The isotopic study indicated the existence of an additional Hg source in the EFPC watershed, possibly atmospheric Hg-deposition. These findings are worth taking into account while planning any Hg remediation effort and developing Hg loading criteria as per the National Pollutant Discharge Elimination System (NPDES) Program.^

Hydrological Conditions Control P Loading and Aquatic Metabolism in an Oligotrophic, Subtropical Estuary

Using high-resolution measures of aquatic ecosystem metabolism and water quality, we investigated the importance of hydrological inputs of phosphorus (P) on ecosystem dynamics in the oligotrophic, P-limited coastal Everglades. Due to low nutrient status and relatively large inputs of terrestrial organic matter, we hypothesized that the ponds in this region would be strongly net heterotrophic and that pond gross primary production (GPP) and respiration (R) would be the greatest during the “dry,” euhaline estuarine season that coincides with increased P availability. Results indicated that metabolism rates were consistently associated with elevated upstream total phosphorus and salinity concentrations. Pulses in aquatic metabolism rates were coupled to the timing of P supply from groundwater upwelling as well as a potential suite of hydrobiogeochemical interactions. We provide evidence that freshwater discharge has observable impacts on aquatic ecosystem function in the oligotrophic estuaries of the Florida Everglades by controlling the availability of P to the ecosystem. Future water management decisions in South Florida must include the impact of changes in water delivery on downstream estuaries.

Sediment and soil organic matter source assessment as revealed by the molecular distribution and carbon isotopic composition of n-alkanes

The assessment of organic matter (OM) sources in sediments and soils is a key to better understand the biogeochemical cycling of carbon in aquatic environments. While traditional molecular marker-based methods have provided such information for typical two end member (allochthonous/terrestrial vs. autochthonous/microbial)-dominated systems, more detailed, biomass-specific assessments are needed for ecosystems with complex OM inputs such as tropical and sub-tropical wetlands and estuaries where aquatic macrophytes and macroalgae may play an important role as OM sources. The aim of this study was to assess the utility of a combined approach using compound specific stable carbon isotope analysis and an n-alkane based proxy (Paq) to differentiate submerged and emergent/terrestrial vegetation OM inputs to soils/sediments from a sub-tropical wetland and estuarine system, the Florida Coastal Everglades. Results show that Paq values (0.13–0.51) for the emergent/terrestrial plants were generally lower than those for freshwater/marine submerged vegetation (0.45–1.00) and that compound specific δ13C values for the n-alkanes (C23 to C31) were distinctively different for terrestrial/emergent and freshwater/marine submerged plants. While crossplots of the Paq and n-alkane stable isotope values for the C23n-alkane suggest that OM inputs are controlled by vegetation changes along the freshwater to marine transect, further resolution regarding OM input changes along this landscape was obtained through principal component analysis (PCA), successfully grouping the study sites according to the OM source strengths. The data show the potential for this n-alkane based multi-proxy approach as a means of assessing OM inputs to complex ecosystems.

Organic Biogeochemistry of Detrital Flocculent Material (Floc) in a Subtropical, Coastal Wetland

Flocculent materials (floc), in aquatic systems usually consist of a non-consolidated layer of biogenic, detrital material relatively rich in organic matter which represents an important food-web component for invertebrates and fish. Thus, variations in its composition could impact food webs and change faunal structure. Transport, remineralization rates and deposition of floc may also be important factors in soil/sediment formation. In spite of its relevance and sensitivity to external factors, few chemical studies have been carried out on the biogeochemistry of floc material. In this study, we focused on the molecular characterization of the flocculent organic matter (OM), the assessment of its origin and its environmental fate at five stations along a freshwater to marine ecotone, namely the Taylor Slough, Everglades National Park (ENP), Florida. To tackle this issue, suspended, unconsolidated, detrital floc samples, soils/sediments and plants were analyzed for bulk properties, biomarkers and pigments. Both geochemical proxies and biomass-specific biomarkers were used to assess OM sources and transformations. Our results show that the detrital organic matter of the flocculent material is largely regulated by local vegetation inputs, ranging from periphyton, emergent and submerged plants and terrestrial plants such as mangroves, with molecular evidence of different degrees of diagenetic reworking, including fungal activity. Evidence is presented for both hydrodynamic transport of floc materials, and incorporation of floc OM into soils/sediments. However, some molecular parameters showed a decoupling between floc and underlying soil/sediment OM, suggesting that physical transport, incorporation and degradation/remineralization of OM in floc may be controlled by a combination of a variety of complex biogeochemical variables including hydrodynamic transport, hydroperiod characteristics, primary productivity, nutrient availability, and OM quality among others. Further investigations are needed to better understand the ecological role of floc in freshwater and coastal wetlands.

A Hydrological Budget (2002–2008) for a Large Subtropical Wetland Ecosystem Indicates Marine Groundwater Discharge Accompanies Diminished Freshwater Flow

Water budget parameters are estimated for Shark River Slough (SRS), the main drainage within Everglades National Park (ENP) from 2002 to 2008. Inputs to the water budget include surface water inflows and precipitation while outputs consist of evapotranspiration, discharge to the Gulf of Mexico and seepage losses due to municipal wellfield extraction. The daily change in volume of SRS is equated to the difference between input and outputs yielding a residual term consisting of component errors and net groundwater exchange. Results predict significant net groundwater discharge to the SRS peaking in June and positively correlated with surface water salinity at the mangrove ecotone, lagging by 1 month. Precipitation, the largest input to the SRS, is offset by ET (the largest output); thereby highlighting the importance of increasing fresh water inflows into ENP for maintaining conditions in terrestrial, estuarine, and marine ecosystems of South Florida.

