Two adsorption/microcoulometric methods have been investigated for total organic halogen (TOX) in water. TOX, a proposed water-quality parameter, is a rapid, surrogate method to detect halides microcoulometrically and does not require compound identification before water quality can be judged. An XAD resin is used to concentrate organic halides that are eluted by a two-step, two-solvent procedure, followed by analysis using :chromatography or pyrolysis to convert organic halides to halide. In the granular activated carbon (GAC) method, the entire GAC-organic halide sample is pyrolyzed. TOX measurements of model compounds are comparable by both methods, but GAC was found to be superior to XAD for adsorption of chlorinated humics in drinking water and chlorinated lake water.

This thesis work aims to develop electrochemical sensors for sub-ppb level detection of inorganic and organic pollutants in drinking water with environmentally benign materials and processes. While traditional laboratory-based methods such as mass spectroscopy, and chromatography have been used to analyze the concentration of contaminants in drinking water, miniaturized electrochemical sensors offer a compelling alternative to those methods, enabling rapid on-site cost-effective detection of low concentrations of pollutants. In this research, a set of three-electrode sensors was designed and fabricated on a flexible substrate using a screen-printing technique. Additionally, an in-situ electrochlorination process was implemented to create the reference electrode. These sensors were utilized to precisely detect lead ions and perfluorooctane sulfonate (PFOS) in drinking water. The first set of sensors was fabricated to measure the concentration of lead ions, a toxic inorganic pollutant, in potable water. The novelty of the proposed research lies in using non-toxic, biodegradable sodium alginate grafted with 2- acrylamido-2-methyl propane sulfonic acid (AMPS) and conductive fillers for trace-level lead ion detection in water. The principle of square wave anodic square wave stripping voltammetry (SWASV) was used to determine the trace level lead ion concentration. Employing a similar approach with a different material, a PFOS sensor was developed. Utilizing chitosan, one of the sustainable and biodegradable biopolymers found in crustacean shells, rapid parts-per-trillion (ppt) level PFOS detection by electrochemical impedance spectroscopy (EIS) was demonstrated. The proposed sensors made low-cost electrochemical detection of contaminants such as lead ions and PFOS possible with eco-friendly materials and processes.

In an electrochemical sensor, the sensing performance is mainly dependent on the mass transport of the analyte towards the working electrode-electrolyte interface and working electrode properties. Carbon nanomaterials like carbon nanotubes are widely employed to modify the working electrode properties for sensitive detection. A simulation model is formulated to investigate the effects of modifying a planar bare electrode with carbon nanotubes on electrochemical detection of fenitrothion (FT, an organophosphate). The model revealed that porous electrodes caused the change in mass transport regime and influenced FT’s electrochemical response. The results aided in understanding the influence of the porous electrode on analyte detection and thus assisted in the fabrication of an ultrasensitive electrochemical sensor. Simulation supported synthesis of a highly sensitive ink to produce highly porous and electrocatalytic electrodes. Activated carbon (AC) possesses high porosity and surface area, but they suffer from lower electrical conductivity. To enhance their conductivity, AC was co-doped with nitrogen and sulfur. Multiwalled carbon nanotubes were incorporated to further improve their porosity and electrocatalytic properties. The synthesized nitrogen-sulfur co-doped activated carbon coated multiwalled carbon nanotube (NS-AC-MWCNT) ink produced highly porous electrocatalytic electrodes. The sensor revealed a 4.9 nM limit of detection (LOD) under optimized conditions. However, it failed to overcome the enzymatic sensors’ performances. The ultrasensitive performance was achieved by incorporating a detecting agent in the ink that instilled analyte capture ability. Metal oxides like ZrO2, MnO2, and MgO possessed affinity towards organophosphate (fenitrothion), heavy-metal ion (lead), and nutrient (nitrite). Metal oxides were modified with 3,4-dihydroxylbenzaldehyde (DHBA) – Chitosan (CHIT) to produce well dispersed and uniformly coated stable electrodes. The ZrO2-DHBA-CHIT/NS-AC-MWCNT sensor achieved a remarkable limit of detection of 1.69 nM for FT. The sensor's performance exceeded the enzymatic-based sensors. The commonly found chemical interferents had negligible interference. The sensor produced reliable and satisfactory performance in lake and tap water. The MnO2-DHBA-CHIT/NS-AC-MWCNT/GCE and MgO-DHBA-CHIT/NS-AC-MWCNT/GCE sensors produced an enormous improvement in the sensor performance compared to unmodified electrodes for lead and nitrite detection. The preliminary results on detecting other pollutants like lead and nitrite showed the importance of the methodology in providing a platform for a new class of metal oxide-based sensors. / Thesis / Doctor of Philosophy (PhD) / The growing population and rapid industrial development are affecting the water quality worldwide. The major water pollutants are organophosphates, heavy metal ions, and nutrients. These water pollutants are harmful, and their bioaccumulation poses a major health concern. In the USA alone, water quality issues are predicted to cost $210 billion annually. Therefore, sensors to detect water pollutants are developed to monitor their environmental footprints. Electrochemical sensors are popularly used to detect water pollutants owing to their low-cost and high sensitivity. The objective of this dissertation was to fabricate highly sensitive and specific electrochemical sensors to detect organophosphate (e.g., fenitrothion, FT), heavy metal ion (e.g., lead), and nutrient (e.g., nitrite). The sensors were fabricated with ink based on nanomaterials like carbon nanotubes and detecting agents like metal oxides. The fabricated sensors achieved very high sensitivity and specificity and can detect water pollutants in lake and tap water.

