In some environmental situations, environmental effects caused by elevated metals resulting from past mining and smelting activities can be observed in nearby receiving water bodies several decades after mine and smelter closure. There is a growing need for managing the hazardous solid wastes such as mining wastes as well as for assessing water quality and for sustainable management of sediment quality. The work presented in this thesis examined the mobilization of metals from two metal sources: mining wastes from a mine site in Vietnam and sediments from a contaminated lake in Sweden in order to test the hypothesis that mobilization of metals will be increased, when the environmental conditions change by e.g. exposure of mining wastes to oxidative weathering, change of redox conditions at the water-sediment interface and resuspension of sediments. The results from this work under field and laboratory conditions have verified the hypothesis. The exposure of sulphidic mining wastes in oxidative weathering conditions may cause long-term production of ARD and the resultant long-term mobility of metals. The oxidation/resuspension of sediments is an important factor for the release of trace metals Zn, Cu and Cd into the solution and substantial amounts of particles and, hence, associated metals into overlying water. The concomitant changes in pH during oxidation/resuspension of sediment play a significant role in the metal release both to redox sensitive elements Fe and Mn and trace elements Zn, Cu and Cd. The concomitant change in DOC during oxidation/resuspension can also contribute to the increased mobility of study metals. The field study was coupled to intermittent operation of a hydropower plant. The mobility of the metals was higher under operation compared to non-operation and, thus, the potential impacts on dispersal of metal pollution to downstream aquatic environments. The sudden increase in water flow upon the hydropower plant upon shifts from inactive to active state could cause immediate release of particles and thus particulate metals in the overlying water. However, the magnitude and its integrated effects in fluxes of metals over the season call for further research. There is a need to further investigate the impacts of hydropower generation in a longer period of time and at a higher frequency of observations at the very start of the hydropower operation. The results from this multidisciplinary approach would give a basis for an optimal operation of the hydropower plant to minimize the metal pollution associated with the water flow. / <p>The series number is changed from 410 to 430 and the ISBN is changed from 978-91-85895-56-4 to 978-91-7393-926-3.</p>

Arsenic contamination in drinking water is a severe problem worldwide. The best way to prevent hazardous diseases from chronic arsenic exposure is to remove the exposure. Efforts to remediate arsenic in drinking water have taken two tracks. One is to provide surface or shallow well water sources as an alternative to the arsenic contaminated deep wells. Another approach is to remove arsenic from the contaminated water. Different removal technologies like oxidation, chemical coagulation, precipitation, adsorption and others are available. There are problems and benefits associated with each of these approaches that can be related to cultural, socio-economic and engineering influences. The method proposed in this research is adsorption of arsenic to iron coated limestone. Different iron coated limestone samples were prepared. Standard solutions of 100ppb arsenic were prepared and batch and kinetic experiments were conducted. The final solution concentrations were analyzed by Graphite Furnace Atomic Adsorption Spectroscopy (GFAAs) and the results showed that iron coated limestone removed arsenic below 10ppb with 5 grams of material. Variations in iron coverage impacted efficiency of arsenic removal.

Antibiotics are added to animal feeds as prophylactic agents and to encourage weight gain in livestock. However, there is concern that the widespread use of antibiotics in animal agriculture encourages for the selection of resistance genes and has contributed to the rise of multiply antibiotic resistant strains of pathogenic bacteria. For this reason, there is interest in quantifying antibiotics in environmental samples. The determination of three antibiotics in swine waste, namely chlortetracycline, tetracycline and oxytetracycline, using LC-MS with electrospray ionization is presented here in. Antibiotics from swine waste were quantified across the lifespan of the swine. Trends were present in each of the four life stages (gestation, farrowing, nursery, and finishing). The nursery stage of life presented the most dominate concentrations and the most consistent trend in antibiotic concentrations.

