Comparative study of dissolved organic matter from groundwater and surface water in the Florida coastal Everglades using multi-dimensional spectrofluorometry combined with multivariate statistics

Dissolved organic matter (DOM) in groundwater and surface water samples from the Florida coastal Everglades were studied using excitation–emission matrix fluorescence modeled through parallel factor analysis (EEM-PARAFAC). DOM in both surface and groundwater from the eastern Everglades S332 basin reflected a terrestrial-derived fingerprint through dominantly higher abundances of humic-like PARAFAC components. In contrast, surface water DOM from northeastern Florida Bay featured a microbial-derived DOM signature based on the higher abundance of microbial humic-like and protein-like components consistent with its marine source. Surprisingly, groundwater DOM from northeastern Florida Bay reflected a terrestrial-derived source except for samples from central Florida Bay well, which mirrored a combination of terrestrial and marine end-member origin. Furthermore, surface water and groundwater displayed effects of different degradation pathways such as photodegradation and biodegradation as exemplified by two PARAFAC components seemingly indicative of such degradation processes. Finally, Principal Component Analysis of the EEM-PARAFAC data was able to distinguish and classify most of the samples according to DOM origins and degradation processes experienced, except for a small overlap of S332 surface water and groundwater, implying rather active surface-to-ground water interaction in some sites particularly during the rainy season. This study highlights that EEM-PARAFAC could be used successfully to trace and differentiate DOM from diverse sources across both horizontal and vertical flow profiles, and as such could be a convenient and useful tool for the better understanding of hydrological interactions and carbon biogeochemical cycling.

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.

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.

Impact of Water Supply and Sanitation on Diarrheal Morbidity among Young Children in the Socioeconomic and Cultural Context of Rwanda (Africa)

This project studied the frequency and of water contamination at the source, during transportation, and at home to determine the causes of contamination and its impact on the health of children aged 0 to 5 years. The methods used were construction of the infrastructure for three sources of potable water, administration of a questionnaire about socioeconomic status and sanitation behavior, anthropometric measurement of children, and analysis of water and feces. The contamination, first thought to be only a function of rainfall, turned out to be a very complex phenomenon. Water in homes was contaminated (43.4%) with more than 1100 total coliforms/100 ml due to the use of unclean utensils to transport and store water. This socio-economic and cultural problem should be ad- dressed with health education about sanitation, The latrines (found in 43.8% of families) presented a double-edged problem. The extremely high population density reduced the surface area of land per family, which resulted in a severe nutritional deficit (15% of the children) affecting mainly young children, rendering them more susceptible to diarrhea (three episodes/child/year).

Water resources assessment and geographic information system (GIS)-based stormwater runoff estimates for artificial recharge of freshwater aquifers in New Providence, Bahamas

The Bahamas is a small island nation that is dealing with the problem of freshwater shortage. All of the country’s freshwater is contained in shallow lens aquifers that are recharged solely by rainfall. The country has been struggling to meet the water demands by employing a combination of over-pumping of aquifers, transport of water by barge between islands, and desalination of sea water. In recent decades, new development on New Providence, where the capital city of Nassau is located, has created a large area of impervious surfaces and thereby a substantial amount of runoff with the result that several of the aquifers are not being recharged. A geodatabase was assembled to assess and estimate the quantity of runoff from these impervious surfaces and potential recharge locations were identified using a combination of Geographic Information Systems (GIS) and remote sensing. This study showed that runoff from impervious surfaces in New Providence represents a large freshwater resource that could potentially be used to recharge the lens aquifers on New Providence.

Seasonal plant water uptake patterns in the saline southeast Everglades ecotone

The purpose of this study was to determine the seasonal water use patterns of dominant macrophytes coexisting in the coastal Everglades ecotone. We measured the stable isotope signatures in plant xylem water of Rhizophora mangle, Cladium jamaicense, and Sesuvium portulacastrum during the dry (DS) and wet (WS) seasons in the estuarine ecotone along Taylor River in Everglades National Park, FL, USA. Shallow soilwater and deeper groundwater salinity was also measured to extrapolate the salinity encountered by plants at their rooting zone. Average soil water oxygen isotope ratios (δ 18O) was enriched (4.8 ± 0.2‰) in the DS relative to the WS (0.0 ± 0.1‰), but groundwater δ 18O remained constant between seasons (DS: 2.2 ± 0.4‰; WS: 2.1 ± 0.1‰). There was an inversion in interstitial salinity patterns across the soil profile between seasons. In the DS, shallow water was euhaline [i.e., 43 practical salinity units (PSU)] while groundwater was less saline (18 PSU). In the WS, however, shallow water was fresh (i.e., 0 PSU) but groundwater remained brackish (14 PSU). All plants utilized 100% (shallow) freshwater during the WS, but in the DS R. mangle switched to a soil–groundwater mix (δ 55% groundwater) while C. jamaicense and S. portulacastrum continued to use euhaline shallow water. In the DS, based on δ 18O data, the roots of R. mangle roots were exposed to salinities of 25.4 ± 1.4 PSU, less saline than either C. jamaicense(39.1 ± 2.2 PSU) or S. portulacastrum (38.6 ± 2.5 PSU). Although the salinity tolerance of C. jamaicense is not known, it is unlikely that long-term exposure to high salinity is conducive to the persistence of this freshwater marsh sedge. This study increases our ecological understanding of how water uptake patterns of individual plants can contribute to ecosystem levels changes, not only in the southeast saline Everglades, but also in estuaries in general in response to global sea level rise and human-induced changes in freshwater flows.

