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. ^

Natural organic matter and colloid-facilitated arsenic transport and transformation in porous soil media

Prediction of arsenic transport and transformation in soil environment requires understanding the transport mechanisms and proper estimation of arsenic partitioning tong all three phases in soil/aquifer systems: mobile colloids, mobile soil solution, and immobile soil solids. The primary purpose of this research is to study natural dissolved organic matter (DOM)/colloid-facilitated transport of arsenic and understand the role of soil derived carriers in the transport and transformation of both inorganic and organoarsenicals in soils. ^ DOM/colloid facilitated arsenic transport and transformation in porous soil media were investigated using a set of experimental approaches including batch experiment, equilibrium membrane dialysis experiment and column experiment. Soil batch experiment was applied to investigate arsenic adsorption on a variety of soils with different characteristics; Equilibrium membrane dialysis was employed to determine the 'free' and 'colloid-bound/complexed' arsenic in water extracts of chosen soils; Column experiments were also set up in the laboratory to simulate arsenic transport and transformation through golf course soils in the presence and absence of soil-derived dissolved substances. ^ The experimental results revealed that organic matter amendments effectively reduced soil arsenic adsorption. The majority of arsenic present in the soil extracts was associated with small substances of molecular weight (MW) between 500 and 3,500 Da, Only a small fraction of arsenic was associated with higher MW substances (MW > 3,500 Da), which was operationally defined as colloidal part in this study. The association of arsenic and DOM in the soil extracts strongly affected arsenic bioavailability, arsenic transport and transformation in soils. The results of column experiments revealed arsenic complicated behavior with various processes occurring in soils studied, including: soil arsenic' adsorption, facilitated arsenic transportation by dissolved substances presented in soil extracts and microorganisms involved arsenic species transformation. ^ Soil organic matter amendments effectively reduce soil arsenic adsorption capability either by scavenging 'soil arsenic adsorption sites or by interactions between arsenic species and dissolved organic chemicals in soil solution. Close attention must be paid for facilitated arsenic transport by dissolved substances presented in soil solution and microorganisms involved arsenic species transformation in arsenic-contaminated soils.^

Lattice Boltzmann modeling of fluid flow and solute transport in karst aquifers

A novel modeling approach is applied to karst hydrology. Long-standing problems in karst hydrology and solute transport are addressed using Lattice Boltzmann methods (LBMs). These methods contrast with other modeling approaches that have been applied to karst hydrology. The motivation of this dissertation is to develop new computational models for solving ground water hydraulics and transport problems in karst aquifers, which are widespread around the globe. This research tests the viability of the LBM as a robust alternative numerical technique for solving large-scale hydrological problems. The LB models applied in this research are briefly reviewed and there is a discussion of implementation issues. The dissertation focuses on testing the LB models. The LBM is tested for two different types of inlet boundary conditions for solute transport in finite and effectively semi-infinite domains. The LBM solutions are verified against analytical solutions. Zero-diffusion transport and Taylor dispersion in slits are also simulated and compared against analytical solutions. These results demonstrate the LBM’s flexibility as a solute transport solver. The LBM is applied to simulate solute transport and fluid flow in porous media traversed by larger conduits. A LBM-based macroscopic flow solver (Darcy’s law-based) is linked with an anisotropic dispersion solver. Spatial breakthrough curves in one and two dimensions are fitted against the available analytical solutions. This provides a steady flow model with capabilities routinely found in ground water flow and transport models (e.g., the combination of MODFLOW and MT3D). However the new LBM-based model retains the ability to solve inertial flows that are characteristic of karst aquifer conduits. Transient flows in a confined aquifer are solved using two different LBM approaches. The analogy between Fick’s second law (diffusion equation) and the transient ground water flow equation is used to solve the transient head distribution. An altered-velocity flow solver with source/sink term is applied to simulate a drawdown curve. Hydraulic parameters like transmissivity and storage coefficient are linked with LB parameters. These capabilities complete the LBM’s effective treatment of the types of processes that are simulated by standard ground water models. The LB model is verified against field data for drawdown in a confined aquifer.

Characteristics of surface-water flows in the ridge and slough landscape of Everglades National Park: implications for particulate transport

