Variables affecting the precision and accuracy of the Intoxilyzer 5000

The Intoxilyzer 5000 was tested for calibration curve linearity for ethanol vapor concentration between 0.020 and 0.400g/210L with excellent linearity. Calibration error using reference solutions outside of the allowed concentration range, response to the same ethanol reference solution at different temperatures between 34 and 38$\sp\circ$C, and its response to eleven chemicals, 10 mixtures of two at the time, and one mixture of four chemicals potentially found in human breath have been evaluated. Potential interferents were chosen on the basis of their infrared signatures and the concentration range of solutions corresponding to the non-lethal blood concentration range of various volatile organic compounds reported in the literature. The result of this study indicates that the instrument calibrates with solutions outside the allowed range up to $\pm$10% of target value. Headspace FID dual column GC analysis was used to confirm the concentrations of the solutions. Increasing the temperature of the reference solution from 34 to 38$\sp\circ$C resulted in linear increases in instrument recorded ethanol readings with an average increase of 6.25%/$\sp\circ$C. Of the eleven chemicals studied during this experiment, six, isopropanol, toluene, methyl ethyl ketone, trichloroethylene, acetaldehyde, and methanol could reasonably interfere with the test at non-lethal reported blood concentration ranges, the mixtures of those six chemicals showed linear additive results with a combined effect of as much as a 0.080g/210L reading (Florida's legal limit) without any ethanol present. ^

New fuel cells system for portable application with low temperature cofired ceramic (LTCC) technology

Miniature direct methanol fuel cells (DMFCs) are promising micro power sources for portable appliction. Low temperature cofired ceramic (LTCC), a competitive technology for current MEMS based fabrication, provides cost-effective mass manufacturing route for miniature DMFCs. Porous silver tape is adapted as electrodes to replace the traditional porous carbon electrodes due to its compatibility to LTCC processing and other electrochemical advantages. Electrochemical evaluation of silver under DMFCs operating conditions demonstrated that silver is a good electrode for DMFCs because of its reasonable corrosion resistance, low passivating current, and enhanced catalytic effect. Two catalyst loading methods (cofiring and postfiring) of the platinum and ruthenium catalysts are evaluated for LTCC based processing. The electrochemical analysis exhibits that the cofired path out-performs the postfiring path both at the anode and cathode. The reason is the formation of high surface area precipitated whiskers. Self-constraint sintering is utilized to overcome the difficulties of the large difference of coefficient of thermal expansion (CTE) between silver and LTCC (Dupont 951) tape during cofiring. The graphite sheet employed as a cavity fugitive insert guarantees cavity dimension conservation. Finally, performance of the membrane electrode assembly (MEA) with the porous silver electrode in the regular graphite electrode based cell and the integrated cofired cell is measured under passive fuel feeding condition. The MEA of the regular cell performs better as the electrode porosity and temperature increased. The power density of 10 mWcm-2 was obtained at ambient conditions with 1M methanol and it increased to 16 mWcm -2 at 50°C from an open circuit voltage of 0.58V. For the integrated prototype cell, the best performance, which depends on the balance methanol crossover and mass transfer at different temperatures and methanol concentrations, reaches 1.13 mWcm-2 at 2M methanol solution at ambient pressure. The porous media pore structure increases the methanol crossover resistance. As temperature increased to 60°C, the device increases to 2.14 mWcm-2.

Development of Gene Expression Markers of Acute Heat-Light Stress in Reef-Building Corals of the Genus Porites

Coral reefs are declining worldwide due to increased incidence of climate-induced coral bleaching, which will have widespread biodiversity and economic impacts. A simple method to measure the sub-bleaching level of heat-light stress experienced by corals would greatly inform reef management practices by making it possible to assess the distribution of bleaching risks among individual reef sites. Gene expression analysis based on quantitative PCR (qPCR) can be used as a diagnostic tool to determine coral condition in situ. We evaluated the expression of 13 candidate genes during heat-light stress in a common Caribbean coral Porites astreoides, and observed strong and consistent changes in gene expression in two independent experiments. Furthermore, we found that the apparent return to baseline expression levels during a recovery phase was rapid, despite visible signs of colony bleaching. We show that the response to acute heat-light stress in P. astreoides can be monitored by measuring the difference in expression of only two genes: Hsp16 and actin. We demonstrate that this assay discriminates between corals sampled from two field sites experiencing different temperatures. We also show that the assay is applicable to an Indo-Pacific congener, P. lobata, and therefore could potentially be used to diagnose acute heat-light stress on coral reefs worldwide.

