Recent research has shown that the Arctic may be a sink for mercury, however, the fate of this deposited mercury in the environment is not known. The objective of this project was to determine the factors affecting methyl mercury (MeHg) production in Arctic organic soil on the Truelove Lowlands, Devon Island, Canada. In the field we observed a steady decrease in MeHg over time, with MeHg concentration at many sampling locations declining below detection limits. This decrease did not correlate to any chemical or biophysical parameter measured. During the study the Lowlands appeared to be mildly reducing with dissolved Fe(II) being present in the porewater, however, no correlation was observed between MeHg production and the variables measured. The dissolved organic matter concentration of the porewater was quite high, the pH was circumneutral and it would seem that in the absence of more highly reducing conditions that mercury would be unavailable for methylation.<p> It seems likely under field conditions MeHg was much more bioavailable then inorganic mercury. This would lead to a higher rate of demethylation then methylation and a net decrease in MeHg. Little research has been done on demethylation and the effect of environmental conditions on demethylation, especially in arctic environments. However, it is possible that the rate of demethylation was not affected by changes in temperature or any other parameter measured over the course of the field study. <p> Laboratory microcosm studies using saturated soil from the organic horizons demonstrated little potential for unspiked organic soil to produce significant amounts of MeHg. The spiked treatment, however, had an eight fold increase in MeHg concentration and the sterile treatment showed no change in MeHg concentration over 40 days of freeze (-5 0C) and 59 days of thaw (4 oC). <p> Our data suggests that a combination of atmospheric and in-situ processes maintain a cycle of MeHg production (spring) and loss (summer) in arctic soils. It would seem that Arctic wetland soils are not a significant source of MeHg to the Arctic ecosystem and that snowmelt is the dominant source.

This thesis dealt with the techniques that could be used for the pre-assessment of contaminated sites. The goals of the thesis were based on a simple fact that every contaminated site possesses certain potential to degrade natural resources, specifically groundwater and land resources. The thesis focused on using mathematical and statistical techniques to predict the maximum length of contaminated plumes or Lmax, which it considered as a key parameter that could be used for the site assessment. As the first thesis work, data from KORA sites were compiled and analysed. From the analyses, it was found that the Lmax for BTEX plumes are in average under 150 m long. Further, for this work, Analytical Models that can be used to estimate Lmax were reviewed and, examples comparing model and fifield Lmax were presented. The second work for the thesis focused on a development and analysis of a new 3D-analytical model for a fifinite planar and fully penetrating source. An implicit expression for predicting Lmax was obtained. The analysis of the developed model suggested that the longest Lmax will result if the source takes an approximately square shape. The last part of the thesis improved the 3D-analytical model obtained in the second work by presenting an expression for a fifinite planar source that only partially penetrates the aquifer. For this work, a very simple numerical technique was developed that not only simplififies numerical analysis of the scenarios considered in this thesis but it also bears potentials to be used for very complex subsurface reaction transport scenarios. This thesis has been successful in narrowing research-gaps on problems related to contaminated sites management. / Diese Doktorarbeit befasste sich mit Methoden, welche für eine Vorabbewertung von kontaminierten Standorten genutzt werden können. Die Ziele der Arbeit basierten auf dem einfachen Fakt, dass jeder kontaminierte Standort ein bestimmtes Potential besitzt, natürliche Ressourcen, speziell Grundwasser- und Bodenressourcen, in ihrer Qualität negativ zu beeinträchtigen. Die Arbeit war auf die Nutzung mathematischer und statistischer Techniken zur Abschätzung der maximalen Schadstofffahnenlänge, auch Lmax, fokussiert, welche als entscheidender Parameter für die Standortbewertung genutzt werden kann. Der erste Teil der Doktorarbeit beinhaltete die Zusammenstellung und Analyse von Daten einer Vielzahl von KORA-Standorten. Anhand dieser Untersuchungen konnte festgestellt werden, dass Lmax von BTEX-Fahnen im Mittel unterhalb von 150 m liegt. Des Weiteren wurden für diese Arbeit analytische Modelle, welche für die Abschätzung von Lmax genutzt werden können, kritisch bewertet und vergleichende Beispiele zwischen mit Modellierung bestimmter und im Feld ermittelter Lmax präsentiert. Der zweite Teil der Doktorarbeit zielte auf die Entwicklung und Analyse eines neuen dreidimensionalen, analytischen Models für eine finite, planare und über die komplette Mächtigkeit vorherrschende Quelle ab. Es konnte ein impliziter mathematischer Ausdruck zur Vorhersage von Lmax gewonnen werden. Die Analyse des Models wies darauf hin, dass maximale Lmax erreicht werden, wenn die Quelle eine annähernd quadratische Form aufweist. Der letzte Teil der Doktorarbeit diente der Weiterentwicklung des dreidimensionalen, analytischen Modells aus dem zweiten Teil durch die Entwicklung eines Ausdrucks für eine finite, planare Quelle, welche jedoch nur teilweise die Mächtigkeit des Grundwasserleiters kontaminiert. Für diese Arbeit wurde ein sehr einfacher numerischer Ansatz entwickelt, welcher die numerische Analyse der in dieser Arbeit berücksichtigten Szenarien nicht einfach nur erleichtert, sondern auch das Potential beinhaltet diesen auf komplexe, reaktive Transportszenarien im Untergrund anzuwenden. Abschließend kann gesagt werden, dass diese Arbeit erfolgreich zur Verringerung von Forschungslücken in der Problematik des Managements kontaminierter Standorte beigetragen hat.