Over the last one hundred years, compartmentalization and water management activities have reduced water flow to the ridge and slough landscape of the Everglades. As a result, the once corrugated landscape has become topographically and vegetationally uniform. The focus of this study was to quantify variation in surface flow in the ridge and slough landscape and to relate flow conditions to particulate transport and deposition. Over the 2002–2003 and 2003–2004 wet seasons, surface velocities and particulate accumulation were measured in upper Shark River Slough in Everglades National Park. Landscape characteristics such as elevation, plant density and biomass also were examined to determine their impact on flow characteristics and material transport. The results of this study demonstrate that the release of water during the wet season not only increases water levels, but also increased flow speeds and particulate transport and availability. Further, flow speeds were positively and significantly correlated with water level thereby enhancing particulate transport in sloughs relative to ridges especially during peak flow periods. Our results also indicate that the distribution of biomass in the water column, including floating plants and periphyton, affects velocity magnitude and shape of vertical profiles, especially in the sloughs where Utricularia spp. and periphyton mats are more abundant. Plot clearing experiments suggest that the presence of surface periphyton and Utricularia exert greater control over flow characteristics than the identity (i.e., sawgrass or spike rush) or density of emergent macrophytes, two parameters frequently incorporated into models describing flow through vegetated canopies. Based on these results, we suggest that future modeling efforts must take the presence of floating biomass, such as Utricularia, and presence of periphyton into consideration when describing particulate transport.

Influence of hydrobiogeochemistry on transport of chromium through manganese -containing sediments: Experimental and modeling approaches

Chromium (Cr) is a metal of particular environmental concern, owing to its toxicity and widespread occurrence in groundwater, soil, and soil solution. A combination of hydrological, geochemical, and microbiological processes governs the subsurface migration of Cr. Little effort has been devoted to examining how these biogeochemical reactions combine with hydrologic processes influence Cr migration. This study has focused on the complex problem of predicting the Cr transport in laboratory column experiments. A 1-D reactive transport model was developed and evaluated against data obtained from laboratory column experiments. ^ A series of dynamic laboratory column experiments were conducted under abiotic and biotic conditions. Cr(III) was injected into columns packed with β-MnO 2-coated sand at different initial concentrations, variable flow rates, and at two different pore water pH (3.0 and 4.0). In biotic anaerobic column experiments Cr(VI) along with lactate was injected into columns packed with quartz sand or β-MnO2-coated sand and bacteria, Shewanella alga Simidu (BrY-MT). A mathematical model was developed which included advection-dispersion equations for the movement of Cr(III), Cr(VI), dissolved oxygen, lactate, and biomass. The model included first-order rate laws governing the adsorption of each Cr species and lactate. The equations for transport and adsorption were coupled with nonlinear equations for rate-limited oxidation-reduction reactions along with dual-monod kinetic equations. Kinetic batch experiments were conducted to determine the reduction of Cr(VI) by BrY-MT in three different substrates. Results of the column experiments with Cr(III)-containing influent solutions demonstrate that β-MnO2 effectively catalyzes the oxidation of Cr(III) to Cr(VI). For a given influent concentration and pore water velocity, oxidation rates are higher, and hence effluent concentrations of Cr(VI) are greater, at pH 4 relative to pH 3. Reduction of Cr(VI) by BrY-MT was rapid (within one hour) in columns packed with quartz sand, whereas Cr(VI) reduction by BrY-MT was delayed (57 hours) in presence of β-MnO 2-coated sand. BrY-MT grown in BHIB (brain heart infusion broth) reduced maximum amount of Cr(VI) to Cr(III) followed by TSB (tryptic soy broth) and M9 (minimum media). The comparisons of data and model results from the column experiments show that the depths associated with Cr(III) oxidation and transport within sediments of shallow aquatic systems can strongly influence trends in surface water quality. The results of this study suggests that carefully performed, laboratory column experiments is a useful tool in determining the biotransformation of redox-sensitive metals even in the presence of strong oxidant, like β-MnO2. ^

Simulating everglades national park hydrology and phosphorus transport under existing and future scenarios using numerical modeling

The Florida Everglades has a long history of anthropogenic changes which have impacted the quantity and quality of water entering the system. Since the construction of Tamiami Trail in the 1920's, overland flow to the Florida Everglades has decreased significantly, impacting ecosystems from the wetlands to the estuary. The MIKE Marsh Model of Everglades National Park (M3ENP) is a numerical model, which simulates Everglades National Park (ENP) hydrology using MIKE SHE/MIKE 11software. This model has been developed to determine the parameters that effect Everglades hydrology and understand the impact of specific flow changes on the hydrology of the system. ^ As part of the effort to return flows to the historical levels, several changes to the existing water management infrastructure have been implemented or are in the design phase. Bridge construction scenarios were programed into the M3ENP model to review the effect of these structural changes and evaluate the potential impacts on water levels and hydroperiods in the receiving Northeast Shark Slough ecosystem. These scenarios have shown critical water level increases in an area which has been in decline due to low water levels. Results from this work may help guide future decisions for restoration designs. ^ Excess phosphorus entering Everglades National Park in South Florida may promote the growth of more phosphorus-opportunistic species and alter the food chain from the bottom up. Two phosphorus transport methods were developed into the M3ENP hydrodynamic model to determine the factors affecting phosphorus transport and the impact of bridge construction on water quality. Results showed that while phosphorus concentrations in surface waters decreased overall, some areas within ENP interior may experience an increase in phosphorus loading which the addition of bridges to Tamiami Trail. Finally, phosphorus data and modeled water level data was used to evaluate the spectral response of Everglades vegetation to increasing phosphorus availability using Landsat imagery.^

