published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

The rapid rising anthropogenic emissions driven by economic growth over China documented by satellite observations and bottom-up inventories have led to severely degraded air quality, and also have been suggested to be linked to the recent upward trends of tropospheric O₃ over the regions downwind of China. Multi-scale modeling analyses facilitated by ground-level, aircraft and satellite observations have been conducted to understand the atmospheric chemistry over China. Analyses using a 1-D photochemical model constrained by measurements at Beijing in August of 2007 suggest that reactive aromatic VOCs are the major source (~75%) of peroxy acetyl nitrate (PAN). Detailed radical budget analyses reveal the very fast ROₓ (OH + HO₂ + RO₂) production, recycling and destruction driven by VOC oxidation and heterogeneous processes. Photoenhanced aerosol surface uptake of NO₂ is found to be the predominant source of nitrous acid (HONO) during daytime (~70%). 3-D regional modeling analyses of tropospheric vertical column densities of glyoxal (CHOCHO) from SCIAMACHY show that anthropogenic emissions of aromatic VOCs are substantially underestimated (by a factor of 5 - 6, regionally varied) over China. Such an underestimation is the main cause of a large missing source of CHOCHO over the region in current global models, and could also partly explain the underestimation of organic aerosols in previous modeling studies.

Building environmental conditions such as ventilation and contaminant concentrations are important factors that influence occupant health and comfort. The objective of the present work is to investigate how personal exposure to gaseous and particulate pollutants depends on indoor airflow, source characteristics, and occupant activity in commercial and residential environments. The study examines airflow and pollutant transport using experimental measurements in conjunction with computational fluid dynamics (CFD). The results demonstrate that breathing has a measurable influence on the airflow in an occupant breathing zone, but it has very small impacts on the occupant thermal plume. The results also show that breathing can significantly affect inhaled particle concentrations, even though the influence varies with source position and particle size. Also, localized hand motions of a sitting manikin do not significantly disrupt the upward thermal plume. In typical US residences, forced convection driven mixing airflow or buoyancy driven stratified airflow occurs depending on the HVAC fan operation (fan on or fan off, respectively). The measured transition period between mixing flow (fan on) and stratified flow (fan off) is approximately one minute, implying that most airflow in the residence is either dominated by mixing or stratification. A high level of exposure to short-term pollutant sources, such as resuspension of particles from floor surfaces due to human activity, more likely occurs with stratified flow than with highly mixed airflow. This is due to the strong influence of the occupant thermal plume that transports the pollutants into the breathing zone. Furthermore, by transporting air containing ozone across the reactive occupant surface, the occupant thermal plume has a large effect on exposure to ozone reaction products. Due to the reaction of ozone with the skin oils and clothing surfaces, the occupant surface boundary layer becomes depleted of ozone and conversely enriched with ozone reaction products. The parameter ventilation effectiveness quantifies the effectiveness of airflow distribution and can be used for assessment of exposure to gaseous pollutants. Based on the study results, the usefulness of ventilation effectiveness as an indicator of exposure to particulate pollutants depends on the particle size. For small particles (~1 [mu]m), an increase of ventilation effectives caused a decrease in occupant exposure, while for large particles (~7 [mu]m), source location and airflow around the pollutant source are significant factors for the exposure, and the ventilation effectiveness has very little to no effect. / text

The current work determined whether there is a constant tissue residue associated with narcotic compounds. In this investigation, the cladoceran, Daphnia magna was exposed to lethal levels (48h LC50) of ten, $ sp{14}$C-labelled, narcotic organic chemicals in a closed system. Exposure times, ambient concentrations, and body sizes were varied to evaluate their effects. The $ sp{14}$C-method developed in current work can detect chemicals in single D. magna in concentrations ranging from 0.02 to 6310 mmol/kg. Moreover, the technique detected phobic and lipophilic chemicals equally well. The technique's sensitivity (nmol/kg) allowed for detection of differences in the internal concentrations of pollutants among the unaffected, immobilized, and dead D. magna. Immobilized D. magna contained between 0.14 mmol/kg and 200 mmol/kg of narcotics. On the average, however, the internal residues were 3.1 mmol/kg (95%CL = 3.1 $ pm$ 2.0). This agreed with literature values. The effects of time of exposure, ambient concentration, and body size on the tissue residues of narcotics varied with the chemical compound.

