9 resultados para organic photonic materials
em Digital Commons at Florida International University
Resumo:
The presences of heavy metals, organic contaminants and natural toxins in natural water bodies pose a serious threat to the environment and the health of living organisms. Therefore, there is a critical need to identify sustainable and environmentally friendly water treatment processes. In this dissertation, I focus on the fundamental studies of advanced oxidation processes and magnetic nano-materials as promising new technologies for water treatments. Advanced oxidation processes employ reactive oxygen species (ROS) which can lead to the mineralization of a number of pollutants and toxins. The rates of formation, steady-state concentrations, and kinetic parameters of hydroxyl radical and singlet oxygen produced by various TiO2 photocatalysts under UV or visible irradiations were measured using selective chemical probes. Hydroxyl radical is the dominant ROS, and its generation is dependent on experimental conditions. The optimal condition for generation of hydroxyl radical by of TiO2 coated glass microspheres is studied by response surface methodology, and the optimal conditions are applied for the degradation of dimethyl phthalate. Singlet oxygen (1O2) also plays an important role for advanced processes, so the degradation of microcystin-LR by rose bengal, an 1O2 sensitizer was studied. The measured bimolecular reaction rate constant between MC-LR and 1O2 is ∼ 106 M-1 s-1 based on competition kinetics with furfuryl alcohol. The typical adsorbent needs separation after the treatment, while magnetic iron oxides can be easily removed by a magnetic field. Maghemite and humic acid coated magnetite (HA-Fe3O4) were synthesized, characterized and applied for chromium(VI) removal. The adsorption of chromium(VI) by maghemite and HA-Fe3O4 follow a pseudo-second-order kinetic process. The adsorption of chromium(VI) by maghemite is accurately modeled using adsorption isotherms, and solution pH and presence of humic acid influence adsorption. Humic acid coated magnetite can adsorb and reduce chromium(VI) to non-toxic chromium (III), and the reaction is not highly dependent on solution pH. The functional groups associated with humic acid act as ligands lead to the Cr(III) complex via a coupled reduction-complexation mechanism. Extended X-ray absorption fine structure spectroscopy demonstrates the Cr(III) in the Cr-loaded HA-Fe 3O4 materials has six neighboring oxygen atoms in an octahedral geometry with average bond lengths of 1.98 Å.
Resumo:
The purpose of this research is design considerations for environmental monitoring platforms for the detection of hazardous materials using System-on-a-Chip (SoC) design. Design considerations focus on improving key areas such as: (1) sampling methodology; (2) context awareness; and (3) sensor placement. These design considerations for environmental monitoring platforms using wireless sensor networks (WSN) is applied to the detection of methylmercury (MeHg) and environmental parameters affecting its formation (methylation) and deformation (demethylation). ^ The sampling methodology investigates a proof-of-concept for the monitoring of MeHg using three primary components: (1) chemical derivatization; (2) preconcentration using the purge-and-trap (P&T) method; and (3) sensing using Quartz Crystal Microbalance (QCM) sensors. This study focuses on the measurement of inorganic mercury (Hg) (e.g., Hg2+) and applies lessons learned to organic Hg (e.g., MeHg) detection. ^ Context awareness of a WSN and sampling strategies is enhanced by using spatial analysis techniques, namely geostatistical analysis (i.e., classical variography and ordinary point kriging), to help predict the phenomena of interest in unmonitored locations (i.e., locations without sensors). This aids in making more informed decisions on control of the WSN (e.g., communications strategy, power management, resource allocation, sampling rate and strategy, etc.). This methodology improves the precision of controllability by adding potentially significant information of unmonitored locations.^ There are two types of sensors that are investigated in this study for near-optimal placement in a WSN: (1) environmental (e.g., humidity, moisture, temperature, etc.) and (2) visual (e.g., camera) sensors. The near-optimal placement of environmental sensors is found utilizing a strategy which minimizes the variance of spatial analysis based on randomly chosen points representing the sensor locations. Spatial analysis is employed using geostatistical analysis and optimization occurs with Monte Carlo analysis. Visual sensor placement is accomplished for omnidirectional cameras operating in a WSN using an optimal placement metric (OPM) which is calculated for each grid point based on line-of-site (LOS) in a defined number of directions where known obstacles are taken into consideration. Optimal areas of camera placement are determined based on areas generating the largest OPMs. Statistical analysis is examined by using Monte Carlo analysis with varying number of obstacles and cameras in a defined space. ^
Resumo:
Concentrations and fluxes of C, N, and P were measured in dwarf and fringe mangrove wetlands along the Taylor River, Florida, USA from 1996 to 1998. Data from these studies revealed considerable spatial and temporal variability. Concentrations of C, N, and P in the dwarf wetland showed seasonal trends, while water source was better at explaining concentrations in the fringe wetland. The total and dissolved organic carbon (TOC and DOC), total nitrogen (TN), and total phosphorus (TP) content of both wetlands was higher during the wet season or when water was flowing to the south (Everglades source). Concentrations of nitrate plus nitrite (NOx –), ammonium (NH4 +), and soluble reactive phosphorus (SRP) in the fringe wetland were all highest during the dry season or northerly flow (bay source). Nutrient concentrations most effectively explained patterns of flux in both wetlands. Increased wetland uptake of a given constituent was usually a function of its availability in the water column. However, the release of NOx – from the dwarf wetland was related to the NH4 + concentration, suggesting a nitrification signal. Nitrogen flux in the dwarf wetland was also related to surface water salinity and temperature. Our findings indicate that freshwater Everglades marshes are an important source of dissolved organic matter to these wetlands, while Florida Bay may be a source of dissolved inorganic nutrients. Our data also suggest that temperature, salinity, and nutrient concentrations (as driven by season and water source) influence patterns of materials flux in this mangrove wetland. Applying long-term water quality data to the relationships we extracted from these flux data, we estimated that TN and TP were imported by the dwarf wetland 87 ± 10 and 48 ± 17% of the year, respectively. With Everglades restoration, modifications in freshwater delivery may have considerable effects on the exchanges of nutrients and organic matter in these transitional mangrove wetlands.
Resumo:
Water samples were collected from rivers and estuarine environments within the Florida Coastal Everglades (FCE) ecosystem, USA, and ultrafiltered dissolved organic matter (UDOM; 1 kDa) was isolated for characterization of its source, bioavailability and diagenetic state. A combination of techniques, including 15N cross-polarization magic angle spinning nuclear magnetic resonance (15N CPMAS NMR) and X-ray photoelectron spectroscopy (XPS), were used to analyze the N components of UDOM. The concentrations and compositions of total hydrolysable amino acids (HAAs) were analyzed to estimate UDOM bioavailability and diagenetic state. Optical properties (UV–visible and fluorescence) and the stable isotope ratios of C and N were measured to assess the source and dynamics of UDOM. Spectroscopic analyses consistently showed that the major N species of UDOM are in amide form, but significant contributions of aromatic-N were also observed. XPS showed a very high pyridinic-N concentration in the FCE–UDOM (21.7 ± 2.7%) compared with those in other environments. The sources of this aromatic-N are unclear, but could include soot and charred materials from wild fires. Relatively high total HAA concentrations (4 ± 2% UDOC or 27 ± 4% UDON) are indicative of bioavailable components, and HAA compositions suggest FCE–UDOM has not undergone extensive diagenetic processing. These observations can be attributed to the low microbial activity and a continuous supply of fresh UDOM in this oligotrophic ecosystem. Marsh plants appear to be the dominant source of UDOM in freshwater regions of the FCE, whereas seagrasses and algae are the dominant sources of UDOM in Florida Bay. This study demonstrates the utility of a multi-technique and multi-proxy approach to advance our understanding of DON biogeochemistry.
Resumo:
This study demonstrates the compositional heterogeneity of a protein-like fluorescence emission signal (T-peak; excitation/emission maximum at 280/325 nm) of dissolved organic matter (DOM) samples collected from subtropical river and estuarine environments. Natural water samples were collected from the Florida Coastal Everglades ecosystem. The samples were ultrafiltered and excitation–emission fluorescence matrices were obtained. The T-peak intensity correlated positively with N concentration of the ultrafiltered DOM solution (UDON), although, the low correlation coefficient (r2=0.140, p<0.05) suggested the coexistence of proteins with other classes of compounds in the T-peak. As such, the T-peak was unbundled on size exclusion chromatography. The elution curves showed that the T-peak was composed of two compounds with distinct molecular weights (MW) with nominal MWs of about >5×104 (T1) and ∼7.6×103 (T2) and with varying relative abundance among samples. The T1-peak intensity correlated strongly with [UDON] (r2=0.516, p<0.001), while T2-peak did not, which suggested that the T-peak is composed of a mixture of compounds with different chemical structures and ecological roles, namely proteinaceous materials and presumably phenolic moieties in humic-like substances. Natural source of the latter may include polyphenols leached from senescent plant materials, which are important precursors of humic substances. This idea is supported by the fact that polyphenols, such as gallic acid, an important constituent of hydrolysable tannins, and condensed tannins extracted from red mangrove (Rhizophora mangle) leaves exhibited the fluorescence peak in the close vicinity of the T-peak (260/346 and 275/313 nm, respectively). Based on this study the application of the T-peak as a proxy for [DON] in natural waters may have limitations in coastal zones with significant terrestrial DOM input.
