The Microwave-Assisted Process (MAP$ sp{ rm TM}$) is an enhanced extraction technology patented by Environment Canada. MAP uses microwaves to rapidly transfer target compounds from one phase to another by selectively heating the phase containing the target compounds. This thesis presents the results of research performed to determine whether the MAP technique can be further developed into a large-scale soil treatment process that overcomes the limitations of conventional remediation technologies. / The dielectric properties of several mixtures of acetone and hexane over a temperature range from 25$ sp circ$C to 50$ sp circ$C were measured. The dielectric constants of these mixtures were found not to vary significantly with temperature. / A study of microwave absorption by heterogeneous mixtures showed that adding a solid material to a low dielectric constant solvent resulted in energy being preferentially absorbed by the solid. / The results of laboratory extraction tests showed that the ability of the MAP technique to extract contaminants was affected by the organic matter content of soil, particularly in the presence of water. / Use of a closed-vessel system yielded a 60% to 175% increase in the extraction of PAHs from a low organic-content soil relative to that achieved in an open-vessel system. (Abstract shortened by UMI.)

Isoprene is the most abundant volatile organic compound (VOC) emitted from vegetation, mainly trees. Because it plays an important role in tropospheric chemistry leading to formation of pollutants and enhancing the lifetime of the greenhouse gas methane, concern about the response of isoprene emissions to the rise in atmospheric CO2 concentration and global climate change has been increasing over the last few years. The consequences of predicted climate change will have complex repercussions on global isoprene emission. The increasing atmospheric CO2 per se will have direct effects on terrestrial vegetation since CO2 is the substrate of photosynthesis. Because photosynthesis is limited by CO2 at current ambient concentrations, an increase in CO2 is expected to increase leaf biomass (i.e. isoprene emitting surface). Predicted warmer climate, extended drought periods, the possible shift in plant species in favour of isoprene emitters and the increase in length of growing season, may cause an increase in global isoprene emissions with profound perturbations of air quality and the global carbon cycle. The aim of this thesis was to investigate the effect of environmental variables such as light, temperature, drought and leaf-to-air vapour pressure deficit (VPD), and the short- and long-term effect of atmospheric [CO2] on isoprene emission from temperate and tropical tree species. Both leaf and whole ecosystem level fluxes were studied. At the leaf scale, a short-term experiment with leaves of potted two-year old trees of Quercus virginiana was carried out, exposing plants to two drying-rewatering cycles. Leaf isoprene emission fell, but the process was considerably less sensitive to water stress than photosynthesis and stomatal conductance. In drought conditions, the large reduction in photosynthesis caused the percentage of fixed carbon lost as isoprene to increase as plants became more stressed, reaching peaks of 50% when photosynthesis was almost zero. Isoprene emissions also showed a strong negative linear relationship with pre-dawn leaf water potential (psi-leaf). In another experiment carried out at the large enclosed facility of Biosphere 2 (B2L, Arizona, USA), studying isoprene emission from leaves of three-year-old plants of Populus deltoides grown at three CO2 atmospheric concentrations (430, 800 and 1200 mu mol mol-1 CO2) in non-stressed conditions, instantaneous increases in atmospheric [CO2] always resulted in a reduction of isoprene emission and a stimulation of photosynthesis. Moreover, in the long-term, the CO2 inhibition effect for isoprene emission became a permanent feature for plants growing under elevated [CO2]. Again, isoprene emission was less responsive to drought than photosynthesis. Both water-stress and high VPD strongly stimulated isoprene emission and depressed photosynthetic rate as a result of stomatal closure and the resulting decreases in intercellular [CO2] (Ci). This also led to a dramatic increase in the proportion of assimilated carbon lost as isoprene. The effect of atmospheric elevated [CO2] and its interaction with high VPD and water stress on ecosystem gross isoprene production (GIP) and net ecosystem exchange of CO2 (NEE) in the Populus deltoides plantations was also studied. Although GIP and NEE showed a similar response to light and temperature, NEE was stimulated by elevated CO2 by 72% and depressed by high VPD, while GIP was inhibited by elevated CO2 by 58% and stimulated by high VPD. Similar to what was observed at leaf level, under water stress conditions GIP was stimulated in the short term and declined only when the stress was severe, whereas NEE started to decrease from the beginning of the experiment. This contrasting response led the percentage of assimilated carbon lost by the ecosystem as isoprene to increase as water stress progressed from 2.5% and 0.6% in well-watered conditions to 60% and 40% for the ambient and the elevated CO2 treatments, respectively. Again, we found water limitation and high VPD off-set the inhibitory effect of elevated CO2, leading to increased isoprene emissions. The effect of a mild water stress on GIP and gross primary production (GPP) was also observed in the model tropical rainforest mesocosm of B2L. Although GPP was reduced by 32% during drought, GIP was not affected and correlated very well with both light and temperature. The percentage of fixed C lost as isoprene tended to increase during drought because of the reduction in GPP. Consumption of isoprene by soil was observed in both systems. The isoprene sink capacity of litter-free soil of the agroforest stands showed no significant response to different CO2 treatments, while isoprene production was strongly depressed by elevated atmospheric [CO2]. In both mesocosms, drought suppressed the sink capacity, but the full sink capacity of dry soil was recovered within a few hours upon rewetting. In summary, elevated CO2 increased biomass production and photosynthesis while depressing isoprene production. However, both drought and VPD may off-set the CO2 effect and lead to enhanced isoprene emission. We conclude that the overall effect of global climate change could be of enhancing global isoprene emissions while depressing the soil sink, and that the soil uptake of atmospheric isoprene is likely to be modest but significant and needs to be taken into account for a comprehensive estimate of the global isoprene budget.