The objectives of this study were to determine: (1) whether or not heterotrophic microorganisms exert an effect on the trihalomethane (THM) or total organic halogen (TOX) formation potentials of algal extracellular products (ECP), and (2) whether or not diurnal cycling of THM and TOX precursors occurs in vitro. These objectives were addressed through culture studies of heterotrophic microorganisms and pure algae from both the green and blue-green divisions. Culture conditions were varied to study different aspects of algal and bacterial interactions. Results from continuous light assays indicated that heterotrophs, grown in the same culture vessel with algae, affected an increase in the potential of chlorinated culture filtrate to form THMs. No significant changes in TOX-formation potential were observed. Heterotrophs grown in volumes of algal ECP (cell-free filtrates of algal cultures) used the algal-produced organic carbon as their sole carbon source. These microorganisms further reduced both the dissolved organic carbon (DOC) concentration and the concentration of the DOC fraction that reacted to form TOXs. The fraction which produced THMs was not reduced. Heterotrophic microorganism metabolic activity increased the rate at which THMs fanned from chlorinated algal ECP but did not alter the seven-day THM-formation potentials. Their activity also increased the initial rate of TOX formation, but decreased the seven-day formation potential of these compounds. Attempts to demonstrate diurnal cycling of the concentration of THM precursors and other halogenated organic precursors, a phenomenon previously demonstrated in a eutrophic reservoir, were unsuccessful. / M.S.

The molecular size, charge, and solubility, distributions of natural DOC in raw and treated surface waters were investigated to determine the types of organic compounds removed by coagulation and settling. The distribution of organic precursors that react with chlorine to form organic halide compounds was also determined, along with the reaction rates. DOC removal by coagulation was size dependent. Compounds over 5,000 d were readily removed while compounds under 1,000 d were largely unaffected. Acidic and basic molecules were precipitated much more effectively than neutral ones. Both hydrophilic and hydrophobic molecules were selectively removed compared to compounds of intermediate solubility. Two groups of organic halide precursors were identified. Fulvic acids had high specific organic halide yields, and fast reaction rates with chlorine, but could be effectively removed by coagulation. Nonpolar neutral compounds were lower in molecular weight, slower to react with chlorine, and produced less organic halide, but could not be precipitated by coagulation. / Ph. D. / incomplete_metadata

The Arctic has long been considered to be a pristine environment, far from population centers and pollution sources. The detection of synthetic organochlorine compounds in various elements of the Arctic food web has confirmed the global dispersion of pollutants, particularly of persistent compounds such as organochlorines and heavy metals. Levels of heavy metals, although elevated, appear to be naturally so throughout much of the Arctic. Arctic pollution is both a humanitarian and ecological concern. Many arctic coastal communities depend heavily on marine mammal fat for sustenance, and are therefore potentially exposed to high levels of organochlorines and some metals. From an ecological perspective, the structure of arctic food webs, the importance of lipid mobilization for winter survival, and the adaptive physiologies of arctic organisms may result in an enhanced response to contaminant exposure. This thesis assesses the exposure and effect of organochlorine and heavy metal exposure in inland freshwater ecosystems of Arctic Alaska, and evaluates the physiological response of arctic grayling to experimental polychlorinated biphenyl (PCB) exposure. / Graduation date: 1995

Mémoire (M.P.Aquat.)--Université du Québec à Chicoutimi, 1990. / Document électronique également accessible en format PDF. CaQCU

Thesis (M.S.)--Oregon State University, 2011. / Printout. Includes bibliographical references (leaves 69-74). Also available on the World Wide Web.

M.Sc. / The contamination of water by toxic compounds is one of the most serious environmental problems today. These toxic compounds mostly originate from industrial effluents, agriculture runoff, natural sources (e.g. heavy metals in water from rocks and soil erosion) and human waste. The contamination, which is both “organic” and “inorganic” has an impact on the environment and human health. The demand for water and the pressure to re-use this valuable resource has increased the need for improved techniques and materials to remove pollutants from water. The Nanomaterials Science research group at the University of Johannesburg has focused on developing synthetic polymers that can be employed in water treatment and pollutant monitoring. Recently, cyclodextrins (CD) and carbon nanotubes (CNTs) have been included in polymers for this application. For example, CD-co-hexamethylene-/toluene-diisocyanate polyurethanes and CNT-modified equivalents have been developed and have been successfully applied in removing organic contaminants from water to very low levels.1 Calixarenes are synthetic analogues of cyclodextrins that can be exploited via chemical modification to express a range of properties. In the present study, calixarenes, thiacalixarenes and carbon nanotube-based polymeric materials incorporating these molecules have been synthesised, characterised and tested for removing both organic pollutants (such as p-nitrophenol) and inorganic pollutants (Cd2+, Pb2+) from water. Lead(II) and Cadmium(II) are a threat in South Africa because of their toxicity, and while p-nitrophenol is much less of a problem it represents a useful model organic pollutant. The absorption capacity of the polymers towards heavy metals and organic contaminants was tested by mixing the polymer with synthetic water containing known concentration of the contaminants at about 10 mg/L. Atomic absorption spectrometry (AAS) and ultraviolet-visible spectrometry (UV-vis) were used to determine the levels of heavy metals and organic contaminants, respectively. The target pollutants (Cd2+, 1 see KL Salipira MTech dissertation, University of Johannesburg 2008 Pb2+ and p-nitrophenol) were all successfully removed from water by the various polymers, however the degree of removal and loading capacities of the polymers differed. This information gives some insight into what functional components are needed for making successful adsorbents. It was observed, for example, that ptert- butylcalix[8]arene/hexamethylene diisocyanate (C8A/HMDI) had a higher adsorption capacity towards p-nitrophenol and Pb2+ than towards Cd2+, and also a higher capacity than the corresponding calix[4]arene polymers with smaller calixarene cavities.

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