The disposal of combustible wastes by incineration is a controversial issue that is strongly debated by both scientists and environmental activists due to the resulting emissions of noxious compounds, including (inter alia) polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), heavy metals and acid gases like sulfur dioxide. Currently available air pollution control devices are capable of effectively cleaning flue gases, and PCDD/F emissions to air from modern municipal solid waste (MSW) incinerators are low. However, the PCDD and PCDF end up in ash fractions that, in Sweden, are usually deposited in landfills. The European Union has recently set a maximum permitted total concentration of 15 µg TEQ/kg for PCDD/F species in waste. Fly ash from municipal solid waste (MSW) incineration containing PCDD/Fs at concentrations above this limit will have to be remediated to avoid disposing of them in landfills; an expensive and environmentally unfriendly option. Therefore, effective, reliable and cost-effective methods for degrading PCDD/F in fly ash are required, and a better understanding of the behavior of PCDDs and PCDFs during thermal treatment will be needed to develop them. In the studies this thesis is based upon both the formation and degradation of PCDDs and PCDFs in ashes from MSW incineration were studied. The main findings of the investigations regarding PCCD/F formation were: - The concentrations of PCDD and PCDF in fly ash increased with reductions in the temperature in the post-combustion zone. - The homologue profile in the ash changed when the temperature in the post-combustion zone changed. - The final amounts of PCDD and PCDF present were affected by their rates of both formation and degradation, and the mechanisms involved differ between PCDDs and PCDFs. The main findings from the degradation studies were: - The chemical composition of ash has a major impact on the degradation potential of PCDD and PCDF. - The presence of oxygen during thermal treatment can enhance the degradation of PCDD and PCDF. - Thermal treatment is a viable option for degrading PCDD and PCDF in ashes from MSW. - Shifts in chlorination degree occur during thermal treatment. - Rapid heat transfer into the ash is a key factor for ensuring fast degradation of PCDD and PCDF. - Degradation of other chlorinated organic compounds, e.g. PCB and HCB, also occurs during thermal treatment of ash. - Reductions in levels of PCDD and PCDF were not solely due to their desorption to the gas phase. - Differences between the behavior of 2378-substituted congeners of PCDD and PCDF and the other congeners during thermal treatment were observed. - Differences in isomer patterns of both PCDD and PCDF were observed between the ash and gas phases after thermal treatment at both 300 and 500 oC. Overall, the results show that the formation and degradation mechanisms of PCDDs differ substantially from those of PCDFs. Thus these groups of compounds should be separately considered in attempts to identify ways to reduce their concentrations.

Although wood floor production does not use water in the production process, water consumptionis related to cleaning and washing of floor and machineries in different steps of the process line,which generate a number of small flows that are highly polluted.Besides this, the industry has a need to store large amounts of wood outside to be able to havecontinuity in the production. This takes up a lot of space outdoors and once it rains the water thathas been in contact with wood, oil and metals forms stormwater, which transports pollutants.Stormwater has for a long time not been seen as a problem and has often been discharged intorecipient water bodies without any treatment. During cold seasons, this also involves snowmelt thatcan transport high concentrations of different pollutants.This report describes the composition of process- and stormwater from a wood floor industry inNybro, Sweden regarding parameters such as COD, phenol, tannin and lignin. The concentrationsof phenols in the stormwater were found in a range considered toxic to marine life.Regarding the process water, high values was found for COD (Chemical Oxygen Demand) and forother substances and elements potentially toxic (e.g. formaldehyde, wood resins, detergents andmetals). If these waters are directly released to a sewage treatment plant without any pre-treatmentprocess it can disturb the plant treatment efficiency; if released to a recipient water body, it cancause oxygen deficiency and consequently, death to marine life.The possibility of reducing the levels of pollutants through the use of electrocoagulation has beenexamined in this study. This has been done both for process water and stormwater from the woodfloor industry. A 250 ml batch unit for electrocoagulation EC was setup with iron (Fe) andaluminium (Al) electrodes for treating process water and stormwater. The results show that the ECprocess can reduce COD concentration from stormwater at least 70%. On the other hand, lessefficiency of EC for treating process water was observed.A method for simulating a snowmelt period in lab scale was also developed. Snow collected from awood floor industry was melted according to real temperature and the quality of these samples hasthen been compared to on-site samples of stormwater / Development of an integrated approach for industrial wastewater and stormwater management in the wood-industry sector