Please read the abstract in the section 00front of this document / Thesis (PhD (Applied Science: Chemistry))--University of Pretoria, 2007. / Chemistry / unrestricted

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An online, semi-continuous instrument to measure both total and gas phase atmospheric reactive oxygen species (ROS) and determine the concentration of ROS in the particle phase (ROS(p)) was developed. This instrument was based on a fluorescent probe for quantifying ambient ROS, specifically 2'7'-dichlorodihydrofluorescin, or DCFH probe. This probe was analyzed for sensitivity to a variety of offline and online parameters for efficient use in a field instrument. The ROS(p) instrument measures the peak light intensity at 530 nm to determine ambient ROS concentrations. ROS particles and gases are collected in a mist chamber in a nebulized mist. The instrument alternates measurements of ROS(p+g), or ROS(tot) by means of an inline filter. Fine (PM₂.₅) (ROS(p) is determined by subtraction of the ROS(g) concentration from the ROS(tot), as the ROS(g) signal could not be excluded. This instrument was tested during the summer (May-July) of 2012 at urban and rural sites in the metropolitan Atlanta and surrounding region. Concentrations of ROS(p) determined from this instrument were often below limit of detection. Average concentrations of ROS(p) were found to be 0.25 nmol/m³ in urban Atlanta (Jefferson St. and Georgia Tech), and 0.15 nmol/m³ in Yorkville, a rural site. A side by side comparison of this method with a filter collection method was made in July. The average ROS(p) offline concentrations were 0.15 nmol/m³. These concentrations were comparable to the online average concentrations of 0.21 nmol/m³ for the same period of time. This average and the majority of the measurements comprising it is dominated by the high limit of detection. The ROS instrument as constructed and operated is an efficient way to conduct ROS(p) measurements at the level of a filter study while reducing the labor intensive filter collection and extraction. In order for this instrument to be successful at measuring ambient ROS in the particle phase, the removal of the gas phase from the current sampling scheme is critical as the ROS(g) concentrations are over 90% of the measured ROS. The system as currently operable is best suited for source measurements, including biomass burning plumes or fresh exhaust to capture immediate formation.

Experiments were conducted to determine the photocatalytic degradation of three types of gas-phase compounds, NOX, VOCs, and chloramines, by TiO2 impregnated tiles. The oxides of nitrogen NO and NO2 (NOx) have a variety of negative impacts on human and environmental health ranging from serving as key precursors for the respiratory irritant ozone, to forming nitric acid, which is a primary component of acid rain. A flow tube reactor was designed for the experiments that allowed the UV illumination of the tiles under exposure to both NO and NO2 concentrations in simulated ambient air. The reactor was also used to assess NOx degradation for sampled ambient air. The PV values for NO and NO2 were 0.016 cm s-1 and 0.0015 cm s-1, respectively. For ambient experiments a decrease in ambient NOx of ~ 40% was observed over a period of roughly 5 days. The mean PV for NOx for ambient air was 0.016 cm s-1 and the maximum PV was .038 cm s-1. Overall, the results indicate that laboratory conditions generally simulate the efficiency of removing NOx by TiO2 impregnated tiles. Volatile organic compounds (VOC's) are formed in a variety of indoor environments, and can lead to respiratory problems (US EPA, 2010). The experiments determined the photocatalytic degradation of formaldehyde and methanol, two common VOCs, by TiO2 impregnated tiles. The same flow tube reactor used for the previous NOX experiments was used to test a standardized gas-phase concentration of formaldehyde and methanol. The extended UV illumination of the tiles resulted in a 50 % reduction in formaldehyde, and a 68% reduction in methanol. The deposition velocities (or the photocatalytic velocities, PV) were estimated for both VOC's. The PV for formaldehyde was 0.021 cm s-1, and the PV for methanol was 0.026 cm s-1. These PV values are slightly higher than the mean value determined for NO from the previous experiments which was 0.016 cm s-1. The results suggest that the TiO2 tiles could effectively reduce specific VOC levels in indoor environments. Chlorination is a widespread form of water disinfection. However, chlorine can produce unwanted disinfection byproducts when chlorine reacts with nitrogen containing compounds or other organics. The reaction of chlorine with ammonia produces one of three chloramines, (mono-, di-, and tri-chloramine). The production of chloramines compounds in indoor areas increases the likelihood of asthma in pool professionals, competitive swimmers, and children that frequently bath in indoor chlorinated swimming pools (Jacobs, 2007; Nemery, 2002; Zwiener, 2007). A modified flow tube reactor in conjunction with a standardized solution of monochloramine, NH2Cl, determined the photocatalytic reactions over the TiO2 tiles and seven concrete samples. The concrete samples included five different concrete types, and contained either 5 % or 15 % TiO2 by weight. The PV for the tiles was 0.045 cm s-1 for the tiles manufactured by TOTO Inc. The highest PV from the concrete samples was 0.054 cm s-1. Overall the commercial tiles were most efficient at reducing NH2Cl, compared to NOX and VOC compounds. However, the concrete samples had an even higher PV for NH2Cl than the tiles. The reason for this is unknown; however, distinct surface characteristics and a higher concentration of TiO2 in the concrete may have contributed to these findings.