No description available.

Thesis (MTech (Chemical Engineering))--Peninsula Technikon, 2001 / Certain fungi have been shown to excrete extracellular enzymes, including peroxidases, laccases, etc. These enzymes are useful for bioremediation of aromatic pollutants present in industrial effluents (Leukes, 1999; Navotny et aI, 1999). Leukes (1999) made recent significant development in the form of a capillary membrane gradostat (fungal) bioreactor that offers optimal conditions for the production of these enzymes in high concentrations. This system also offers the possibility for the polluted effluent to be treated directly in the bioreactor. Some operating problems relating to continuous production of the enzymes and scale-up of the capillary modules, were, however, indentified. In an attempt to solve the above-mentioned identified problems the research group at Peninsula Technikon considered a number of alternative bioreactor configurations. A pulsed packed bed bioreactor concept suggested by Moreira et at. (1997) was selected for further study. Their reactor used polyurethane pellets as the support medium for the fungal biofilm and relied upon pulsing of the oxygen supply and recycle of nutrient solution in order to control biomass accumulation. These authors reported accumulation due to the recycle of proteases that were believed to destroy the desired ligninases. We experimented with a similar concept without recycle to avoid backrnixing and thereby overcome protease accumulation. In our work, a maximum enzyme productivity of 456 Units.L1day·1 was attained. Since this was significantly greater than the maximum reported by Moreira et aI, 1997 (202 Units.L-1day-I) it appeared that the elimination of recycle had significant benefits. In addition to eliminating recycle we also used a length / diameter (L / D) ratio of 14: 1 (compared with 2.5: 1 used by Moreira et aI, 1997) in order to further reduce backrnixing. Residence time distributions were investigated to gain insight into mechanisms of dispersion in the reactor. It was found that the pulsed packed bed concept presented problems with regard to blockage by excess biomass. This led us to consider the advantages of a fluidized bed using resin beads. Accordingly, growth of fungi on resin beads in shake flasks was investigated with favorable results. An experimental program is proposed to further investigate the fluidized bed concept with a view to extending the operation time of the bioreactor. From our literature survey to date, packed bed fungal bioreactors are still the best reactor configuration for continuous production ofligninolytic enzymes. An interesting study of the application of laccases to the degradation of naphthalene and MTBE is described in an addendum to this thesis.

Water is an important resource. It is used for domestic, industrial, agricultural and recreational purposes. The quality of water is, however, significantly deteriorating due to the accumulation of organic species in aqueous system. Domestic, industrial and commercial activities comprise the biggest source of organic pollutants in municipal water. The increase of water pollution by these organics has led to the development of several water purification measures. Among others, water treatment technologies that are in place consist of ion exchange, activated carbon adsorption, reverse osmosis, molecular sieves and zeolites. However, none of these techniques have been reported to remove organic pollutants to parts-per-billion (ppb) or microgram-per-litre (ìg/L) levels. Recently, it has been reported that cyclodextrin nanoporous polymers are capable of absorbing these pollutants from water to such desirable levels. Cyclodextrins (CDs), basically starch derivatives, are cyclic oligomers consisting of glucopyranosyl units linked together through á-1,4-glycosidic linkages. They behave as molecular hosts capable of interacting with a range of guest molecules in a noncovalent manner within their cylindrical hydrophobic cavities. These interactions are a basis for the inclusion of various organic species. However, the high solubility of cyclodextrins in aqueous medium limits their application in the removal of organic pollutants from water. To make them insoluble, they are converted into highly cross-linked polymers. This is achieved by polymerizing the cyclodextrins with suitable difunctional linkers. In this project, a wide variety of monofunctionalized CDs have been effectively prepared using efficient modification strategies and successfully characterized by Infra-red (IR) and Nuclear Magnetic Resonance (NMR) spectroscopy. From these monofunctionalized CDs and corresponding linkers, insoluble nanoporous polymers with different physical properties were synthesized (Scheme 1). / Dr. B.B. Mamba

