Rozprawy doktorskie na temat „Natural organic matter”

Electrodialysis (ED) experiments were conducted on reverse osmosis (RO)-concentrated solutions of NOM from six rivers. The ED processes successfully recovered 88 11% of TOC, and removed 83% 19% of SO42- and 67% 18% of H4SiO4. More importantly, the molar ratios of SO42- /TOC and H4SiO4 /TOC were reduced to a mean value of 0.0046 and 0.032, respectively, surpassing the goal for removal of SO42- (0.008) and almost achieving the goal for removal of H4SiO4 (0.021). The ED process can lower the SO42- /TOC ratio in samples whose initial SO42- /TOC ratios are already far below the limit of 0.008 used in this study. The coupled RO/ED process that has been described here offers a fast, simple, chemically mild (relative to other methods), and reproducible method of isolation of large quantities of relatively unfractionated, low-ash NOM from freshwaters. RO/ED was also successfully used for isolating and concentrating marine dissolved organic matter (DOM). The effort successfully recovered a median of 72% of the TOC from 200 L samples within six to nine hours of processing through a combination of ED and RO, greatly exceeding the current norm of 30%. The relatively high recovery of DOM implies that classes of DOM previously missing are included in these samples and should yield new insight into the chemistry of marine DOM. Freshwater samples processed by electrodialysis were analyzed for elemental composition and by capillary zone electrophoresis (CZE), 1H and 13C nuclear magnetic resonance spectroscopy (NMR), and electro-spray ionization mass spectrometry (ESI-MS). Bulk elemental composition, 1H- and 13C-NMR, and ESI-MS data provide evidence linking bioavailabilty to the bulk chemistry of NOM: the H/C and N/C molar ratios are positively and strongly correlated with bioavailability, as hypothesized. Using an independent dataset (STORET) of water quality parameters, calculated BOD/TOC ratios were found to be moderately correlated with measured bioavailabilities and can be used as a surrogate for bioavailability of geochemically diverse riverine DOM.

Thesis (Ph. D.)--Earth and Atmospheric Sciences, Georgia Institute of Technology, 2007.
Perdue, E. Michael, Committee Chair ; Ingall, Ellery, Committee Member ; Stack, Andrew, Committee Member ; Nenes, Athanasios, Committee Member ; Pfromm, Peter, Committee Member.

Flocculation is an important part of the carbon cycle. It is therefore crucial to understand how flocculation is regulated and how different environmental factors impact. A dilemma is that it has been found difficult to measure flocculation experimentally. In this thesis, flocculation of dissolved organic carbon in a Swedish lake was measured in a series of laboratory experiments. The method used was Dynamic Light Scattering (DLS). DLS is used to determine the size distribution profile of, for instance, small particles in suspension. DLS measures Brownian motion and relates it to the particle size by measuring the fluctuation in scattering intensity. It is not very effective to measure the frequency spectrum contained in the intensity fluctuations directly, so instead, a digital auto correlator is used. Since factors such as pH, salinity and calcium chloride content varies in lakes and is thought to have an impact on flocculation, this was investigated as well. As pH was changed in a range of 3 to 9, small changes in size distribution could be detected. Salinity and calcium chloride content have quite an impact on flocculation. Time also has a great impact, samples that were set to rest for a week showed a significant increase in particle size. For DLS to work, the samples need to be filtered of centrifuged to get rid of large particles. Different types of filters were tested to see which filter material was the best to use. When filtering the water we only want to filter out the large particles. Natural organic matter has a hydrophobic component which adsorbs to some filter types but not to others. It is crucial to know which filters this hydrophobic component adsorbs to, so that the loss of dissolved organic carbon during filtration can be minimalized.