There is a growing need to develop rapid and cost-effective ecotoxicological tools for risk assessment because traditional methods examine endpoints such as mortality, which do not provide any insight into the mode of action (MOA) of the chemical. Research presented within this thesis illustrates the potential of 1H NMR-based metabolomics as a rapid and routine ecotoxicological tool that can elucidate a chemical’s MOA and also aid in the identification of metabolites of exposure. Metabolomics involves measuring the fluctuations in the endogenous metabolites of an organism within a cell, tissue, bio-fluid or whole organism in response to an external stressor. We focused on the model polycyclic aromatic hydrocarbon (PAH) phenanthrene, and the perfluoroalkyl acids (PFAAs) perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), due to their recalcitrant nature and widespread prevalence in soil environments. 1H NMR-based metabolomics analysis of the exposure of Eisenia fetida earthworms to sub-lethal phenanthrene exposure via filter paper contact tests revealed a concentration-dependent two-phased MOA: a linear correlation between the metabolic response and exposure concentration at low concentrations followed by a plateau in the responses at high concentrations. Alanine, glutamate, maltose, cholesterol and phosphatidylcholine emerged as potential indicators of phenanthrene exposure. An increased energy demand and an interruption in the conversion of succinate to fumarate in the Krebs cycle were observed due to phenanthrene exposure. Sub-lethal PFOA and PFOS exposure to E. fetida via contact tests for two days revealed heightened responses with higher PFOA and PFOS concentrations. Leucine, arginine, glutamate, maltose, and ATP were identified as potential indicators of PFOA or PFOS exposure. E. fetida responses were then investigated after exposure for two, seven and fourteen days to an artificial soil that was spiked with sub-lethal PFOS concentrations. An exposure time-dependent operation of two separate MOAs were identified. Both the contact tests and artificial soil exposure studies identified an elevation in fatty acid oxidation, a disruption in energy metabolism and biological membrane structure, and also an interruption of ATP synthesis following PFOA and PFOS exposure. This thesis illustrates the promise of NMR-based metabolomics as a routine tool for ecotoxicological assessment of contaminated sites.

Despite its phasing out in numerous countries, such as Germany and the U.S.A., co-disposal of hazardous waste with municipal solid waste continues to be widely practised in South Africa. Co-disposal utilises properties and microbial activities in the refuse to attenuate the hazardous waste and thus obviate its environmental impact potential. All landfill operations require careful planning in not only site selection criteria but also the type and amount of various wastes accepted for disposal. It is clear, however, that the practice of co-disposal requires special precautions and management as the methods employed in the landfill operation determine to a large extent the environmental effects and, thus, the public acceptability of the operations. Although co-disposal is not suitable for all industrial wastes the results of recent research efforts, conducted mainly in the U.K., have indicated that, when properly managed, co-disposal can be regarded as a safe and efficient disposal option for many hazardous wastes. Environmental awareness in many European countries ensures that numerous hazardous compounds are either recycled or recovered. Unfortunately, in South Africa the lack of similar concern has resulted in increased concentrations of toxic compounds being co-disposed on a regular basis. Since fundamental studies of this technology, pertaining to South African conditions, have been lacking laboratory models/microcosms were built to address this paucity. Model. To effect the separation of species habitat domains of component species of growth rate-dependent interacting microbial associations responsible for terminal catabolic processes of the refuse fermentation, with retention of overlapping activity domains, and so facilitate examination of species in isolation without violating the integrity of each association, multi-stage models were constructed. The accidental overgassing of the culture with liquid petroleum gas (LPG) effected interesting fermentation balance changes which also emphasised the need for an Anaerobic Bioassay Test to assess the impacts of specific perturbants. Evidence of differential susceptibility of the component species to phenol was demonstrated in this study. Microcosm. A total of 42 refuse packed single-stage glass column bioreactors were commissioned and subjected to phenol and/or anaerobically digested sewage sludge codisposal. The effects of four different operational modes: leachate discard (single elution); leachate recycle; batch; and simulated rain on the co-disposals as well as refuse catabolism per se were examined. The results of these studies indicated that protracted periods of adaption to phenol (1000 and 2000 mg l -1) could have resulted from nutrient (elemental) limitation. Circumstantial evidence was also gained which indicated that the nitrate- and sulphate-reducing bacteria (SRB) were particularly sensitive to the added xenobiotic. Further, without the effective participation of the nitrate- and SRB the active and total fermentation of both the phenol and refuse components were depressed. It was also determined that the operating regime employed was a key factor in refuse degradation although with time, and especially following the phenol resupplementations, the operating conditions played a less significant role. In general, the single elution operated columns demonstrated increased phenol removal rates which were, unfortunately, coincident with low pH values and increased leachate residual phenol concentrations. Leachate recycle, on the other hand, unlike the batch operated columns, facilitated increased pH values and methane evolutions. The simulated rain columns were characterised by rapid washout of the added phenol as well as methanogenic precursors. The sewage sludge co-disposal experiments, likewise, demonstrated that, depending on the sludge:refuse ratio, the operating regime was extremely important in optimising the refuse degradation processes although, in general, leachate recycle appeared to be the most favoured method of operation. / Thesis (Ph.D.)-University of Natal, Pietermaritzburg, 1996.

