The Influence of Hydrologic Restoration on Groundwater-Surface Water Interactions in a Karst Wetland, the Everglades (FL, USA)

Efforts to rehydrate and restore surface water flow in karst wetlands can have unintended consequences, as these highly conductive and heterogeneous aquifers create a close connection between groundwater and surface water. Recently, hydrologic restoration efforts in the karstic Taylor Slough portion of the Everglades has changed from point source delivery of canal water (direct restoration), to the use of a series of surface water recharge retention basins (diffuse restoration). To determine the influence of restoration on groundwater-surface water interactions in the Taylor Slough headwaters, a water budget was constructed for 1997–2011 using 70 hydro-meteorological stations. With diffuse restoration, groundwater seepage from the Everglades toward the urban boundary increased, while the downstream delivery of surface water to the main portion of the slough declined. The combined influence of diffuse restoration and climate led to increased intra-annual variability in the volume of groundwater and surface water in storage but supported a more seasonally hydrated wetland compared to the earlier direct tactics. The data further indicated that hydrologic engineering in karst wetland landscapes enhances groundwater-surface water interactions, even those designed for restoration purposes.

The Influence of Phosphorus on Periphyton Mats from the Everglades and Three Tropical Karstic Wetlands

The distinctive karstic, freshwater wetlands of the northern Caribbean and Central American region support the prolific growth of calcite-rich periphyton mats. Aside from the Everglades, very little research has been conducted in these karstic wetlands, which are increasingly threatened by eutrophication. This study sought to (i) test the hypothesis that water depth and periphyton total phosphorus (TP) content are both drivers of periphyton biomass in karstic wetland habitats in Belize, Mexico and Jamaica, (ii) provide a taxonomic inventory of the periphytic diatom species in these wetlands and (iii) examine the relationship between periphyton mat TP concentration and diatom assemblage at Everglades and Caribbean locations. ^ Periphyton biomass, nutrient and diatom assemblage data were generated from periphyton mat samples collected from shallow, marl-based wetlands in Belize, Mexico and Jamaica. These data were compared to a larger dataset collected from comparable sites within Everglades National Park. A diatom taxonomic inventory was conducted on the Caribbean samples and a combination of ordination and weighted-averaging modeling techniques were used to compare relationships between periphyton TP concentration, periphyton biomass and diatom assemblage composition among the locations. ^ Within the Everglades, periphyton biomass showed a negative correlation with water depth and mat TP, while periphyton mat percent organic content was positively correlated with these two variables. These patterns were also exhibited within the Belize, Mexico and Jamaica locations, suggesting that water depth and periphyton TP content are both drivers of periphyton biomass in karstic wetland systems within the northern Caribbean region. ^ A total of 146 diatom species representing 39 genera were recorded from the three Caribbean locations, including a distinct core group of species that may be endemic to this habitat type. Weighted averaging models were produced that effectively predicted mat TP concentration from diatom assemblages for both Everglades (R2=0.56) and Caribbean (R2=0.85) locations. There were, however, significant differences among Everglades and Caribbean locations with respect to species TP optima and indicator species. This suggests that although diatoms are effective indicators of water quality in these wetlands, differences in species response to water quality changes can reduce the predictive power of these indices when applied across systems. ^

Relating precipitation and water management to nutrient concentrations in the oligotrophic ‘‘upside-down’’ estuaries of the Florida Everglades

