Cavity-enhanced spectroscopies for applications of remote sensing, chemical kinetics and detection of radical species

This thesis describes applications of cavity enhanced spectroscopy towards applications of remote sensing, chemical kinetics and detection of transient radical molecular species. Both direct absorption spectroscopy and cavity ring-down spectroscopy are used in this work. Frequency-stabilized cavity ring-down spectroscopy (FS-CRDS) was utilized for measurements of spectral lineshapes of O₂ and CO₂ for obtaining laboratory reference data in support of NASA’s OCO-2 mission. FS-CRDS is highly sensitive (> 10 km absorption path length) and precise (> 10000:1 SNR), making it ideal to study subtle non-Voigt lineshape effects. In addition, these advantages of FS-CRDS were further extended for measuring kinetic isotope effects: A dual-wavelength variation of FS-CRDS was used for measuring precise D/H and ¹³C/¹²C methane isotope ratios (sigma>0.026%) for the purpose of measuring the temperature dependent kinetic isotope effects of methane oxidation with O(¹D) and OH radicals. Finally, direct absorption spectroscopic detection of the trans-DOCO radical via a frequency combs spectrometer was conducted in collaboration with professor Jun Ye at JILA/University of Colorado.

NUMERICAL STUDY OF DAMMANN ARRAY ILLUMINATORS

The numerical solutions of binary-phase (0, tau) gratings for one-dimensional array illuminators up to 32 are presented. Some fabrication errors, which are due to position-quantization errors, phase errors, dilation (or erosion) errors, and the side-slope error, are calculated and show that even-number array illuminators are superior to odd-number array illuminators when these fabrication errors are considered. One (0, tau) binary-phase, 8 x 16 array illuminator made with the wet-chemical-etching method is given in this paper.

Applications of nuclear magnetic resonance spectroscopy to the study of medium-sized rings. I. Conformational properties of cycloheptane. II. Conformational properties of cycloöctane

Conformational equilibrium in medium-sized rings has been investigated by the temperature variation of the fluorine-19 n.m.r. spectra of 1, 1-difluorocycloalkanes and various substituted derivatives of them. Inversion has been found to be fast on the n.m.r. time scale at -180˚ for 1, 1-difluorocycloheptane, but slow for 1, 1-difluoro-4, 4-dimethylcycloheptane at -150˚. At low temperature, the latter compound affords a single AB pattern with a chemical-shift difference of 841 cps. which has been interpreted in terms of the twist-chair conformation with the methyl groups on the axis position and the fluorine atoms in the 4-position. At room temperature, the n.m.r. spectrum of 1, 1-difluoro-4-t-butylcycloheptane affords an AB pattern with a chemical-shift difference of 185 cps. The presence of distinct trans and gauche couplings from the adjacent hydrogens has been interpreted to suggest the existence of a single predominant form, the twist chair with the fluorine atoms on the axis position.

Investigation of 1, 1-difluorocycloöctane and 1, 1, 4, 4-tetrafluorocycloöctane has led to the detection of two kinetic processes both having activation energies of 8-10 kcal./mole but quite different A values. In light of these results eleven different conformations of cycloöctane along with a detailed description of the ways in which they may be interconverted are discussed. An interpretation involving the twist-boat conformation rapidly equilibrating through the saddle and the parallel-boat forms at room temperature is compatible with the results.

Studies of chemical speciation in naturally anoxic basins

The chemical speciation of both metals and non-metals, the use of polarographic techniques, and application to the study of the chemistry of anoxic waters are considered. In the first part of the paper unfamiliar terminology is explained and then an example of simple lake chemistry is presented to illustrate why the concept of speciation is necessary.

Origin of Chinese ancient glasses;study on the earliest Chinese ancient glasses

The earliest Chinese ancient glasses before the West Han Dynasty (200 BC) from different regions are studied. The glass samples were unearthed from Hunan, Hubei, Yunnan, Sichuan, Guizhou, Guangdong and Xinjiang of China. The chemical composition of these glasses samples is analyzed by proton induced X-ray emission (PIXE) technique, energy dispersive X-ray fluorescence (EDXRF) method and inductively coupled plasma atomic emission spectrometry (ICP-AES). It is shown that the glass chemical compositions belong to barium-lead silicate BaO-PbO-SiO2, potash soda lime silicate K2O (Na2O)-CaO-SiO2 (K2O/Na2O > 1), soda potash lime silicate Na2O (K2O)-CaO-SiO2 (K2O/Na2O < 1) and potash silicate K2O-SiO2 glass systems, respectively. The origins of the earliest Chinese ancient glasses are discussed from the archaeological and historical points of view. These four types of Chinese ancient glasses were all made in Chinese territory using local raw materials. The glass preparation technology was related to the Chinese ancient bronze metallurgy and proto-porcelain glaze technology. The glass technology relationship between the East and the West is analyzed at the same time.