Extraction processes employing emulsion liquid membranes (ELMs), water-in-oil emulsions dispersed in aqueous phase, have been shown to be highly efficient in removing a variety of organic and inorganic contaminants from industrial wastewaters. As a result, they have been considered as alternative technologies to other more common separation processes such as pressure-driven membrane processes. Unfortunately, a widespread use of the ELM process has been limited due to the instability of emulsion globules against fluid shear. Breakup of emulsions and subsequent release of the internal receptor phase to the external donor phase would nullify the extraction process. Numerous studies have been, therefore, made in the past to enhance the stability of ELMs. Examples include adding more surfactants into the membrane phase and increasing the membrane viscosity. However, increased stability has been unfortunately accompanied by loss in extraction efficiency and rate in most reported attempts. The primary objective of this research is to apply the ELMs in a unique contacting device, a Taylor-Couette column, which provides a relatively low and uniform fluid shear that helps maintaining the stability of emulsion without compromising the extraction efficiency of a target compound. The ELM used in this study is made of membrane phase converted into non-Newtonian fluid by polymer addition, which provides additional uncommon remedy for the problem. This innovative ELM process was optimized to treat various types of simulated industrial wastewaters containing selected phenolic compounds and heavy metals. Experiments performed in this study suggested that the newly developed ELM process achieved exceptionally high overall removal efficiencies for the removal of these target compounds in relatively short contact time. Mechanistic predictive models were further developed and verified with the experimental data. Combined with the experimental data and novel mathematical predictive models, this study is expected to have a high impact on immediate practices of emulsion liquid membrane technologies in relevant industries.

This study investigated the spatial distribution and seasonal variation of pharmaceuticals and personal care products (PPCPs) and illicit drugs in western Hengchun peninsula and Kenting coastal tourist area in Taiwan. We used solid phase extraction (SPE) followed by liquid-chromatography tandem mass spectrometry (HPLC-MS/MS) to determine 22 PPCPs and 10 illicit drugs in water samples. The detected concentrations of PPCPs and illicit drugs ranged from below detection limit to 9350 ng/L, and the most frequently five detected compounds in this area were ampicillin (79%), codeine (63%), caffeine (62%), carbamazepine (61%) and pseudoephedrine (57%). The impact of the special event- Kenting music festival, such as ¡§spring scream¡¨ was also discussed in this study, and the results from PCA and HCA both showed that the concentrations and distributions of PPCPs and illicit drugs were affected by the tourists. In addition, two wastewater treatments plants (WWTPs) were also investigated for seven days during Kenting music festival period. The results indicated that WWTPs did not show enough removal efficiencies in Kenting tourist area during the special event. The impact of the PPCPs and illicit drugs to the aquatic environment and ecology still needs to be further monitored.