Dissolved organic matter (DOM) is the most dynamic and least understood part of the global oceanic carbon cycle. Furthermore the molecular composition of DOM is largely unknown. This study focused on the distribution pattern, removal processes and molecular characterisation of DOM in a range of estuaries and coastal zones in New Zealand. Doubtful Sound, the longest fjord in Fiordland National Park, South Island, New Zealand was of particular interest, because of the combination of extreme rainfall, enhanced production of DOM within the temperate rainforest which largely appears in the relatively deep ([greater than or equal to] 5 m) low salinity layer (LSL) at the fjord surface. A typical river estuary (Freshwater River) located in Stewart Island, New Zealand was also investigated. Optical water properties such as the UV/Vis absorption coefficient at 355 nm (a[CDOM](355)) and excitation-emission matrix fluorescence (EEM) were determined for samples from freshwater, across the LSL into open ocean water. These optical properties showed a marked decrease with salinity and highest levels of EEM fluorescence and a[CDOM] (355) in the brackish surface water. In addition to the observed changes in the optical properties, ultrahigh resolution Electrospray Ionisation Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (ESI-FT-ICR-MS) determination of molecular formulae revealed that in the fjord about 20 % of these formulae changed along a vertical salinity gradient across the LSL between the brackish surface water and the saline water at 5 m depth. This trend was even more pronounced along the salinity gradient of the Fresh Water River Estuary in Stewart Island, where 60 % of all assigned molecular masses changed from freshwater over the mixing zone to ocean water. Associated with these changes was a marked increase in aromaticity with increasing salinity. Comparable behaviour with increasing salinity was also observed in estuarine samples from the Cape Fear River system, North Carolina, USA. In contrast, only minor changes were determined in molecular formulae for surface water samples collected along a transect off the Otago Coast and across the Subtropical Convergence (STC) into Subantarctic Water (SAW). However, a comparison of the molecular formulae assigned to the DOM pool for the STC water and a freshwater stream in Doubtful Sound, revealed that 75 % of all the assigned formulae for the open ocean sample were common to these two markedly different types of natural waters. This seemingly refractory DOM contained nearly 600 assigned molecular formulae, which were all very similar (only spaced by two hydrogen and CH₂ groups) and could be explained with only 9 general molecular formulae. However, the comparison of all assigned formulae for the freshwater sample suggested that about 90 % of the assigned molecular formulae for the terrestrially-derived DOM changed as it moved from rivers to the open ocean and that only 10 % remained the same. Singlet oxygen showed a very close relationship with the optical properties such as the absorption coefficients (a[CDOM](355)) and the EEM fluorescence intensities and these results suggested that singlet oxygen steady state concentrations are linked to CDOM. Photodegradation processes were confirmed to be responsible for a significant destruction of CDOM. Samples collected from different salinity waters showed major differences in wavelength-dependent photo-decay of CDOM suggesting that the rate of photodegradation in the UV range decreased with increase in salinity whereas it was enhanced for longer wavelength radiation ([greater than or equal to]400 nm). Additionally, the predominantly unsaturated compounds produced during estuarine mixing were found to be highly photolabile and were either destroyed or new unsaturated compounds were produced within 21 h of solar irradiation.

The removal of natural organic matter (NOM) at water treatment works (WTW) is essential in order to prevent toxic compounds forming during subsequent disinfection. Coagulation and flocculation processes remain the most common way of removing NOM. The properties of the resulting flocs that form are fundamental to the efficient removal of organic material. Periods of elevated NOM loads at WTW can lead to operational problems as a result of the deterioration in floc structural quality. Assessment of floc physical characteristics can therefore be a crucial tool in order to determine and predict solid-liquid removal performance at WTW. Here the growth, size, breakage, strength, re-growth, fractal dimension and settling velocity were measured for flocs formed from a NOM rich water source. NOM floc structural characteristics were measured and evaluated over a one year period in order to monitor the seasonal variation in floc structure. The results showed that a significant improvement in floc size and strength was seen during autumn and summer months. It was subsequently shown that as the organic fraction in the floc increases the floc size, settling velocity and fractal dimension all decrease. A model was proposed showing how these changes were dependent upon the adsorption of NOM onto primary particle surfaces. A range of different chemical coagulant treatment options were applied for NOM removal and the resulting floc structure compared. Considering both floc structure and optimum NOM removal the treatment systems were of the following order (best to worst): MIEX® + Fe > Fe > Fe + polymer > Al > polyDADMAC. NOM floc re-growth was shown to be limited for all the treatment systems investigated. The practical implications of the results were: (1) The requirement for careful coagulant dosing or order to achieve optimum floc characteristics. (2) The use of a pre-treatment anionic ion-exchange stage prior to coagulation. (3) A comparison of alum and ferric based coagulants suggested the ferric coagulants gave better floc structure and improved NOM removal rates.