Vegetation:environment relationships and water management in Shark Slough, Everglades National Park

The hydrologic regime of Shark Slough, the most extensive long hydroperiod marsh in Everglades National Park, is largely controlled by the location, volume, and timing of water delivered to it through several control structures from Water Conservation Areas north of the Park. Where natural or anthropogenic barriers to water flow are present, water management practices in this highly regulated system may result in an uneven distribution of water in the marsh, which may impact regional vegetation patterns. In this paper, we use data from 569 sampling locations along five cross-Slough transects to examine regional vegetation distribution, and to test and describe the association of marsh vegetation with several hydrologic and edaphic parameters. Analysis of vegetation:environment relationships yielded estimates of both mean and variance in soil depth, as well as annual hydroperiod, mean water depth, and 30-day maximum water depth within each cover type during the 1990’s. We found that rank abundances of the three major marsh cover types (Tall Sawgrass, Sparse Sawgrass, and Spikerush Marsh) were identical in all portions of Shark Slough, but regional trends in the relative abundance of individual communities were present. Analysis also indicated clear and consistent differences in the hydrologic regime of three marsh cover types, with hydroperiod and water depths increasing in the order Tall Sawgrass , Sparse Sawgrass , Spikerush Marsh. In contrast, soil depth decreased in the same order. Locally, these differences were quite subtle; within a management unit of Shark Slough, mean annual values for the two water depth parameters varied less than 15 cm among types, and hydroperiods varied by 65 days or less. More significantly, regional variation in hydrology equaled or exceeded the variation attributable to cover type within a small area. For instance, estimated hydroperiods for Tall Sawgrass in Northern Shark Slough were longer than for Spikerush Marsh in any of the other regions. Although some of this regional variation may reflect a natural gradient within the Slough, a large proportion is the result of compartmentalization due to current water management practices within the marsh.We conclude that hydroperiod or water depth are the most important influences on vegetation within management units, and attribute larger scale differences in vegetation pattern to the interactions among soil development, hydrology and fire regime in this pivotal portion of Everglades.

Water source utilization and foliar nutrient status differs between upland and flooded plant communities in wetland tree islands

Tree islands in the Everglades wetlands are centers of biodiversity and targets of restoration, yet little is known about the pattern of water source utilization by the constituent woody plant communities: upland hammocks and flooded swamp forests. Two potential water sources exist: (1) entrapped rainwater in the vadose zone of the organic soil (referred to as upland soil water), that becomes enriched in phosphorus, and (2) phosphorus-poor groundwater/surface water (referred to as regional water). Using natural stable isotope abundance as a tracer, we observed that hammock plants used upland soil water in the wet season and shifted to regional water uptake in the dry season, while swamp forest plants used regional water throughout the year. Consistent with the previously observed phosphorus concentrations of the two water sources, hammock plants had a greater annual mean foliar phosphorus concentration over swamp forest plants, thereby supporting the idea that tree island hammocks are islands of high phosphorus concentrations in the oligotrophic Everglades. Foliar nitrogen levels in swamp forest plants were higher than those of hammock plants. Linking water sources with foliar nutrient concentrations can indicate nutrient sources and periods of nutrient uptake, thereby linking hydrology with the nutrient regimes of different plant communities in wetland ecosystems. Our results are consistent with the hypotheses that (1) over long periods, upland tree island communities incrementally increase their nutrient concentration by incorporating marsh nutrients through transpiration seasonally, and (2) small differences in micro-topography in a wetland ecosystem can lead to large differences in water and nutrient cycles.

Independent Monitoring the Cuban Economic Zone Oil Development

The extensive impact and consequences of the 2010 Deep Water Horizon oil drilling rig failure in the Gulf of Mexico, together with expanding drilling activities in the Cuban Exclusive Economic zone, have cast a spotlight on Cuban oil development. The threat of a drilling rig failure has evolved from being only hypothetical to a potential reality with the commencement of active drilling in Cuban waters. The disastrous consequences of a drilling rig failure in Cuban waters will spread over a number of vital interests of the US and of nations in the Caribbean in the general environs of Cuba. The US fishing and tourist industries will take major blows from a significant oil spill in Cuban waters. Substantial ecological damage and damage to beaches could occur for the US, Mexico, Haiti and other countries as well. The need exists for the US to have the ability to independently monitor the reality of Cuban oceanic oil development. The advantages of having an independent US early warning system providing essential real-time data on the possible failure of a drilling rig in Cuban waters are numerous. An ideal early warning system would timely inform the US that an event has occurred or is likely to occur in, essentially, real-time. Presently operating monitoring systems that could provide early warning information are satellite-based. Such systems can indicate the locations of both drilling rigs and operational drilling platforms. The system discussed/proposed in this paper relies upon low-frequency underwater sound. The proposed system can complement existing monitoring systems, which offer ocean-surface information, by providing sub-ocean surface, near-real time, information. This “integrated system” utilizes and combines (integrates) many different forms of information, some gathered through sub-ocean surface systems, and some through electromagnetic-based remote sensing (satellites, aircraft, unmanned arial vehicles), and other methods as well. Although the proposed integrated system is in the developmental stage, it is based upon well-established technologies.

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.