We present 8 yr of long-term water quality, climatological, and water management data for 17 locations in Everglades National Park, Florida. Total phosphorus (P) concentration data from freshwater sites (typically ,0.25 mmol L21, or 8 mg L21) indicate the oligotrophic, P-limited nature of this large freshwater–estuarine landscape. Total P concentrations at estuarine sites near the Gulf of Mexico (average ø0.5 m mol L21) demonstrate the marine source for this limiting nutrient. This ‘‘upside down’’ phenomenon, with the limiting nutrient supplied by the ocean and not the land, is a defining characteristic of the Everglade landscape. We present a conceptual model of how the seasonality of precipitation and the management of canal water inputs control the marine P supply, and we hypothesize that seasonal variability in water residence time controls water quality through internal biogeochemical processing. Low freshwater inflows during the dry season increase estuarine residence times, enabling local processes to control nutrient availability and water quality. El Nin˜o–Southern Oscillation (ENSO) events tend to mute the seasonality of rainfall without altering total annual precipitation inputs. The Nin˜o3 ENSO index (which indicates an ENSO event when positive and a La Nin˜a event when negative) was positively correlated with both annual rainfall and the ratio of dry season to wet season precipitation. This ENSO-driven disruption in seasonal rainfall patterns affected salinity patterns and tended to reduce marine inputs of P to Everglades estuaries. ENSO events also decreased dry season residence times, reducing the importance of estuarine nutrient processing. The combination of variable water management activities and interannual differences in precipitation patterns has a strong influence on nutrient and salinity patterns in Everglades estuaries.

Importance of water source in controlling leaf leaching losses in a dwarf red mangrove (Rhizophora mangle L.) wetland

The southern Everglades mangrove ecotone is characterized by extensive dwarf Rhizophora mangle L. shrub forests with a seasonally variable water source (Everglades – NE Florida Bay) and residence times ranging from short to long. We conducted a leaf leaching experiment to understand the influence that water source and its corresponding water quality have on (1) the early decay of R. mangle leaves and (2) the early exchange of total organic carbon (TOC) and total phosphorus (TP) between leaves and the water column. Newly senesced leaves collected from lower Taylor River (FL) were incubated in bottles containing water from one of three sources (Everglades, ambient mangrove, and Florida Bay) that spanned a range of salinity from 0 to 32‰, [TOC] from 710 to 1400 μM, and [TP] from 0.17 to 0.33 μM. We poisoned half the bottles in order to quantify abiotic processes (i.e., leaching) and assumed that non-poisoned bottles represented both biotic (i.e., microbial) and abiotic processes. We sacrificed bottles after 1,2, 5, 10, and 21 days of incubation and quantified changes in leaf mass and changes in water column [TOC] and [TP]. We saw 10–20% loss of leaf mass after 24 h—independent of water treatment—that leveled off by Day 21. After 3 weeks, non-poisoned leaves lost more mass than poisoned leaves, and there was only an effect of salinity on mass loss in poisoned incubations—with greatest leaching-associated losses in Everglades freshwater. Normalized concentrations of TOC in the water column increased by more than two orders of magnitude after 21 days with no effect of salinity and no difference between poisoned and non-poisoned treatments. However, normalized [TP] was lower in non-poisoned incubations as a result of immobilization by epiphytic microbes. This immobilization was greatest in Everglades freshwater and reflects the high P demand in this ecosystem. Immobilization of leached P in mangrove water and Florida Bay water was delayed by several days and may indicate an initial microbial limitation by labile C during the dry season.

Theoretical study of chloroperoxidase catalyzed chlorination of beta-cyclopentanedione and role of water in the chlorination mechanism

Chloroperoxidase (CPO) is a potential biocatalyst for use in asymmetric synthesis. The mechanisms of CPO catalysis are therefore of interest. The halogenation reaction, one of several chemical reactions that CPO catalyzes, is not fully understood and is the subject of this dissertation. The mechanism by which CPO catalyzes halogenation is disputed. It has been postulated that halogenation of substrates occurs at the active site. Alternatively, it has been proposed that hypochlorous acid, produced at the active site via oxidation of chloride, is released prior to reaction, so that halogenation occurs in solution. The free-solution mechanism is supported by the observation that halogenation of most substrates often occurs non-stereospecifically. On the other hand, the enzyme-bound mechanism is supported by the observation that some large substrates undergo halogenation stereospecifically. The major purpose of this research is to compare chlorination of the substrate β-cyclopentanedione in the two environments. One study was of the reaction with limited hydration because such a level of hydration is typical of the active site. For this work, a purely quantum mechanical approach was used. To model the aqueous environment, the limited hydration environment approach is not appropriate. Instead, reaction precursor conformations were obtained from a solvated molecular dynamics simulation, and reaction of potentially reactive molecular encounters was modeled with a hybrid quantum mechanical/molecular mechanical approach. Extensive work developing parameters for small molecules was pre-requisite for the molecular dynamics simulation. It is observed that a limited and optimized (active-site-like) hydration environment leads to a lower energetic barrier than the fully solvated model representative of the aqueous environment at room temperature, suggesting that the stable water network near the active site is likely to facilitate the chlorination mechanism. The influence of the solvent environment on the reaction barrier is critical. It is observed that stabilization of the catalytic water by other solvent molecules lowers the barrier for keto-enol tautomerization. Placement of water molecules is more important than the number of water molecules in such studies. The fully-solvated model demonstrates that reaction proceeds when the instantaneous dynamical water environment is close to optimal for stabilizing the transition state.