Mestrado em Química
For the purpose of resolving the chemical heterogeneity of natural organic matter (NOM), comprehensive two-dimensional liquid chromatography (LC x LC) was employed for the first time to map the hydrophobicity and polarity vs. molecular weight (MW) distribution of the following complex organic mixtures: Suwannee River (SR-FA) and Pony Lake (PL-FA) Fulvic Acids, both obtained from the International Humic Substances Society, and water-soluble organic matter (WSOM) from atmospheric aerosols. Two methods have been developed using either a conventional reversed-phase silica column (RP-C18) or a mixed-mode hydrophilic interaction column (mixed-mode HILIC) in the first dimension, and a size-exclusion column (SEC) in the second dimension. The RP-C18 x SEC and mixed-mode HILIC x SEC fractions were screened on-line by UV at 254 nm, molecular fluorescence at excitation/emission wavelengths (Exc/Em) of 240/450 nm, and by evaporative light scattering. The MW distributions of these NOM samples were further characterized by number average molecular weight (Mn), weight average molecular weight (MW), and polydispersity (Mn/Mw). Findings suggest that the combination of two independent separation mechanisms is promising in extend the range of NOM separation. The complete range of Mw values obtained in this study varied within 745-2122 Da, 637-1950 Da, and 157-891 Da for the SR-FA, PL-FA and WSOM, respectively. The obtained results were associated to the different origin and formation pathways of the three NOM samples, which strongly influence their chemical composition and MW distribution.
Com o objetivo de avaliar a heterogeneidade química da matéria orgânica natural (MON), foi aplicada pela primeira vez a técnica de cromatografia líquida compreensiva bidimensional (CL x CL) a três misturas orgânicas complexas: ácidos fúlvicos do Rio Suwannee (AF-RS) e do Lago Pony (AF-LP), ambos obtidos da Sociedade Internacional de Substâncias Húmicas, e matéria orgânica solúvel em água (MOSA) de aerossóis atmosféricos. Com esta nova técnica analítica, pretendeu-se efectuar a separação cromatográfica das amostras de MON tendo em conta a hidrofobicidade e polaridade vs. massa molar. Para o efeito, foram desenvolvidos dois métodos distintos, utilizando na primeira dimensão ou uma coluna de fase reversa convencional (C18) ou uma coluna de interação hidrofílica/fase reversa (HILIC, sigla inglesa), e na segunda dimensão uma coluna de exclusão por tamanhos (SEC, sigla inglesa). Os perfis cromatográficos das frações resultantes dos sistemas C18 x SEC e HILIC x SEC foram registados por três detetores: UV a 254 nm, fluorescência molecular a comprimentos de onda de excitação/emissão (Exc/Em) de 240/450 nm e detector evaporativo de dispersão de luz. A distribuição da massa molar das amostras foi caracterizada pelas grandezas massa molar média em número (Mn), massa molar média em peso (Mw), e índice de polidispersão (Mn/Mw). Os resultados obtidos sugerem que a combinação de dois mecanismos de separação independentes constitui um método promissor na separação de amostras de MON. A distribuição de Mw obtida neste estudo foi de 745 a 2122 Da, 637 a 1950 Da e 157 a 891 Da para as amostras de AF-RS, AF-LP e MOSA de aerossóis atmosféricos, respectivamente. A gama de valores obtidos para a distribuição de Mw foram associados às diferentes origens e mecanismos de formação das amostras de MON, os quais podem influenciar a respectiva composição química e distribuição de tamanhos moleculares.