There is a growing need to develop rapid and cost-effective ecotoxicological tools for risk assessment because traditional methods examine endpoints such as mortality, which do not provide any insight into the mode of action (MOA) of the chemical. Research presented within this thesis illustrates the potential of 1H NMR-based metabolomics as a rapid and routine ecotoxicological tool that can elucidate a chemical’s MOA and also aid in the identification of metabolites of exposure. Metabolomics involves measuring the fluctuations in the endogenous metabolites of an organism within a cell, tissue, bio-fluid or whole organism in response to an external stressor. We focused on the model polycyclic aromatic hydrocarbon (PAH) phenanthrene, and the perfluoroalkyl acids (PFAAs) perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), due to their recalcitrant nature and widespread prevalence in soil environments. 1H NMR-based metabolomics analysis of the exposure of Eisenia fetida earthworms to sub-lethal phenanthrene exposure via filter paper contact tests revealed a concentration-dependent two-phased MOA: a linear correlation between the metabolic response and exposure concentration at low concentrations followed by a plateau in the responses at high concentrations. Alanine, glutamate, maltose, cholesterol and phosphatidylcholine emerged as potential indicators of phenanthrene exposure. An increased energy demand and an interruption in the conversion of succinate to fumarate in the Krebs cycle were observed due to phenanthrene exposure. Sub-lethal PFOA and PFOS exposure to E. fetida via contact tests for two days revealed heightened responses with higher PFOA and PFOS concentrations. Leucine, arginine, glutamate, maltose, and ATP were identified as potential indicators of PFOA or PFOS exposure. E. fetida responses were then investigated after exposure for two, seven and fourteen days to an artificial soil that was spiked with sub-lethal PFOS concentrations. An exposure time-dependent operation of two separate MOAs were identified. Both the contact tests and artificial soil exposure studies identified an elevation in fatty acid oxidation, a disruption in energy metabolism and biological membrane structure, and also an interruption of ATP synthesis following PFOA and PFOS exposure. This thesis illustrates the promise of NMR-based metabolomics as a routine tool for ecotoxicological assessment of contaminated sites.

