Controls on sensible heat and latent energy fluxes from a short-hydroperiod Florida Everglades marsh

Little is known of energy balance in low latitude wetlands where there is a year-round growing season and a climate best defined by wet and dry seasons. The Florida Everglades is a highly managed and extensive subtropical wetland that exerts a substantial influence on the hydrology and climate of the south Florida region. However, the effects of seasonality and active water management on energy balance in the Everglades ecosystem are poorly understood. An eddy covariance and micrometeorological tower was established in a short-hydroperiod Everglades marsh to examine the dominant environmental controls on sensible heat (H) and latent energy (LE) fluxes, as well as the effects of seasonality on these parameters. Seasonality differentially affected H and LE fluxes in this marsh, such that H was principally dominant in the dry season and LE was strongly dominant in the wet season. The Bowen ratio was high for much of the dry season (1.5–2.4), but relatively low (H and LE fluxes across nearly all seasons and years (). However, the 2009 dry season LE data were not consistent with this relationship () because of low seasonal variation in LE following a prolonged end to the previous wet season. In addition to net radiation, H and LE fluxes were significantly related to soil volumetric water content (VWC), water depth, air temperature, and occasionally vapor pressure deficit. Given that VWC and water depth were determined in part by water management decisions, it is clear that human actions have the ability to influence the mode of energy dissipation from this ecosystem. Impending modifications to water management under the Comprehensive Everglades Restoration Plan may shift the dominant turbulent flux from this ecosystem further toward LE, and this change will likely affect local hydrology and climate.

The construction and optimization of an ion mobility spectrometer for the analysis of explosives and drugs

Today, over 15,000 Ion Mobility Spectrometry (IMS) analyzers are employed at worldwide security checkpoints to detect explosives and illicit drugs. Current portal IMS instruments and other electronic nose technologies detect explosives and drugs by analyzing samples containing the headspace air and loose particles residing on a surface. Canines can outperform these systems at sampling and detecting the low vapor pressure explosives and drugs, such as RDX, PETN, cocaine, and MDMA, because these biological detectors target the volatile signature compounds available in the headspace rather than the non-volatile parent compounds of explosives and drugs.^ In this dissertation research volatile signature compounds available in the headspace over explosive and drug samples were detected using SPME as a headspace sampling tool coupled to an IMS analyzer. A Genetic Algorithm (GA) technique was developed to optimize the operating conditions of a commercial IMS (GE Itemizer 2), leading to the successful detection of plastic explosives (Detasheet, Semtex H, and C-4) and illicit drugs (cocaine, MDMA, and marijuana). Short sampling times (between 10 sec to 5 min) were adequate to extract and preconcentrate sufficient analytes (> 20 ng) representing the volatile signatures in the headspace of a 15 mL glass vial or a quart-sized can containing ≤ 1 g of the bulk explosive or drug.^ Furthermore, a research grade IMS with flexibility for changing operating conditions and physical configurations was designed and fabricated to accommodate future research into different analytes or physical configurations. The design and construction of the FIU-IMS were facilitated by computer modeling and simulation of ion’s behavior within an IMS. The simulation method developed uses SIMION/SDS and was evaluated with experimental data collected using a commercial IMS (PCP Phemto Chem 110). The FIU-IMS instrument has comparable performance to the GE Itemizer 2 (average resolving power of 14, resolution of 3 between two drugs and two explosives, and LODs range from 0.7 to 9 ng). ^ The results from this dissertation further advance the concept of targeting volatile components to presumptively detect the presence of concealed bulk explosives and drugs by SPME-IMS, and the new FIU-IMS provides a flexible platform for future IMS research projects.^

Ecophysiological characteristics of Avicennia germinans and Laguncularia racemosa coexisting in a scrub mangrove forest at the Indian River Lagoon, Florida

The purpose of this work is to increase ecological understanding of Avicennia germinans L. and Laguncularia racemosa (L.) Gaertn. F. growing in hypersaline habitats with a seasonal climate. The area has a dry season (DS) with low temperature and vapour pressure deficit (vpd), and a wet season (WS) with high temperature and slightly higher vpd. Seasonal patterns in interstitial soil water salinity suggested a lack of tidal flushing in this area to remove salt along the soil profile. The soil solution sodium/potassium (Na+/K+) ratio differed slightly along the soil profile during the DS, but during the WS it was significantly higher at the soil surface. Diurnal changes in xylem osmolality between predawn (higher) and midday (lower) were observed in both species. However, A. germinans had higher xylem osmolality compared to L. racemosa. Xylem Na+/K+ suggested higher selectivity of K+ over Na+ in both species and seasons. The water relations parameters derived from pressure–volume P–V curves were relatively stable between seasons for each species. The range of water potentials (Ψ), measured in the field, was within estimated values for turgor maintenance from P–V curves. Thus the leaves of both species were osmotically adapted to maintain continued water uptake in this hypersaline mangrove environment.