LC-MS based methods for phytosterols determination in oenological matrices. Targeted metabolomic study of Rioja grape varieties

221 p.+ anexos

Solid-state NMR study of bioactive binary borosilicate glasses

A series of binary borosilicate glasses prepared by the sol-gel method are shown to be bioactive. Tetraethyl orthosilicate (TEOS) and trimethylborate (TMB) in acidic medium are used to prepare xB(2)O(3)center dot(1-x)SiO2 glass systems for x = 0.045-0.167. The formation of a layer of apatite-like mineral on the glass surface becomes apparent after soaking in simulated body fluid for 48 h. We have measured the B-11-B-11 homonuclear second moments of the borosilicate glasses and inferred that no macroscopic phase separation occurred in our glasses. The B-11 chemical shift data also show that the formation of clustered boroxol rings is negligible in our glass system. Although the bioactivity of our borosilicate glasses is less than that of CaO-SiO2 sol-gel glasses, these simple binary systems could be taken as reference glass systems for the search of new bioactive borosilicate glasses. (C) 2008 Elsevier Ltd. All rights reserved.

Study on the hydrolytic property and thermal stability of LiAlO2 substrate

The hydrolytic property and thermal stability of LiAlO2 (LAO), important factors for its application, were examined by AFM and X-ray rocking curve. We found that H2O may be deleterious for LAO surface polishing when the root mean square (RMS) value is less than 1 nm. However, when the RMS value is more than 1 nm it may be useful for LAO polishing. (100)-plane LAO substrates are annealed in the range of 850-900 degrees C in flux N-2, Slick AlN layer probably is produced on the substrate surface. M-plane GaN layer has grown on the substrate by metal-organic chemical vapor deposition (MOCVD) method. Theses results show that LiAlO2 crystal is a promising substrate of fabricating high-efficiency LEDs by MOCVD. (c) 2006 Elsevier B.V. All rights reserved.

Analytical method development for the uptake study of different organic pollutants by crops cultivated in compost-amended soils

256 p.

Physico-chemical factors and bacteria in fish ponds

Analyses of pond water and mud samples show that nitrifying bacteria (including ammonifying bacteria, nitrite bacteria, nitrobacteria and denitrifying bacteria) are in general closely correlated with various physico-chemical factors, ammonifying bacteria are mainly correlated with dissolved oxygen; denitrifying bacteria are inversely correlated with phosphorus; nitrite bacteria are closely correlated with nitrites, nitrobacteria are inversely correlated with ammoniac nitrogen. The nitrifying bacteria are more closely correlated with heterotrophic bacteria. Nitrobacteria are inversely correlated with anaerobic heterotrophic bacteria. The correlation is quite weak between all the nitrite bacteria which indicates that the nitrite bacteria have a controlling and regulating function in water quality and there is no interdependence as each plays a role of its own. The paper also discusses how the superficial soil (pond mud down to 3.5 cm deep) and different layers of the mud affect the biomass of bacteria. The study shows that the top superficial layer (down to 1.5 cm deep) is the major area for decomposing and converting organic matter.

An assessment of chemical contaminants, toxicity and benthic infauna in sediments from the St. Thomas East End Reserves (STEER)

This report contains a chemical and biological characterization of sediments from the St. Thomas East End Reserves (STEER) in St. Thomas, U.S. Virgin Islands (USVI). The STEER Management Plan (published in 2011) identified chemical contaminants and habitat loss as high or very high threats and called for a characterization of chemical contaminants as well as an assessment of their effects on natural resources. The baseline information contained in this report on chemical contaminants, toxicity and benthic infaunal community composition can be used to assess current conditions, as well as the efficacy of future restoration activities. In this phase of the project, 185 chemical contaminants, including a number of organic (e.g., hydrocarbons and pesticides) and inorganic (e.g., metals) compounds, were analyzed from 24 sites in the STEER. Sediments were also analyzed using a series of toxicity bioassays, including amphipod mortality, sea urchin fertilization impairment, and the cytochrome P450 Human Reporter Gene System (HRGS), along with a characterization of the benthic infaunal community. Higher levels of chemical contaminants were found in Mangrove Lagoon and Benner Bay in the western portion of the study area than in the eastern area. The concentrations of polychlorinated biphenyls (PCBs), DDT (dichlorodiphenyltrichloroethane), chlordane, zinc, copper, lead and mercury were above a NOAA sediment quality guideline at one or more sites, indicating impacts may be present in more sensitive species or life stages in the benthic environment. Copper at one site in Benner Bay, however, was above a NOAA guideline indicating that effects on benthic organisms were likely. The antifoulant boat hull ingredient tributyltin, or TBT, was found at the third highest concentration in the history of NOAA’s National Status and Trends (NS&T) Program, which monitors the Nation’s coastal and estuarine waters for chemical contaminants and bioeffects. Unfortunately, there do not appear to be any established sediment quality guidelines for TBT. Results of the bioassays indicated significant sediment toxicity in Mangrove Lagoon and Benner Bay using multiple tests. The benthic infaunal communities in Mangrove Lagoon and Benner Bay appeared severely diminished.