This work explores the usefulness of fish bile analysis in combination with biomarkers for identifying and evaluating new environmental contaminants in the aquatic environment. It illustrates how bile analysis can be used together with biomarkers to assess the causes of estrogenic effects, to identify chemicals in the aquatic environment that are taken up by fish, and to monitor environmental exposure. In a first application, fish exposed to sewage treatment plant effluent were studied. Elevated levels of vitellogenin in the exposed fish demonstrated that estrogenic effects occurred. Several estrogen disrupting substances were identified in the fish bile, and analysis of water samples confirmed that these substances were present in the effluent. The synthetic estrogen 17a-ethinylestradiol, which is known to be present in sewage treatment plant effluent, was shown for the first time to be taken up by fish. Considering the reported potencies of the detected substances, it was concluded that 17a-ethinylestradiol was the major contributor to the estrogenic effects. Chemical analysis of bile was used to identify rubber additives that were released from tires immersed in water. The bile of rainbow trout held in the water contained high levels of metabolites of PAHs and aromatic nitrogen compounds. Several biomarkers were also measured in the exposed fish, and EROD induction and oxidative stress were observed. Based on the bile analysis observations together with knowledge of toxicological mechanisms, it was postulated that the EROD induction was due to the PAHs, while aromatic nitrogen compounds caused the oxidative stress. Resin acids in fish bile proved to be a good indicator of exposure in a chronic long-term study of rainbow trout exposed to effluent from a total chlorine free (TCF) pulp mill. Elevated levels of GST (gluthatione-S-transferase) and GR (gluthatione reductase) activity, and the presence of DNA adducts after a two month recovery period, indicated that compounds in the pulp mill effluents have persistent effects. In addition to characterising the exposure of the fish to the effluent, the analysis of the resin acids in the bile provided evidence of accidents in the pulp mill that the existing process monitoring system had not detected. Resin acids in bile were also found to be a valuable indicator of exposure to pulp mill effluents for eelpout living in the Baltic Sea. A correlation between resin acid levels in bile and skewed sex ratios provided an important link in the chain of evidence that substances in the pulp mill effluents cause male bias of the eelpout embryos. A particularly good example of the potential of bile analysis was the identification of a previously unknown environmental contaminant. A large peak was observed in the bile extracts of fish that had been exposed to sewage treatment plant effluent. This peak was identified as triclosan, which demonstrated its presence in sewage treatment plant effluent. Other work went on to show that it is a common contaminant of the aquatic environment. The ability of fish to concentrate contaminant metabolites in bile to levels very much higher than in the environment, and the comparatively low levels of analytic interferences, make bile a particularly attractive matrix to search for new, unknown organic pollutants

Characteristic westerly sea breeze carries air over the Los Angeles Basin in Southern California to the Inland Empire approximately 50 miles inland, directly impacting air quality in both of these two highly polluted regions. As particles play a critical role in air quality and human health, this study compares the bulk aerosol profiles of the Los Angeles pollution "source" and Inland Empire "receptor" regions during the 2013 and 2014 NASA Student Airborne Research Program (SARP) campaigns onboard the NASA DC-8 airborne laboratory. The source and receptor regions were characterized by a series of missed approaches at the Los Angeles International Airport, Long Beach Airport, and Los Alamitos Army Airfield (coastal sources) as well as the Ontario International Airport, San Bernardino International Airport, and March Air Reserve Base (inland receptors). The aerosol populations in each region were compared, and the changes evolved were analyzed alongside volatile organic compound (VOC) concentrations from Whole Air Samples. Particle size distributions were collected using a Droplet Measurement Technologies Ultra High Sensitivity Aerosol Spectrometer (DMT-UHSAS). Aerosol concentration, mass, and mode diameter increased significantly between coastal pollution source and inland pollution receptor regions in all cases, along with an increase in mode diameter. The observed changes cannot be accounted for by aerosol aging over the Los Angeles basin alone, suggesting new particle emission/formation over this region could be a dominating factor in the changes. Positive correlations between particle increases at receptor sites and anthropogenic VOC tracers will be discussed.

Despite indications that they are potential contaminant transport systems and threats to groundwater quality, very little effort has been invested in comparing contaminant transport behavior of natural environmental nanocolloids and their corresponding macrocolloid fractions in the presence of As, Se, Pb, and Cu contaminants. This study involved physico-chemical, mineralogical, stability and contaminant-transport characterizations of nano- (< 100 nm) and macro-colloids (100-2000 nm) fractionated from three Kentucky soils and one biosolid waste. Particle size was investigated with SEM/TEM and dynamic light scattering. Surface reactivity was estimated using CEC and zeta potential. Mineralogical composition was determined by XRD, FTIR, and thermogravimetric analyses. Sorption isotherms assessed affinities for Cu2+, Pb2+, AsO3-, and SeO4-2 contaminants, while settling kinetics experiments of suspensions at 0, 2 and 10 mg/L contaminants determined stability and transportability potential. Undisturbed 18x30 cm KY Ashton Loam soil monoliths were also used for transport experiments, involving infusion of 50 mg L-1 colloid suspensions spiked with 2 mg L-1 mixed contaminant loads in unsaturated, steady state, unit gradient downward percolation experiments. Overall, nanocolloids exhibited greater stability over corresponding macrocolloids in the presence and absence of contaminants following specific mineralogy trends. Physicochemical characterizations indicated that extensive organic carbon surface coatings and higher Al/Fe:Si ratios may have induced higher stability in the nanocolloid fractions, in spite of some hindrance by nano-aggregation phenomena. In the transport experiments, nanocolloids eluted significantly higher concentrations of colloids, total, and colloid-bound metals than corresponding macrocolloids. Contaminant elutions varied by colloid type, mineralogy and contaminant, with the following sequences: soil-colloids>bio-colloids, smectitic>mixed≥kaolinitic>biosolid, and Se>Pb/Cu≥As. Our findings demonstrate that even though they behave more like nano-aggregates rather than individual nano-particles, nanocolloids may exhibit significantly higher mobility and contaminant transport potential over great distances in subsoil environments than their corresponding macrocolloid fractions.