The Construction and Optimization on an Ion Mobility Spectrometer for the Analysis of Explosives and Drugs

Today, over 15,000 Ion Mobility Spectrometry (IMS) analyzers are employed at worldwide security checkpoints to detect explosives and illicit drugs. Current portal IMS instruments and other electronic nose technologies detect explosives and drugs by analyzing samples containing the headspace air and loose particles residing on a surface. Canines can outperform these systems at sampling and detecting the low vapor pressure explosives and drugs, such as RDX, PETN, cocaine, and MDMA, because these biological detectors target the volatile signature compounds available in the headspace rather than the non-volatile parent compounds of explosives and drugs. In this dissertation research volatile signature compounds available in the headspace over explosive and drug samples were detected using SPME as a headspace sampling tool coupled to an IMS analyzer. A Genetic Algorithm (GA) technique was developed to optimize the operating conditions of a commercial IMS (GE Itemizer 2), leading to the successful detection of plastic explosives (Detasheet, Semtex H, and C-4) and illicit drugs (cocaine, MDMA, and marijuana). Short sampling times (between 10 sec to 5 min) were adequate to extract and preconcentrate sufficient analytes (> 20 ng) representing the volatile signatures in the headspace of a 15 mL glass vial or a quart-sized can containing ≤ 1 g of the bulk explosive or drug. Furthermore, a research grade IMS with flexibility for changing operating conditions and physical configurations was designed and fabricated to accommodate future research into different analytes or physical configurations. The design and construction of the FIU-IMS were facilitated by computer modeling and simulation of ion’s behavior within an IMS. The simulation method developed uses SIMION/SDS and was evaluated with experimental data collected using a commercial IMS (PCP Phemto Chem 110). The FIU-IMS instrument has comparable performance to the GE Itemizer 2 (average resolving power of 14, resolution of 3 between two drugs and two explosives, and LODs range from 0.7 to 9 ng). The results from this dissertation further advance the concept of targeting volatile components to presumptively detect the presence of concealed bulk explosives and drugs by SPME-IMS, and the new FIU-IMS provides a flexible platform for future IMS research projects.

Ionized cluster beam deposition, and thin film analysis

In 1972 the ionized cluster beam (ICB) deposition technique was introduced as a new method for thin film deposition. At that time the use of clusters was postulated to be able to enhance film nucleation and adatom surface mobility, resulting in high quality films. Although a few researchers reported singly ionized clusters containing 10$\sp2$-10$\sp3$ atoms, others were unable to repeat their work. The consensus now is that film effects in the early investigations were due to self-ion bombardment rather than clusters. Subsequently in recent work (early 1992) synthesis of large clusters of zinc without the use of a carrier gas was demonstrated by Gspann and repeated in our laboratory. Clusters resulted from very significant changes in two source parameters. Crucible pressure was increased from the earlier 2 Torr to several thousand Torr and a converging-diverging nozzle 18 mm long and 0.4 mm in diameter at the throat was used in place of the 1 mm x 1 mm nozzle used in the early work. While this is practical for zinc and other high vapor pressure materials it remains impractical for many materials of industrial interest such as gold, silver, and aluminum. The work presented here describes results using gold and silver at pressures of around 1 and 50 Torr in order to study the effect of the pressure and nozzle shape. Significant numbers of large clusters were not detected. Deposited films were studied by atomic force microscopy (AFM) for roughness analysis, and X-ray diffraction.^ Nanometer size islands of zinc deposited on flat silicon substrates by ICB were also studied by atomic force microscopy and the number of atoms/cm$\sp2$ was calculated and compared to data from Rutherford backscattering spectrometry (RBS). To improve the agreement between data from AFM and RBS, convolution and deconvolution algorithms were implemented to study and simulate the interaction between tip and sample in atomic force microscopy. The deconvolution algorithm takes into account the physical volume occupied by the tip resulting in an image that is a more accurate representation of the surface.^ One method increasingly used to study the deposited films both during the growth process and following, is ellipsometry. Ellipsometry is a surface analytical technique used to determine the optical properties and thickness of thin films. In situ measurements can be made through the windows of a deposition chamber. A method for determining the optical properties of a film, that is sensitive only to the growing film and accommodates underlying interfacial layers, multiple unknown underlayers, and other unknown substrates was developed. This method is carried out by making an initial ellipsometry measurement well past the real interface and by defining a virtual interface in the vicinity of this measurement. ^