Assessment of some physico-chemical parameters of River Ogun (Abeokuta, Ogun State, southwestern Nigeria) in comparison with national and international standards

This study assessed the physico-chemical quality of River Ogun, Abeokuta, Ogun state, Southwestern Nigeria. Four locations were chosen spatially along the water course to reflect a consideration of all possible human activities that are capable of changing the quality of river water. The water samples were collected monthly for seven consecutive months (December 2011 – June 2012) at the four sampling stations. pH, air temperature (℃), water temperature (℃), conductivity (µs/cm) and total dissolved solids (mg/L) were conducted in-situ with the use of HANNA Combo pH and EC multi meter Hi 98129 and Mercury-in-glass thermometer while dissolved oxygen (mg/L), nitrate (mg/L), phosphate (mg/L), alkalinity (mg/L) and hardness (mg/L) were determined ex-situ using standard methods. Results showed that dissolved oxygen, hydrogen ion concentration, total hardness and nitrate were above the maximum permissible limit of National Administration for Food, Drugs and Control (NAFDAC), Standard Organization of Nigeria (SON), Federal Environmental Protection Agency (FEPA), United States Environmental Protection Agency (USEPA), European Union (EU) and World Health Organization (WHO) for drinking water during certain months of the study period. Results also showed that water temperature and conductivity were within the permissible limits of all the standards excluding FEPA. However, total dissolved solids and alkalinity were within the permissible limits of all the standards. Adejuwon and Adelakun, (2012) also reported similar findings on Rivers Lala, Yobo and Agodo in Ewekoro local government area of Ogun state, Nigeria. Since most of the parameters measured were above the maximum permissible limits of the national and international standards, it can be concluded that the water is unfit for domestic uses, drinking and aquacultural purposes and therefore needs to be treated if it is to be used at all. The low dissolved oxygen values for the first four months was too low i.e. < 5 mg/L. This is most likely as a result of the amount of effluents discharged into the river. To prevent mass extinction of aquatic organisms due to anoxic conditions, proper regulations should be implemented to reduce the organic load the river receives.

Evaluation of chemical tests for the quality of prawns

The object of this study was to determine the value of physical, bacteriological and chemical tests used to find out and compare the indices of quality of prawns stored at 0°C and at 18°C. pH value, nature of drip, the total bacterial count, presence or absence of tryptophan, trimethylamine content, glycogen, lactic acid, vitamins such as thiamin, riboflavin and niacin were estimated periodically to evaluate the quality of prawns stored at 0°C, whereas in addition to organoleptic changes, pH, bacterial count, nature of growth in peptone water, soluble protein in salt solution and loss of moisture, glycogen, lactic acid, and changes in vitamin B contents were noted periodically for prawns stored at -l8°C. Riboflavin and niacin were not affected appreciably but the retention of thiamin in prawns was very low.

A comparative study of the morphometrics and the proximate composition of two edible molluscs Crassostrea cuculata (Born) and Perna perna (L.)

The morphometrics and the bio-chemical characteristics of Crassostrea cuculata and Perna perna were studied. In the oyster, the length was found to be positively correlated with breadth and total body weight. There was also a positive relationship between the total body weight and the total muscle weight. In the mytilid the total body weight was positively correlated with length and total muscle weight. The muscle weight was also found to be highly correlated with the length. In both animals the relationship between the length and the total body weight was curvilinear. In the oyster, the protein content was found to increase with the total body weight and the total muscle weight. In the mytilid the protein content increased not only with the total body weight but also with the length. In both animals, the relative content of protein is higher than that of carbohydrates, lipids and ash.