Human exposure to harmful compounds in the environment, from intake via food, occupational exposures or other sources, could have health implications. Exposure to reactive compounds/metabolites can be identified and quantified as hemoglobin (Hb) adducts by mass spectrometry. This thesis aimed at improved synthetic pathways for reference standards, and improved analytical methods for adducts to N-terminal valine in Hb from a range of reactive compounds; isocyanates, aldehydes, methyl vinyl ketone (MVK), and diepoxybutane (DEB). Isocyanates form urea adducts with N-terminal valine by carbamoylation, which are detachable as hydantoins by hydrolysis. A new synthetic pathway for reference standards of adducts from isocyanates and a method for their analysis by liquid chromatography/mass spectrometry (LC/MS) were developed. Aldehydes form reversible imines (Schiff bases) with N-termini in Hb. After stabilisation by reduction and detachment by isothiocyanates using modified Edman methods, these adducts could be analysed by gas chromatography/mass spectrometry (GC/MS) or LC/MS. 5-Hydroxymethylfurfural, its metabolites, and other aldehydes related to exposure via food, were studied with regard to analysis by these methods with synthesised standard references. A considerably improved analytical method for imines was developed. Many of the studied adducts are too short-lived in vivo or in vitro to be used for long-term biomonitoring. However, different approaches for the analysis were evaluated. Through synthesised reference standards, an observed unknown adduct in blood was verified as the adduct from MVK. There exist both natural and anthropogenic sources for MVK. DEB, metabolite of butadiene, forms a cyclic adduct to valine-N. A new approach using hydrazinolysis of protein and enrichment by molecularly imprinted solid-phase extraction was tested on synthesised reference DEB-adduct and gave promising results. Synthesised standards were characterized by NMR, LC/MS and GC/MS. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 1: Submitted. Paper 3: Submitted. Paper 4: Submitted.</p>

Fluorinated chemicals have the advantage of both lipophobic and hydrophobic behaviour, leading to broad industrial and commercial use. Fluorosurfactants, for example, are used in applications, such as grease-proofing food packaging, which result in human exposure. Human blood serum, in this work 100 German serum samples dating from 1982 to 2009, is a common matrix for detection of fluorochemicals. Here the most extensive temporal study to date of one class of fluorosurfactant (polyfluoroalkyl phosphate diesters, diPAPs) in human serum is presented. Additionally, another class of fluorosurfactant (sulfonamide-based PAPs, SAmPAPs) was detected in humans for the first time with temporal trends which echo industrial production. Metabolites of diPAPs and SAmPAPs were also quantified, showing temporal trends that relate to the diPAP and SAmPAP levels. Because diPAP and SAmPAP metabolites are environmentally persistent and raise human health concerns, it is important to understand these indirect sources of exposure.

Fluorinated chemicals have the advantage of both lipophobic and hydrophobic behaviour, leading to broad industrial and commercial use. Fluorosurfactants, for example, are used in applications, such as grease-proofing food packaging, which result in human exposure. Human blood serum, in this work 100 German serum samples dating from 1982 to 2009, is a common matrix for detection of fluorochemicals. Here the most extensive temporal study to date of one class of fluorosurfactant (polyfluoroalkyl phosphate diesters, diPAPs) in human serum is presented. Additionally, another class of fluorosurfactant (sulfonamide-based PAPs, SAmPAPs) was detected in humans for the first time with temporal trends which echo industrial production. Metabolites of diPAPs and SAmPAPs were also quantified, showing temporal trends that relate to the diPAP and SAmPAP levels. Because diPAP and SAmPAP metabolites are environmentally persistent and raise human health concerns, it is important to understand these indirect sources of exposure.