The Formosa Petrochemical Corporation (FPCC) has operated the No. 6 Naphtha Cracking industry site at Mailiao of Yunlin County for 14 years since it completed the construction in 1995. Although the plant were assessed according to the process of environmental impact assessment as required by government¡¦s guidelines before the approval of FPCC establishment at the site, there is a need to re-evaluate the site strictly for problems resulting from the industry activities over the year. The present study is initiated to research and assess the environmental monitoring data collected over the years to determine the spatial and temporal trend of heavy metal contaminants associated with the FPCC operation at site and its coastal areas. The data information used in this study consist of government annual survey reports with regard to the oceanography data of the site, seawater, sediment, and air quality. The FPCC¡¦s monitoring data are also evaluated for including in the environmental quality assessment of Mailiao coastal areas. The present study employed the annual total contaminant discharges reported by the FPCC for obtaining the total burden emitted into the nearby counties Taihsi and Lunbei. The results showed that the coastal marine environment around the industrial site and the Jhuoshuei River have major immediate impacts and problems from the activities. The results of sediment metal content have substantial increase over the years, although the value of metal concentrations is proclaimed that it is within the government provisional guidelines of sediment contaminant standard. In the current circumstance, there are no standard criteria for sediment metal concentration in the marine environment reported elsewhere in the world with exception of Canada. The air quality results showed that Lunbei which is located east side of FPCC site have a decreasing trend of contaminant discharge compared with Taihsi which is located at southern side of FPCC site have a increasing trend of contaminant discharge. Nevertheless, the FPCC site have an increasing total annual discharge. The present study also conducts a survey at Mailiao and Taihsi residences on the social-economic development and the influence associated with the FPCC operation. The survey consists of all stakeholders such as government municipality official, marine aquaculture farmers, non-government organization and fishery cooperation representatives. They are concern the influence on the social-economic development and environment impact from the industry operation. These include the problems of low spat rating in oyster farming and dust falling into the marine farm site to cause the death of bivalves. The health of local residences from FPCC site is of concern due to the expansion program of plan to the site. The present work shows the change and alteration of marine environment resulting from the FPCC activities that have worsened the sustainability development of coastal area.

This study considers airflow simulations to evaluate the impact of different window air-conditioner locations on the thermal comfort in an office room (OR). This thesis compares the air distribution for an office room by using computational fluid dynamics (CFD) modeling to previously studied rooms. The air distribution was modeled on a typical office room window air conditioning unit, air supply from a high pressure on the top and the low pressure exhaust on the bottom considering the existing manufacturing ratios for surface areas. The discharge angle for the supply grill of the AC unit was varied from 20 to 40 degrees. The position of the air conditioner was also varied and studied at 60%, 75% and 90% of the total height of the room. In addition, the location of the occupant within the office room was varied, two locations were studied, one where the occupant is far from the unit and the other to closer to the AC unit at the middle of the room. Predictions of the air movement, room temperature, room relative humidity, comfort level, and distribution of contaminants within the office room are shown. Analysis of these simulations is discussed. Energy estimations are also performed and evaluated. The positions of the air-conditioner unit, the inlet angle and the occupant position in the office room have shown to have an important impact on supply controlling air quality and thermal comfort. Results are in good agreements with the experimental data.The primary function of a HVAC (heating refrigerating and air conditioning) system is the generation and maintenance of comfort for occupants in a conditioned space [1]. This work also provides a detailed analysis of three-dimensional mixed convective flow induced by a window air conditioning system. Using a three dimensional CFD simulation, several characteristics of human comfort are analyzed.