Extended Coverage for Public Safety and Critical Communications Using Multi-hop and D2D Communications

In this thesis, we proposed the use of device-to-device (D2D) communications for extending the coverage area of active base stations, for public safety communications with partial coverage. A 3GPP standard compliant D2D system level simulator is developed for HetNets and public safety scenarios and used to evaluate the performance of D2D discovery and communications underlying cellular networks. For D2D discovery, the benefits of time-domain inter-cell interference coordi- nation (ICIC) approaches by using almost blank subframes were evaluated. Also, the use of multi-hop is proposed to improve, even further, the performance of the D2D discovery process. Finally, the possibility of using multi-hop D2D communications for extending the coverage area of active base stations was evaluated. Improvements in energy and spectral efficiency, when compared with the case of direct UE-eNB communi- cations, were demonstrated. Moreover, UE power control techniques were applied to reduce the effects of interference from neighboring D2D links.

Lattice Boltzmann Modeling of Fluid Flow and Solute Transport in Karst Aquifers

A novel modeling approach is applied to karst hydrology. Long-standing problems in karst hydrology and solute transport are addressed using Lattice Boltzmann methods (LBMs). These methods contrast with other modeling approaches that have been applied to karst hydrology. The motivation of this dissertation is to develop new computational models for solving ground water hydraulics and transport problems in karst aquifers, which are widespread around the globe. This research tests the viability of the LBM as a robust alternative numerical technique for solving large-scale hydrological problems. The LB models applied in this research are briefly reviewed and there is a discussion of implementation issues. The dissertation focuses on testing the LB models. The LBM is tested for two different types of inlet boundary conditions for solute transport in finite and effectively semi-infinite domains. The LBM solutions are verified against analytical solutions. Zero-diffusion transport and Taylor dispersion in slits are also simulated and compared against analytical solutions. These results demonstrate the LBM’s flexibility as a solute transport solver. The LBM is applied to simulate solute transport and fluid flow in porous media traversed by larger conduits. A LBM-based macroscopic flow solver (Darcy’s law-based) is linked with an anisotropic dispersion solver. Spatial breakthrough curves in one and two dimensions are fitted against the available analytical solutions. This provides a steady flow model with capabilities routinely found in ground water flow and transport models (e.g., the combination of MODFLOW and MT3D). However the new LBM-based model retains the ability to solve inertial flows that are characteristic of karst aquifer conduits. Transient flows in a confined aquifer are solved using two different LBM approaches. The analogy between Fick’s second law (diffusion equation) and the transient ground water flow equation is used to solve the transient head distribution. An altered-velocity flow solver with source/sink term is applied to simulate a drawdown curve. Hydraulic parameters like transmissivity and storage coefficient are linked with LB parameters. These capabilities complete the LBM’s effective treatment of the types of processes that are simulated by standard ground water models. The LB model is verified against field data for drawdown in a confined aquifer.

Simulating Everglades National Park hydrology and phosphorus transport under existing and future scenarios using numerical modeling

The Florida Everglades has a long history of anthropogenic changes which have impacted the quantity and quality of water entering the system. Since the construction of Tamiami Trail in the 1920's, overland flow to the Florida Everglades has decreased significantly, impacting ecosystems from the wetlands to the estuary. The MIKE Marsh Model of Everglades National Park (M3ENP) is a numerical model, which simulates Everglades National Park (ENP) hydrology using MIKE SHE/MIKE 11software. This model has been developed to determine the parameters that effect Everglades hydrology and understand the impact of specific flow changes on the hydrology of the system. As part of the effort to return flows to the historical levels, several changes to the existing water management infrastructure have been implemented or are in the design phase. Bridge construction scenarios were programed into the M3ENP model to review the effect of these structural changes and evaluate the potential impacts on water levels and hydroperiods in the receiving Northeast Shark Slough ecosystem. These scenarios have shown critical water level increases in an area which has been in decline due to low water levels. Results from this work may help guide future decisions for restoration designs. Excess phosphorus entering Everglades National Park in South Florida may promote the growth of more phosphorus-opportunistic species and alter the food chain from the bottom up. Two phosphorus transport methods were developed into the M3ENP hydrodynamic model to determine the factors affecting phosphorus transport and the impact of bridge construction on water quality. Results showed that while phosphorus concentrations in surface waters decreased overall, some areas within ENP interior may experience an increase in phosphorus loading which the addition of bridges to Tamiami Trail. Finally, phosphorus data and modeled water level data was used to evaluate the spectral response of Everglades vegetation to increasing phosphorus availability using Landsat imagery.