The focus of this dissertation is the use of aluminum Schiff base compounds, Salen(tBu)AlBr (SAB), in the dealkylation and detection of organophosphates (OPs). Three SAB compounds, Salen(tBu)AlBr (1), Salpen(tBu)AlBr (2), and Salophen(tBu)AlBr (3) were used to dealkylate a variety of trialkyl OPs. These reactions lead to unique organic-soluble aluminum phosphate compounds containing six-coordinate aluminum. Examples include [salen(tBu)AlOP(O)(OCH3)2]n (4), [salen(tBu)AlOP(O)(OCH2CH3)2]n (5), [salen(tBu)AlOP(O)(OPh)2]n (6), [Salophen(tBu)AlOP(O)(OCH3)2 (7), Salpen(tBu)AlOOP(O)(OiPr)2 (8). These compounds are unique examples of polymeric (4, 5, 6 and 7) and dimeric compounds (8) with salenAl units connected by phosphate linkages. The compounds do not decompose in neutral water. This is an advantage in the use of SABs for the deactivation of phosphate esters such as nerve agents. Water-soluble and stable group 13 salen complexes, Salen(SO3Na)MNO3 (M =Al (19), Ga (22)), Salpen(SO3Na)MNO3 (M = Al (20), Ga (23)), and Salophen(SO3Na)M(NO3) (M = Al (21), Ga (24)) were synthesized by using water-soluble Salen(SO3Na) ligand. All the compounds were characterized by various analytical techniques: 1H and 13C NMR, IR, and melting point. One SAB was used to detect the nerve agents (NA). Salen(tBu)Al(Ac), prepared in situ from Salen(tBu)AlBr and NaAc, forms Lewis acid-base adducts with the NAs, GB (sarin) and GD (soman), and the VX hydrolysis product, EMPA, in aqueous solution. The [Salen(tBu)Al(NA)]+ compound is sufficiently stable to allow the identification of the NA with ESI-MS. Molecular ion peak was detected for every compound with little or no fragmentation. The distinctive MS signatures for [Salen(tBu)Al(NA)]+ compounds provide a new technique for identifying NAs in aqueous solution.

Ionic liquids (ILs) are liquid organic salts at room temperature which are composed of only ions (cations and anions). Ionic liquids are regarded as “novel solvents” and have been gaining attention as alternatives to volatile molecular organic solvents. Ionic liquids have outstanding properties, such as negligible vapor pressure (no or limited evaporation or volatilization), low melting point, thermal stability, and ionic conductivity. They can be used in efficient and clean energy production and storage. The synthesis of the low-cost and performance-effective ionic liquids using inexpensive raw materials is presented and characterized. Characterization was done using Thermogravimetric Analysis (TGA), Fourier Transform Infrared Spectroscopy (FTIR), and Scanning Differential Thermometry (DSC-TGA). Cost effective ionic liquids were synthesized and characterized and then compared to commercially available ionic liquids. Results for newly synthesized ionic liquids suggest that these cost effective ionic liquids were electroconductive and thermally stable when compared to the raw materials used for synthesis of ionic liquids. The thermal stability of these ionic liquids was less, however, when compared to the regular higher cost ionic liquids. FTIR characterization also provided secondary evidence on expected functional groups of newly synthesized ionic liquids. Viscosity of the syntehsized ionic liquids was higher when comapred to the commercially avaialable ionic liquids.