Photocatalysis is a promising technique for the remediation of indoor air pollution. Photocatalysis utilizes semiconductor photocatalysts (such as TiO2 or ZnO) and appropriate light to produce strong oxidizing agents (OH*) that are able to break down organic compounds and inactivate bacteria and viruses. The overall goal of the research is to develop an efficient photocatalytic reactor based on mass transfer for indoor air purification. This study has focused on the enhancement of the effectiveness of the photocatalytic process by the introduction of artificial roughness on the reactor catalyst surface. The major effect of artificial roughness elements on the catalytic surface is to create local wall turbulence and enhance the convective mass transfer of the contaminants to the catalyst surface and thus lead to an increase in the effectiveness of photocatalysis. Air flow properties in a model photoreactor channel with various roughness patterns on the interior wall surface were theoretically investigated. The optimum shapes, sizes, and arrangements of roughness were determined for the maximum enhancement of turbulence intensity in the channel. The possible order of photocatalytic reactor performance for various roughness patterns was also determined. In order to verify the theoretical analysis results, experimental studies were carried out. A plate type photocatalytic reactor was designed and fabricated on the basis of the theoretical results. It was determined that the photocatalytic reactor performance is greatly improved with various rough catalyst surfaces. The experimental results verified the theoretical results. The relationship between the overall reaction rate constant (k) of the reactor and the magnitude of the turbulence intensity was found out. An empirical correlation expression was also proposed. This is the first study of the effect mass transfer in a rough catalytic surface for photocatalytic reactor. Photocatalyst development has also been studied. Zinc oxide (ZnO) and iron doped zinc oxide (ZnO/Fe) nanowires were synthesized on glass substrates through a conventional hydrothermal method. The photocatalytic activities under ultraviolet (UV) light and white light irradiation were separately investigated. The ZnO/Fe nanowires exhibited an enhanced photocatalytic activity as compared to ZnO nanowires regardless of the type of contaminants and light sources.

This dissertation is composed of three parts of major contributions. In Chapter II, we discuss analytical study of contaminant transport from a finite source in a finite-thickness aquifer. This chapter provides analytical solutions of contaminant transport from one-, two-, and three-dimensional finite sources in a finite-thickness aquifer using Green's function method. A library of unpublished analytical solutions with different finite source geometry is provided. A graphically integrated software CTINT is developed to calculate the temporal integrations in the analytical solutions and obtain the final solutions of concentration. In Chapter III, we obtained solutions of groundwater flow to a finite-diameter horizontal well including wellbore storage and skin effect in a three-dimensionally anisotropic leaky aquifer. These solutions improve previous line source solutions by considering realistic well geometry and offer better description of drawdown near the horizontal well. These solutions are derived on the basis of the separation of the source and the geometric functions. The graphically integrated computer program FINHOW is written to generate type curves of groundwater flow to a finite-diameter horizontal well. The influence of the finite-diameter of the well, the wellbore storage, the skin effect, the leakage parameter, and the aquifer anisotropy is thoroughly analyzed. In Chapter IV, a general theory of groundwater flow to a fractured or non-fractured aquifer considering wellbore storage and skin effect is provided. Solutions for both leaky confined and water table aquifers are provided. The fracture model used in this study is the standard double-porosity model. The storage of the aquitard (the leaky confining layer) is included in the formula. A program denoted FINHOW2 is written to facilitate the calculation. Sensitivity of the solution to the confined versus unconfined conditions, fractured versus non-fractured conditions, and wellbore storage and skin effects is analyzed.