Fractal analysis of flocs formed in edible oil -water emulsions by image analysis techniques

Edible oil is an important contaminant in water and wastewater. Oil droplets smaller than 40 μm may remain in effluent as an emulsion and combine with other contaminants in water. Coagulation/flocculation processes are used to remove oil droplets from water and wastewater. By adding a polymer at proper dose, small oil droplets can be flocculated and separated from water. The purpose of this study was to characterize and analyze the morphology of flocs and floc formation in edible oil-water emulsions by using microscopic image analysis techniques. The fractal dimension, concentration of polymer, effect of pH and temperature are investigated and analyzed to develop a fractal model of the flocs. Three types of edible oil (corn, olive, and sunflower oil) at concentrations of 600 ppm (by volume) were used to determine the optimum polymer dosage and effect of pH and temperature. To find the optimum polymer dose, polymer was added to the oil-water emulsions at concentration of 0.5, 1.0, 1.5, 2.0, 3.0 and 3.5 ppm (by volume). The clearest supernatants obtained from flocculation of corn, olive, and sunflower oil were achieved at polymer dosage of 3.0 ppm producing turbidities of 4.52, 12.90, and 13.10 NTU, respectively. This concentration of polymer was subsequently used to study the effect of pH and temperature on flocculation. The effect of pH was studied at pH 5, 7, 9, and 11 at 30°C. Microscopic image analysis was used to investigate the morphology of flocs in terms of fractal dimension, radius of oil droplets trapped in floc, floc size, and histograms of oil droplet distribution. Fractal dimension indicates the density of oil droplets captured in flocs. By comparison of fractal dimensions, pH was found to be one of the most important factors controlling droplet flocculation. Neutral pH or pH 7 showed the highest degree of flocculation, while acidic (pH 5) and basic pH (pH 9 and pH 11) showed low efficiency of flocculation. The fractal dimensions achieved from flocculation of corn, olive, and sunflower oil at pH 7 and temperature 30°C were 1.2763, 1.3592, and 1.4413, respectively. The effect of temperature was explored at temperatures 20°, 30°, and 40°C and pH 7. The results of flocculation of oil at pH 7 and different temperatures revealed that temperature significantly affected flocculation. The fractal dimension of flocs formed in corn, olive and sunflower oil emulsion at pH 7 and temperature 20°, 30°, and 40°C were 1.82, 1.28, 1.29, 1.62, 1.36, 1.42, 1.36, 1.44, and 1.28, respectively. After comparison of fractal dimension, radius of oil droplets captured, and floc length in each oil type, the optimal flocculation temperature was determined to be 30°C. ^

Study of Ammonia Borane and its Derivatives: Influence of Nanoconfinements and Pressures

Recently, ammonia borane has increasingly attracted researchers’ attention because of its merging applications, such as organic synthesis, boron nitride compounds synthesis, and hydrogen storage. This dissertation presents the results from several studies related to ammonia borane. The pressure-induced tetragonal to orthorhombic phase transition in ammonia borane was studied in a diamond anvil cell using in situ Raman spectroscopy. We found a positive Clapeyron-slope for this phase transformation in the experiment, which implies that the phase transition from tetragonal to orthorhombic is exothermic. The result of this study indicates that the rehydrogenation of the high pressure orthorhombic phase is expected to be easier than that of the ambient pressure tetragonal phase due to its lower enthalpy. The high pressure behavior of ammonia borane after thermal decomposition was studied by in situ Raman spectroscopy at high pressures up to 10 GPa. The sample of ammonia borane was first decomposed at ~140 degree Celcius and ~0.7 GPa and then compessed step wise in an isolated sample chamber of a diamond anvil cell for Raman spectroscopy measurement. We did not observe the characteristic shift of Raman mode under high pressure due to dihydrogen bonding, indicating that the dihydrogen bonding disappears in the decomposed ammonia borane. Although no chemical rehydrogenation was detected in this study, the decomposed ammonia borane could store extra hydrogen by physical absorption. The effect of nanoconfinement on ammonia borane at high pressures and different temperatures was studied. Ammonia borane was mixed with a type of mesoporous silica, SBA-15, and restricted within a small space of nanometer scale. The nano-scale ammonia borane was decomposed at ~125 degree Celcius in a diamond anvil cell and rehydrogenated after applying high pressures up to ~13 GPa at room temperature. The successful rehydrogenation of decomposed nano-scale ammonia borane gives guidance to further investigations on hydrogen storage. In addition, the high pressure behavior of lithium amidoborane, one derivative of ammonia borane, was studied at different temperatures. Lithium amidoborane (LAB) was decomposed and recompressed in a diamond anvil cell. After applying high pressures on the decomposed lithium amidoborane, its recovery peaks were discovered by Raman spectroscopy. This result suggests that the decomposition of LAB is reversible at high pressures.