This study was to explore the relationships between personal exposure to 10 volatile organic compounds (VOCs) and biochemical liver tests with the application of canonical correlation analysis. Data from a subsample of the 1999-2000 National Health and Nutrition Examination Survey were used. Serum albumin, total bilirubin (TB), alanine aminotransferase (ALT), aspartate aminotransferase (AST), lactate dehydrogenase (LDH), alkaline phosphatase (ALP), and γ-glutamyl transferase (GGT) served as the outcome variables. Personal exposures to benzene, chloroform, ethylbenzene, tetrachloroethene, toluene, trichloroethene, o-xylene, m-,p-xylene, 1,4-dichlorobenzene, and methyl tert-butyl ether (MTBE) were assessed through the use of passive exposure monitors worn by study participants. The first two canonical correlations were 0.3218 and 0.2575, suggesting a positive correlation mainly between the six VOCs (benzene, ethylbenzene, toluene, o-xylene, m-,p-xylene, and MTBE) and the three biochemical liver tests (albumin, ALP, and GGT) and a positive correlation mainly between the two VOCs (1,4-dichlorobenzene and tetrachloroethene) and the two biochemical liver tests (LDH and TB). Subsequent multiple linear regressions show that exposure to benzene, toluene, or MTBE was associated with serum albumin, while exposure to tetrachloroethene was associated with LDH and total bilirubin. In conclusion, exposure to certain VOCs as a group or individually may influence certain biochemical liver test results in the general population.

Corpus Christi among of the largest industrialized coastal urban areas in Texas. The strategic location of the city along the Gulf of Mexico allows for many important industries and an international business to be located. The cluster of industries and businesses in the region contribute to the air pollution from emissions that are harmful to the environment and to the people living in and visiting the area. Volatile organic compounds (VOC) constitute an important class of pollutants measured in the area. The automated gas chromatography (Auto GC) data was collected from Texas Commission of Environmental Quality (TCEQ) and source apportionment analysis was conducted on this data to identify key sources of VOC affecting this study region. EPA PMF 3.0 was employed in this sources apportionment study of measured VOC concentration during 2005 - 2012 in Corpus Christi, Texas. The study identified nine optimal factors (Source) that could explain the concentration of VOC at two urbane monitoring sites in the study region. Natural gas was found to be the largest contributor of VOC in the area, followed by gasoline and vehicular exhaust. Diesel was the third highest contributor with emissions from manufacturing and combustion processes. Refineries gases and evaporative fugitive emissions were other major contributors in the area; Flaring operations, solvents, and petrochemicals also impacted the measured VOC in the urban area. It was noted that he measured VOC concentrations were significantly influenced by the economic downturn in the region and this was highlighted in the annual trends of the apportioned VOC.

No description available.

Rules which correlate structure and insecticidal activity of pyrethroids have evolved over the last thirty years from the results obtained in the testing of various synthetic pyrethroids. The major portion of these rules have dealt either with the development of new alcohol moieties or variations in the unsaturated side chain of the cyclopropane ring. There has been very little work done concerning modifications of the cyclopropane ring. This study was initiated to discover the affect of substituting an aziridin ring for the cyclopropane ring found in pyrethroids.

There is a need for chemical sensors for monitoring volatile organic compounds (VOCs) in air. Acute and chronic inhalation of toxic VOCs can cause adverse health effects in humans, so monitoring these analytes is important for ensuring that their concentrations are maintained below maximum permissible levels. Chemical sensors using polydimethylsiloxane (PDMS) to extract VOCs with partial selectivity, coupled with label-free optical detection methods based on refractive index, can overcome the limitations of conventional VOC detection methods. A variety of tunable and high refractive index PDMS materials were developed by incorporating a range of titanium and zirconium concentrations (2.5 – 30 mol % and 2.5 – 15 mol %, respectively) using a simple sol-gel synthesis and by incorporating a range of titanium concentrations (2.5 – 10 mol %) into naphthyl-functionalized PDMS. These materials ranged in refractive index from 1.4023 ± 0.0002 to 1.5663 ± 0.0001 at 635 nm and 1.3942 ± 0.0003 to 1.5510 ± 0.0007 at 1550 nm. The ability to use tunable refractive index PDMS films to differentiate between m-xylene and cyclohexane was demonstrated by monitoring changes in refractive index and thickness following absorption of these analytes using a refractometer at 1550 nm. The sensitivity of the refractive index response to an analyte using a particular PDMS film was dependent upon the difference between the refractive index of the analyte and film, as well as the film-air partition coefficient of the analyte. The detection limits for m-xylene and cyclohexane were 81 ppm and 4940 ppm, respectively, using PDMS-titanium-oxo nanocomposites with 5 and 10 mol % Ti, respectively. A simple planar waveguide sensor with an input grating coupler was developed to monitor changes in refractive index of the cladding through shifts in peak resonance wavelength. Using high refractive index PDMS materials as the waveguide core, we monitored changes in refractive index arising from absorption of VOCs into the grating. Here, the sensitivity of the waveguide response was dependent upon the difference in refractive index of the analyte and polymer, as well as the film-air partition coefficient of the analyte. The detection limits for m-xylene and cyclohexane were 1980 ppm and 18000 ppm, respectively. / Thesis (Master, Chemistry) -- Queen's University, 2013-08-24 11:45:57.642