Determining Spatial and Temporal Inputs of Freshwater, Including Submarine Groundwater Discharge, to a Subtropical Estuary Using Geochemical Tracers, Biscayne Bay, South Florida

Geochemical mixing models were used to decipher the dominant source of freshwater (rainfall, canal discharge, or groundwater discharge) to Biscayne Bay, an estuary in south Florida. Discrete samples of precipitation, canal water, groundwater, and bay surface water were collected monthly for 2 years and analyzed for salinity, stable isotopes of oxygen and hydrogen, and Sr2+/Ca2+ concentrations. These geochemical tracers were used in three separate mixing models and then combined to trace the magnitude and timing of the freshwater inputs to the estuary. Fresh groundwater had an isotopic signature (δ 18O = −2.66‰, δD −7.60‰) similar to rainfall (δ 18O = −2.86‰, δD = −4.78‰). Canal water had a heavy isotopic signature (δ 18O = −0.46‰, δD  = −2.48‰) due to evaporation. This made it possible to use stable isotopes of oxygen and hydrogen to separate canal water from precipitation and groundwater as a source of freshwater into the bay. A second model using Sr2+/Ca2+ ratios was developed to discern fresh groundwater inputs from precipitation inputs. Groundwater had a Sr2+/Ca2+ ratio of 0.07, while precipitation had a dissimilar ratio of 0.89. When combined, these models showed a freshwater input ratio of canal/precipitation/groundwater of 37%:53%:10% in the wet season and 40%:55%:5% in the dry season with an error of ±25%. For a bay-wide water budget that includes saltwater and freshwater mixing, fresh groundwater accounts for 1–2% of the total fresh and saline water input.

Integrated Carbon Budget Models for the Everglades Terrestrial-Coastal-Oceanic Gradient: Current Status and Needs for Inter-Site Comparisons

Recent studies suggest that coastal ecosystems can bury significantly more C than tropical forests, indicating that continued coastal development and exposure to sea level rise and storms will have global biogeochemical consequences. The Florida Coastal Everglades Long Term Ecological Research (FCE LTER) site provides an excellent subtropical system for examining carbon (C) balance because of its exposure to historical changes in freshwater distribution and sea level rise and its history of significant long-term carbon-cycling studies. FCE LTER scientists used net ecosystem C balance and net ecosystem exchange data to estimate C budgets for riverine mangrove, freshwater marsh, and seagrass meadows, providing insights into the magnitude of C accumulation and lateral aquatic C transport. Rates of net C production in the riverine mangrove forest exceeded those reported for many tropical systems, including terrestrial forests, but there are considerable uncertainties around those estimates due to the high potential for gain and loss of C through aquatic fluxes. C production was approximately balanced between gain and loss in Everglades marshes; however, the contribution of periphyton increases uncertainty in these estimates. Moreover, while the approaches used for these initial estimates were informative, a resolved approach for addressing areas of uncertainty is critically needed for coastal wetland ecosystems. Once resolved, these C balance estimates, in conjunction with an understanding of drivers and key ecosystem feedbacks, can inform cross-system studies of ecosystem response to long-term changes in climate, hydrologic management, and other land use along coastlines.

Evaluating the Distribution of Terrestrial Dissolved Organic Matter in a Complex Coastal Ecosystem Using Fluorescence Spectroscopy

The coastal zone of the Florida Keys features the only living coral reef in the continental United States and as such represents a unique regional environmental resource. Anthropogenic pressures combined with climate disturbances such as hurricanes can affect the biogeochemistry of the region and threaten the health of this unique ecosystem. As such, water quality monitoring has historically been implemented in the Florida Keys, and six spatially distinct zones have been identified. In these studies however, dissolved organic matter (DOM) has only been studied as a quantitative parameter, and DOM composition can be a valuable biogeochemical parameter in assessing environmental change in coastal regions. Here we report the first data of its kind on the application of optical properties of DOM, in particular excitation emission matrix fluorescence with parallel factor analysis (EEM-PARAFAC), throughout these six Florida Keys regions in an attempt to assess spatial differences in DOM sources. Our data suggests that while DOM in the Florida Keys can be influenced by distant terrestrial environments such as the Everglades, spatial differences in DOM distribution were also controlled in part by local surface runoff/fringe mangroves, contributions from seasgrass communities, as well as the reefs and waters from the Florida Current. Application of principal component analysis (PCA) of the relative abundance of EEM-PARAFAC components allowed for a clear distinction between the sources of DOM (allochthonous vs. autochthonous), between different autochthonous sources and/or the diagenetic status of DOM, and further clarified contribution of terrestrial DOM in zones where levels of DOM were low in abundance. The combination between EEM-PARAFAC and PCA proved to be ideally suited to discern DOM composition and source differences in coastal zones with complex hydrology and multiple DOM sources.