Effect of pH and temperature on the carbonate promoted dissolution of sodium meta-autunite

Release of uranium from Na-autunite, an artificial mineral created as a result of polyphosphate injection in the subsurface at the DOE Hanford Site, takes place during slow dissolution of the mineral structure. Stability information of the uranyl-phosphate phases is limited to conditions involving pH, temperature, and a few aqueous organic materials. The carbonate ion, which creates very strong complexes with uranium, is the predominant ion in the groundwater composition. The polyphosphate technology with the formation of autunite was identified as the most feasible remediation strategy to sequester uranium in contaminated groundwater and soil in situ. The objectives of the experimental work were (i) to quantify the effect of bicarbonate on the stability of synthetic sodium meta-autunite created as a result of uranium stabilization through polyphosphate injection, (ii) calculate the kinetic rate law parameters of the uranium release from Na-autunite during dissolution, and (iii) to compare the process parameters with those obtained for natural calcium meta-autunite. Experiments were conducted using SPTF apparatus, which consists of syringe pumps for controlling flow rate, Teflon reactors and a heating/cooling system. 0.25 grams of synthetic Na-autunite was placed in the reactor and buffer solutions with varying bicarbonate concentrations (0.0005 to 0.003 M) at different pH (6 - 11) were pumped through the reactors. Experiments were conducted at four different temperatures in the range of 5 - 60oC. It was concluded that the rate of release of uranium from synthetic Na-autunite is directly correlated to the bicarbonate concentration. The rate of release of uranium increased from 1.90 x 10-12 at pH 6 to 2.64 x 10-10 (mol m-2 s-1) at pH 11 at 23oC over the bicarbonate concentration range tested. The activation energy values were invariant with the change in the bicarbonate concentration; however, pH is shown to influence the activation energy values. Uranyl hydroxides and uranyl carbonates complexes helped accelerate the dissolution of autunite mineral.

Study of ammonia borane and its derivatives: Influence of nanoconfinements and pressures

Recently, ammonia borane has increasingly attracted researchers’ attention because of its merging applications, such as organic synthesis, boron nitride compounds synthesis, and hydrogen storage. This dissertation presents the results from several studies related to ammonia borane. ^ The pressure-induced tetragonal to orthorhombic phase transition in ammonia borane was studied in a diamond anvil cell using in situ Raman spectroscopy. We found a positive Clapeyron-slope for this phase transformation in the experiment, which implies that the phase transition from tetragonal to orthorhombic is exothermic. The result of this study indicates that the rehydrogenation of the high pressure orthorhombic phase is expected to be easier than that of the ambient pressure tetragonal phase due to its lower enthalpy. ^ The high pressure behavior of ammonia borane after thermal decomposition was studied by in situ Raman spectroscopy at high pressures up to 10 GPa. The sample of ammonia borane was first decomposed at ∼140 degree Celcius and ∼0.7 GPa and then compessed step wise in an isolated sample chamber of a diamond anvil cell for Raman spectroscopy measurement. We did not observe the characteristic shift of Raman mode under high pressure due to dihydrogen bonding, indicating that the dihydrogen bonding disappears in the decomposed ammonia borane. Although no chemical rehydrogenation was detected in this study, the decomposed ammonia borane could store extra hydrogen by physical absorption. ^ The effect of nanoconfinement on ammonia borane at high pressures and different temperatures was studied. Ammonia borane was mixed with a type of mesoporous silica, SBA-15, and restricted within a small space of nanometer scale. The nano-scale ammonia borane was decomposed at ∼125 degree Celcius in a diamond anvil cell and rehydrogenated after applying high pressures up to ∼13 GPa at room temperature. The successful rehydrogenation of decomposed nano-scale ammonia borane gives guidance to further investigations on hydrogen storage. ^ In addition, the high pressure behavior of lithium amidoborane, one derivative of ammonia borane, was studied at different temperatures. Lithium amidoborane (LAB) was decomposed and recompressed in a diamond anvil cell. After applying high pressures on the decomposed lithium amidoborane, its recovery peaks were discovered by Raman spectroscopy. This result suggests that the decomposition of LAB is reversible at high pressures.^