Groundwater-surface water interactions on tree islands in the Everglades, south Florida

The marked decline in tree island cover across the Everglades over the last century, has been attributed to landscape-scale hydrologic degradation. To preserve and restore Everglades tree islands, a clear understanding of tree island groundwater-surface water interactions is needed, as these interactions strongly influence the chemistry of shallow groundwater and the location and patterns of vegetation in many wetlands. The goal of this work was to define the relationship between groundwater-surface water interactions, plant-water uptake, and the groundwater geochemical condition of tree islands. Groundwater and surface water levels, temperature, and chemistry were monitored on eight constructed and one natural tree island in the Everglades from 2007–2010. Sap flow, diurnal water table fluctuations and stable oxygen isotopes of stem, ground and soil water were used to determine the effect of plant-water uptake on groundwater-surface water interactions. Hydrologic and geochemical modeling was used to further explore the effect of plant-groundwater-surface water interactions on ion concentrations and potential mineral formation.^

Across-scale patterning of plant-soil-water interactions surrounding tree islands in Southern Everglades landscapes

The freshwater Everglades is a complex system containing thousands of tree islands embedded within a marsh-grassland matrix. The tree island-marsh mosaic is shaped and maintained by hydrologic, edaphic and biological mechanisms that interact across multiple scales. Preserving tree islands requires a more integrated understanding of how scale-dependent phenomena interact in the larger freshwater system. The hierarchical patch dynamics paradigm provides a conceptual framework for exploring multi-scale interactions within complex systems. We used a three-tiered approach to examine the spatial variability and patterning of nutrients in relation to site parameters within and between two hydrologically defined Everglades landscapes: the freshwater Marl Prairie and the Ridge and Slough. Results were scale-dependent and complexly interrelated. Total carbon and nitrogen patterning were correlated with organic matter accumulation, driven by hydrologic conditions at the system scale. Total and bioavailable phosphorus were most strongly related to woody plant patterning within landscapes, and were found to be 3 to 11 times more concentrated in tree island soils compared to surrounding marshes. Below canopy resource islands in the slough were elongated in a downstream direction, indicating soil resource directional drift. Combined multi-scale results suggest that hydrology plays a significant role in landscape patterning and also the development and maintenance of tree islands. Once developed, tree islands appear to exert influence over the spatial distribution of nutrients, which can reciprocally affect other ecological processes.

Temporal and Spatial Variability of Mesozooplankton in a Shallow Sub-Tropical Bay: Influence of Top-Down Control

Quantifying the relationship between mesozooplankton and water quality parameters identifies the factors that structure the mesozooplankton community and can be used to generate hypotheses regarding the mechanisms that control the mesozooplankton population and potentially the trophic network. To investigate this relationship, mesozooplankton and water quality data were collected in Florida Bay from 1994 to 2004. Three key characteristics were found in the mesozooplankton community structure: (1) there are significant differences between the four sub-regions of Florida Bay; (2) there is a break in May of 1997 with significant differences before and after this date; and (3) there is a positive correlation between mesozooplankton abundance and salinity. The latter two characteristics are closely correlated with predator abundance, indicating the importance of top-down control. Hypersaline periods appear to provide a refuge from predators, allowing mesozooplankton to increase in abundance despite the increased physiological stress.