High pressure studies on group VI metal hexacarbonyl molecular solids

Group VI metal hexacarbonyls, M(CO)6 (M = Cr, Mo and W), are of extreme importance as catalysts in industry and also of fundamental interest due to the established charge transfer mechanism between the carbon monoxide and the metal. They condense to molecular solids at ambient conditions retaining the octahedral (Oh) symmetry of gas phase and have been extensively investigated by previous workers to understand their fundamental chemical bonding and possible industrial applications. However little is known about their behavior at high pressures which is the focus of this dissertation. Metal hexacarbonyls were subjected to high pressures in Diamond-Anvil cells to understand the pressure effect on chemical bonding using Raman scattering in situ. The high-pressure results on each of the three metal hexacarbonyls are presented and are followed by a critical analysis of the entire family. The Raman study was conducted at pressures up to 45 GPa and X-ray up to 58 GPa. This is followed by a discussion on infra red spectra in conjunction with Raman and X-ray analysis to provide a rationale for polymerization. Finally the probable synthesis of extremely reactive species under high-pressures and as identified via Raman is discussed. The high-pressure Raman scattering, up to 30 GPa, demonstrated the absence of Π-backbonding. The disappearance of parental Raman spectra for (M = Cr, Mo and W) at 29.6, 23.3 and 22.2 GPa respectively was attributed to the total collapse of the Oh symmetry. This collapse under high-pressure lead to metal-mediated polymeric phase characterized by Raman active δ(OCO) feature, originating from intermolecular vibrational coupling in the parent sample. Further increase in pressures up to 45 GPa, did not affect this feature. The pressure quenched Raman spectra, revealed various chemical groups non-characteristic of the parent sample and adsorption of CO in addition to the characteristic δ(OCO) feature. The thus recorded Raman, complemented with the far and mid-infrared pressure quenched spectra, reveal the formation of novel metal-mediated polymers. The X-ray diffraction on W(CO)6 up to 58 GPa revealed the generation of amorphous polymeric pattern which was retained back to ambient conditions.

Physiological responses of red mangroves to the climate in the Florida Everglades

This manuscript reports the findings of physiological studies of red mangrove (Rhizophora mangle L.) conducted from June to August 2001 and from May to June 2003 in the Florida Everglades. In situ physiological measurements were made using environmentally controlled gas exchange systems. The field investigations were carried out to define how regional climate constrains mangrove physiology and ecosystem carbon assimilation. In addition, maximum carboxylation and photosynthetic active radiation (PAR) limited carbon assimilation capacities were investigated during the summer season to evaluate whether ecophysiological models developed for mesophyte plant species can be applied to mangroves. Under summertime conditions in the Florida Everglades, maximum foliar carbon dioxide (CO2) assimilation rates reached 18 μmol CO2 m−2 s−1. Peak molar stomatal conductance to water vapor (H2O) diffusion reached 300 mmol H2O m−2 s−1. Maximum carboxylation and PAR‐limited carbon assimilation rates at the foliage temperature of 30°C attained 76.1 ± 23.4 μmol CO2 m−2 s−1 and 128.1 ± 32.9 μmol (e−) m−2 s−1, respectively. Environmental stressors such as the presence of hypersaline conditions and high solar irradiance loading (>500 W m−2 or >1000 μmoles of photons m−2 s−1 of PAR) imposed sharp reductions in carbon assimilation rates and suppressed stomatal conductance. On the basis of both field observations and model analyses, it is also concluded that existing ecophysiological models need to be modified to consider the influences of hypersaline and high radiational loadings on the physiological responses of red mangroves.

Multi-objective optimization of the molecular structure of refrigerants

The aim of this work was to develop a new methodology, which can be used to design new refrigerants that are better than the currently used refrigerants. The methodology draws some parallels with the general approach of computer aided molecular design. However, the mathematical way of representing the molecular structure of an organic compound and the use of meta models during the optimization process make it different. In essence, this approach aimed to generate molecules that conform to various property requirements that are known and specified a priori. A modified way of mathematically representing the molecular structure of an organic compound having up to four carbon atoms, along with atoms of other elements such as hydrogen, oxygen, fluorine, chlorine and bromine, was developed. The normal boiling temperature, enthalpy of vaporization, vapor pressure, tropospheric lifetime and biodegradability of 295 different organic compounds, were collected from open literature and data bases or estimated. Surrogate models linking the previously mentioned quantities with the molecular structure were developed. Constraints ensuring the generation of structurally feasible molecules were formulated and used in commercially available optimization algorithms to generate molecular structures of promising new refrigerants. This study was intended to serve as a proof-of-concept of designing refrigerants using the newly developed methodology.