Chlorinated paraffins (CPs) are ubiquitous environmental contaminants. They fulfill all of the criteria (persistent, toxic, and subject to long-range transport) for persistent organic pollutants (POPs) according to the United Nations Economic Commission for Europe (UNECE). CPs are also under consideration for inclusion in the Stockholm Convention on POPs. Their presence has been shown in various environmental matrices in the industrialized parts of the world, as well as in remote regions such as the Arctic. The aim of this thesis was to increase the limited knowledge of the presence of CPs in the environment, their sources to the environment, and the resulting human exposure. An analytical procedure for the determination of CPs in environmental samples based on gas chromatography coupled to electron capture detection (GC-ECD) has been developed. GC-ECD is a relatively inexpensive instrument that is fast and easy to operate. These advantages open up the possibility for a comprehensive screening of the occurrence of CPs in the environment, including developing countries. Furthermore, the occurrence of CPs in ambient air and in indoor air and dust was studied. Elevated CP concentrations in indoor air (&lt;5-210 ng/m3) were observed compared to ambient air (0.7-33 ng/m3), which is indicative of the presence of indoor emission sources. Indoor air and dust concentrations were used to estimate the human exposure to CPs via the indoor environment. Comparison of the estimates to available dietary intake estimates indicated that the indoor exposure pathways are not negligible. CP concentrations in ambient air from urban Stockholm were higher than in rural Aspvreten, Sweden. This indicates the presence of additional (emission) sources in urban areas compared to rural sites. Additionally, a seasonal variation of air concentrations was observed at both locations, suggesting temperature dependent emission sources for CPs. These observations were supported by a substance flow analysis of CPs performed for Stockholm. This study estimated the major emission sources of CPs to the Stockholm environment to be emissions from painted surfaces and in-place sealants. / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 3: Manuscript. Paper 4: Manuscript.

The ever-increasing detection of harmful organic and inorganic compounds in habitable areas throughout the world has led to mounting research into applications and techniques for the treatment of contaminated soils, surface and groundwaters, and chemical and industrial wastewaters. Chemical oxidation technologies, in particular Fenton-based remediation systems, have exhibited considerable potential for the effective treatment and remediation of such contaminated waters and soils. The use of Fenton-based oxidation systems for the treatment of contaminated waters and wastewaters warrants the development of kinetic models capable of accurately simulating system behaviour. In this thesis, the kinetics of Fenton-mediated oxidation systems and kinetic models based on its governing reaction mechanism are investigated in order to highlight those parameters and conditions that effect Fenton chemistry and oxidation performance, and to demonstrate the application of such kinetic models to design and improve treatment systems. Experimental and simulated data describing the oxidation of formic acid by Fenton's reagent at low pH (3 to 4) and under a variety of initial conditions, operating regimes, and solution environments supports a proposed reaction mechanism that nominates the hydroxyl radical (OH) as the active oxidizing intermediate in Fenton-based oxidation systems. Laboratory experiments demonstrate that formic acid oxidation is inhibited in the presence of oxygen, and model simulations of these systems reveals that such behaviour is due to the effect organic radical intermediates and/or by-products have in assisting or hindering the redox cycling of the catalytic iron species. The critical role that iron redox cycling plays in affecting oxidation performance is further highlighted by experimental and simulated studies at alternate pHs and using different target organics, including those that react directly with iron in a redox capacity. Experiments at pH 4 reveal an increase in the redox cycling of iron and improved oxidation performance compared to pH 3 as the higher pH favours the superoxide radical, a stronger reductant than the hydroperoxyl radical that predominates at pH 3. Other laboratory and modelling studies on the Fenton-mediated oxidation of certain aromatic compounds highlight the manner in which quinone and quinone-like compounds, being added directly or generated as oxidation by-products, can improve oxidation performance via redox reactions with iron. Further simulations reveal the type of practical design and operating information kinetic models can provide for treatment processes, though it is noted an appropriate understanding of the oxidation mechanism of the target species is necessary for the accurate application of the model.

Bibliography : leaves i-xxiii. / vi, 95, xxiii, [170] leaves, [4] leaves of plates : ill. (some col.) ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Clinical and Experimental Pharmacology, 1991

Thesis (M.S.)----University of North Carolina Wilmington, 2008. / Title from PDF title page (viewed May 26, 2009) Includes bibliographical references (p. 61)