Resumo:
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.
Resumo:
Detection canines represent the fastest and most versatile means of illicit material detection. This research endeavor in its most simplistic form is the improvement of detection canines through training, training aids, and calibration. This study focuses on developing a universal calibration compound for which all detection canines, regardless of detection substance, can be tested daily to ensure that they are working with acceptable parameters. Surrogate continuation aids (SCAs) were developed for peroxide based explosives along with the validation of the SCAs already developed within the International Forensic Research Institute (IFRI) prototype surrogate explosives kit. Storage parameters of the SCAs were evaluated to give recommendations to the detection canine community on the best possible training aid storage solution that minimizes the likelihood of contamination. Two commonly used and accepted detection canine imprinting methods were also evaluated for the speed in which the canine is trained and their reliability. As a result of the completion of this study, SCAs have been developed for explosive detection canine use covering: peroxide based explosives, TNT based explosives, nitroglycerin based explosives, tagged explosives, plasticized explosives, and smokeless powders. Through the use of these surrogate continuation aids a more uniform and reliable system of training can be implemented in the field than is currently used today. By examining the storage parameters of the SCAs, an ideal storage system has been developed using three levels of containment for the reduction of possible contamination. The developed calibration compound will ease the growing concerns over the legality and reliability of detection canine use by detailing the daily working parameters of the canine, allowing for Daubert rules of evidence admissibility to be applied. Through canine field testing, it has been shown that the IFRI SCAs outperform other commercially available training aids on the market. Additionally, of the imprinting methods tested, no difference was found in the speed in which the canines are trained or their reliability to detect illicit materials. Therefore, if the recommendations discovered in this study are followed, the detection canine community will greatly benefit through the use of scientifically validated training techniques and training aids.
Resumo:
Surface freshwater samples from Everglades National Park, Florida, were used to investigate the size distributions of natural dissolved organic matter (DOM) and associated fluorescence characteristics along the molecular weight continuum. Samples were fractionated using size exclusion chromatography (SEC) and characterized by spectroscopic means, in particular Excitation-Emission Matrix fluorescence modeled with parallel factor analysis (EEM-PARAFAC). Most of the eight components obtained from PARAFAC modeling were broadly distributed across the DOM molecular weight range, and the optical properties of the eight size fractions for all samples studied were quite consistent among each other. Humic-like components presented a similar distribution in all the samples, with enrichment in the middle molecular weight range. Some variability in the relative distribution of the different humic-like components was observed among the different size fractions and among samples. The protein like fluorescence, although also generally present in all fractions, was more variable but generally enriched in the highest and lowest molecular weight fractions. These observations are in agreement with the hypothesis of a supramolecular structure for DOM, and suggest that DOM fluorescence characteristics may be controlled by molecular assemblies with similar optical properties, distributed along the molecular weight continuum. This study highlights the importance of studying the molecular structure of DOM on a molecular size distribution perspective, which may have important implications in understanding the environmental dynamics such materials.
Resumo:
Detection canines represent the fastest and most versatile means of illicit material detection. This research endeavor in its most simplistic form is the improvement of detection canines through training, training aids, and calibration. This study focuses on developing a universal calibration compound for which all detection canines, regardless of detection substance, can be tested daily to ensure that they are working with acceptable parameters. Surrogate continuation aids (SCAs) were developed for peroxide based explosives along with the validation of the SCAs already developed within the International Forensic Research Institute (IFRI) prototype surrogate explosives kit. Storage parameters of the SCAs were evaluated to give recommendations to the detection canine community on the best possible training aid storage solution that minimizes the likelihood of contamination. Two commonly used and accepted detection canine imprinting methods were also evaluated for the speed in which the canine is trained and their reliability. As a result of the completion of this study, SCAs have been developed for explosive detection canine use covering: peroxide based explosives, TNT based explosives, nitroglycerin based explosives, tagged explosives, plasticized explosives, and smokeless powders. Through the use of these surrogate continuation aids a more uniform and reliable system of training can be implemented in the field than is currently used today. By examining the storage parameters of the SCAs, an ideal storage system has been developed using three levels of containment for the reduction of possible contamination. The developed calibration compound will ease the growing concerns over the legality and reliability of detection canine use by detailing the daily working parameters of the canine, allowing for Daubert rules of evidence admissibility to be applied. Through canine field testing, it has been shown that the IFRI SCAs outperform other commercially available training aids on the market. Additionally, of the imprinting methods tested, no difference was found in the speed in which the canines are trained or their reliability to detect illicit materials. Therefore, if the recommendations discovered in this study are followed, the detection canine community will greatly benefit through the use of scientifically validated training techniques and training aids.