Bibliography: pages 103-119. / The aims of this study were (a) to examine the profile of hospital admissions for selected respiratory illnesses for two major hospitals in Cape Town, and (b) to analyse the association of such admissions with air pollution indicators and meteorological variables. The first part of the study investigated the admission patterns of coloured and African children under twelve years of age who were diagnosed as suffering from asthma or acute respiratory infections at two major teaching hospitals in Cape Town. Computerized hospital admission records covering the years 1988-1990 from the overnight holding wards of the Red Cross War Memorial Children's Hospital and Tygerberg Hospital were used to determine patterns with respect to diagnosis, gender, race, age and date of admission. During the three year study period, respiratory admissions at both hospitals accounted for 15 078 (47.3%) out of a total of 31 887 admissions. Acute respiratory infections accounted for 63.6% and asthma 37.4 % of these respiratory admissions. Two factors of interest were noted: (1) Considerably more males than females were admitted with both asthma and acute respiratory infections. (2) Asthma admissions to Red Cross Hospital among African children were proportionally much less than those of coloured children when compared to the proportions of admissions for acute respiratory infections. After removal of the seasonal effect, a multiple linear regression model was fitted to the data to determine the individual associations between admissions and ambient environmental variables. Significant associations were found between: (1) acute respiratory infections and oxides of nitrogen, soiling index, and temperature; (2) asthma and oxides of nitrogen (3) total admissions and soiling index, average temperature and minimum temperature (negative). The study concluded that despite generally low levels of air pollution in Cape Town, childhood respiratory admissions to Red Cross War Memorial Children's Hospital and Tygerberg Hospital were statistically significantly associated with some ambient air pollutants as well as temperature. However, given the nature of both the exposure and admissions databases, these results should be treated with caution. More representative site selections for air pollution monitors, as well as searching and controlling for possible confounding factors (i.e. indoor air pollution, parental smoking, overcrowding), would allow a better understanding of the current air pollution problem and the possible effects on the respiratory health of children in metropolitan Cape Town.

Municipal treated wastewater entering rivers contain biologically active pharmaceuticals capable of inducing effects in aquatic life. Phytoremediation of three of these pharmaceuticals and an herbicide was investigated using Sandbar willow (Salix exigua) and Arabidopsis thaliana. Both plants were effective at removing compounds from solution, with removal of 86% of the synthetic estrogen, 17α-ethynylestradiol, 65% of the anti-hypertensive, diltiazem, 60% of the anti-convulsant, diazepam (Valium®), and 51% of the herbicide atrazine, in 24 hours. Distribution of compounds within roots and shoots, in soluble and bound forms, differed among compounds. Uptake and distribution of pharmaceuticals within the study plants confirmed pharmaceutical behaviour can be predicted based on a physiochemical property, their octanol-water partitioning coefficients. An effective method for detection of 17α-ethynylestradiol within surface water using solid phase extraction and gas chromatography-mass spectrometry was developed. Previously unreported breakdown of 17α-ethynylestradiol into another common estrogen, estrone, during preparative steps and gas chromatography was resolved. / xv, 216 leaves ; 29 cm.