Smoke on the water: the interplay of fire and water flow on Everglades restoration

Recent research makes clear that much of the Everglade’s flora and fauna have evolved to tolerate or require frequent fires. Nevertheless, restoration of the Everglades has thus far been conceptualized as primarily a water reallocation project. These two forces are directly linked by the influence of water flows on fire fuel moisture content, and are indirectly linked through a series of complex feedback loops. This interaction is made more complex by the alteration and compartmentalization of current water flows and fire regimes, the lack of communication between water and fire management agencies, and the already imperiled state of many local species. It is unlikely, therefore, that restoring water flows will automatically restore the appropriate fire regimes, leaving the prospect of successful restoration in some doubt. The decline of the Cape Sable seaside sparrow, and its potential for recovery, illustrates the complexity of the situation.

Mangrove tannins in aquatic ecosystems: Their fate and possible influence on dissolved organic carbon and nitrogen cycling

We describe the fate of mangrove leaf tannins in aquatic ecosystems and their possible influence on dissolved organic nitrogen (DON) cycling. Tannins were extracted and purified from senescent yellow leaves of the red mangrove (Rhizophora mangle) and used for a series of model experiments to investigate their physical and chemical reactivity in natural environments. Physical processes investigated included aggregation, adsorption to organic matter-rich sediments, and co-aggregation with DON in natural waters. Chemical reactions included structural change, which was determined by excitation–emission matrix fluorescence spectra, and the release of proteins from tannin–protein complexes under solar-simulated light exposure. A large portion of tannins can be physically eliminated from aquatic environments by precipitation in saline water and also by binding to sediments. A portion of DON in natural water can coprecipitate with tannins, indicating that mangrove swamps can influence DON cycling in estuarine environments. The chemical reactivity of tannins in natural waters was also very high, with a half-life of less than 1 d. Proteins were released gradually from tannin–protein complexes incubated under light conditions but not under dark conditions, indicating a potentially buffering role of tannin– protein complexes on DON recycling in mangrove estuaries. Although tannins are not detected at a significant level in natural waters, they play an important ecological role by preserving nitrogen and buffering its cycling in estuarine ecosystems through the prevention of rapid DON export/loss from mangrove fringe areas and/or from rapid microbial mineralization.

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. ^

The Influence of Vegetation on the Hydrodynamics and Geomorphology of a Tree Island in Everglades National Park (Florida, United States)

Transpiration-driven nutrient accumulation has been identified as a potential mechanism governing the creation and maintenance of wetland vegetation patterning. This process may contribute to the formation of nutrient-rich tree islands within the expansive oligotrophic marshes of the Everglades (Florida, United States). This study presents hydrogeochemical data indicating that tree root water uptake is a primary driver of groundwater ion accumulation across one of these islands. Sap flow, soil moisture, water level, water chemistry, and rainfall were measured to identify the relationships between climate, transpiration, and groundwater uptake by phreatophytes and to examine the effect this uptake has on groundwater chemistry and mineral formation in three woody plant communities of differing elevations. During the dry season, trees relied more on groundwater for transpiration, which led to a depressed water table and the advective movement of groundwater and dissolved ions, including phosphorus, from the surrounding marsh towards the centre of the island. Ion exclusion during root water uptake led to elevated concentrations of all major dissolved ions in the tree island groundwater compared with the adjacent marsh. Groundwater was predominately supersaturated with respect to aragonite and calcite in the lower-elevation woody communities, indicating the potential for soil formation. Elevated groundwater phosphorous concentrations detected in the highest-elevation woody community were associated with the leaching of inorganic sediments (i.e. hydroxyapatite) in the vadose zone. Understanding the complex feedback mechanisms regulating plant/groundwater/surface water interactions, nutrient dynamics, and potential soil formation is necessary to manage and restore patterned wetlands such as the Everglades.