Degassing and in situ formation of a mobile gas phase takes place when an aqueous phase equilibrated with a gas at a pressure higher than the subsurface pressure is injected in water-saturated porous media. This process, which has been termed supersaturated water injection (SWI), is a novel and hitherto unexplored means of introducing a gas phase into the subsurface. Herein is a first macroscopic account of the SWI process on the basis of continuum scale simulations and column experiments with CO2 as the dissolved gas. A published empirical mass transfer correlation (Nambi and Powers, Water Resour Res, 2003) is found to adequately describe the non-equilibrium transfer of CO2 between the aqueous and gas phases. Remarkably, the dynamics of gas-water two-phase flow, observed in a series of SWI experiments in homogeneous columns packed with silica sand or glass beads, are accurately predicted by traditional two-phase flow theory which allows the corresponding gas phase relative permeability to be determined. A key consequence of the finding, that the displacement of the aqueous phase by gas is compact at the macroscopic scale, is consistent with pore scale simulations of repeated mobilization, fragmentation and coalescence of large gas clusters (i.e., large ganglion dynamics) driven entirely by mass transfer. The significance of this finding for the efficient delivery of a gas phase below the water table in relation to the alternative process of in-situ air sparging and the potential advantages of SWI are discussed. SWI has been shown to mobilize a previously immobile oil phase in the subsurface of 3-phase systems (oil, water and gas). A macroscopic account of the SWI process is given on the basis of continuum-scale simulations and column experiments using CO2 as the dissolved gas and kerosene as the trapped oil phase. Experimental observations show that the presence of oil ganglia in the subsurface alters gas phase mobility from 2-phase predictions. A corresponding 3-phase gas relative permeability function is determined, whereas a published 3-phase relative permeability correlation (Stone, Journal of Cana Petro Tech, 1973) is found to be inadequate for describing oil phase flow during SWI. A function to predict oil phase relative permeability is developed for use during SWI at high aqueous phase saturations with a disconnected oil phase and quasi-disconnected gas phase. Remarkably, the dynamics of gas-water-oil 3-phase flow, observed in a series of SWI experiments in homogeneous columns packed with silica sand or glass beads, are accurately predicted by traditional continuum-scale flow theory. The developed relative permeability function is compared to Stone’s Method and shown to approximate it in all regions while accurately describing oil flow during SWI. A published validation of Stone’s Method (Fayers and Matthews, Soc of Petro Eng Journal, 1984) is cited to validate this approximation of Stone’s Method.

Endocrine disruption and high occurrences of intersex have been observed in wild fish associated with wastewater treatment plant (WWTP) effluents in the urbanized reaches of the Grand River watershed located in southern Ontario, Canada. WWTP effluent is a complex matrix with diverse aquatic environmental contaminants and stressors. This study aimed to: (1) characterize the spatio-temporal distribution and fate of antiandrogenic personal care products (triclosan, chlorophene, and dichlorophene), along with selected pharmaceuticals (carbamazepine, ibuprofen, naproxen, and venlafaxine) and the herbicide, atrazine in the Grand River watershed and (2) model the behaviour of these contaminants in the aquatic environment. Water sampling of 29 sites which covered six municipal WWTPs and ~100 km of river length was completed during summer low flows (July 2012). Monthly samples were also collected immediately upstream and downstream of a major WWTP (Kitchener) from August to November 2012. Many of the target pharmaceuticals and triclosan were detected in WWTP effluents in the Grand River watershed, especially those that did not nitrify (minimal treatment with high ammonia). Chlorophene was either undetected or was only found at trace levels in the effluents. Under low flow conditions, triclosan and several other pharmaceuticals exhibited a spatial pattern where concentrations increased directly downstream of the WWTPs, then decreased with distance downstream (dilution and/or degradation). Chlorophene, in contrast, was not found downstream of most of the WWTP outfalls but was first detected at a site 5 km upstream of a WWTP and then continued with relatively constant concentrations for approximately 29 km downstream. It was also only found during the summer sampling period. Atrazine was consistently found in all sampling locations which reflected the agricultural non-point source nature of this compound. The WASP 7.5 model (US Environmental Protection Agency) was adapted and calibrated to a reach of the Grand River associated with the Kitchener WWTP. The simulation of the fate and transport of the target compounds revealed that flow-driven transport processes (advection and dispersion) greatly influence their behaviour in the aquatic environment. However, fate mechanisms such as biodegradation and photolysis also potentially play an important role in the attenuation of most compounds. The exception was carbamazepine where it was shown to act as a conservative tracer compound for wastewater specific contaminants in the water phase. The fate model developed can be applied in the future to predict the fate of a wide variety of contaminants of emerging concern across the watershed to help define the exposure of these biologically active chemicals to sensitive ecosystems.