Nanoparticles have gained growing attention of the scientific community over the past few decades due to their high potential to be used in diverse industrial applications. Nanoparticles often possess superior characteristics, such as catalytic activity, photochemical activity, and mechanical strength, compared to their bulk counterparts, making them more desirable in different industrial applications. During the past few decades, the use of the nanoparticles in various industries has been increased. With increasing usage release of nanoparticles into the environment has also increased. There is a growing concern about the nanoparticle toxicity and numerous studies have shown the toxic effects of different nanoparticles on various plants, animals, and microorganisms in the environment. Toxicity of nanoparticles is often attributed to their morphology and their ability to undergo different transformations in the environment. These transformations include aggregation, dissolution, and surface adsorption. Natural organic matter (NOM) are the most abundant natural ligands in the environment which include Humic acid and Fulvic acid. These high molecular weight organic molecules have complex structures and contain many different functional groups such as carboxylic acid groups, hydroxyl, amino and phenolic groups that can interact with the nanoparticle surface. The nature and the intensity of the interaction are dependent on several factors including the size and the surface functionality of nanoparticles and pH of the medium. The smaller the nanoparticle, the higher the adsorption of NOM due to the high surface to volume ratio of smaller particles. Functional groups on the surface dictate the surface charge of the nanoparticles in water depending on the acidity. The higher the acidity, higher the adsorption of NOM due to increased electrostatic attractions between positively charged nanoparticles and the negatively charged NOM molecules. Adsorbed NOM on nanoparticles affect the other transformations such as aggregation and dissolution and can in turn alter the reactivity and toxicity of the nanoparticles. Therefore, effect of NOM is an important factor that should be considered in environmental toxicity related studies of nanoparticles.

The existence of trihalomethanes (THMs) in a drinking water plant of Nicaragua has been investigated in order to see whether the concentration exceeded the maximum contaminant level recommended by the environmental protection agency of the United States (USEPA) and the Nicaragua guidelines. The influence of pH, temperature, chlorine dose and contact time on the formation of THMs were studied. The contents of organic matter measured by surrogate parameters such as total organic carbon, dissolved organic carbon, ultraviolet absorbance and specific ultraviolet absorbance were also determined in order to show which type of organic matter is most reactive with chlorine to form THMs. Models developed by other researchers to predict the formation of trihalomethanes were tested to see whether they can be used to estimate the trihalomethane concentration. In addition, empirical models were development to predict the THM concentration of the drinking water plant analysed. The raw water was treated by conventional and enhanced coagulation and these processes were compared with regard to the removal of natural organic matter (NOM). The significance of the results was assessed using statistic procedures.

The average concentration of THMs found at the facility is below the USEPA and Nicaragua guideline values. Nevertheless the maximum contaminant level set by USEPA is sometimes exceeded in the rainy season when the raw water is rich in humic substances. Comparison between the water treated by conventional and enhanced coagulation shows that enhanced coagulation considerably diminished the trihalomethane formation and the value after enhanced coagulation never exceeded the guidelines. This is because enhanced coagulation considerably decreases the organic matter due to the high coagulant dose applied. The study of the trihalomethane formation when varying pH, time, temperature and chlorine dose using water treated by conventional and enhanced coagulation showed that higher doses of chlorine, higher pH, higher temperature and a longer time increases the formation of THMs. However, combinations of two and three factors are the opposite. The predicted THM formation equations cannot be used for the water at this facility, since the results shown that the measured THM differs significantly from the THM concentration predicted. Two empirical models were developed from the data for enhanced coagulation, using linear and non-linear regression. These models were tested using the database obtained with conventional coagulation. The non-linear model was shown to be able to predict the formation of THMs in the Boaco drinking water plant.

Doctor of Philosophy
Department of Civil Engineering
David R. Steward
Groundwater contamination with arsenic (As), a naturally occurring metalloid, is a worldwide problem. Over 100 million people are at health risk due to arsenic contaminated groundwater, especially in the Bengal Basin in south-east Asia. Dissolved organic matter (DOM), geology and geomicrobiology are important factors affecting arsenic mobility. This study focuses on interactions of different aspects of natural organic matter in arsenic-contaminated environments. A literature review specifically includes past studies done on fundamentals of arsenic geology, geomicrobiology, DOM characterization and relevant analytical methods and tools. Based on background information already collected, this research is focused on specific research questions and corresponding hypotheses. The overarching goal of this investigation is to better understand the mechanisms by which DOM influences arsenic mobilization. The specific goals of this research are: 1) to evaluate role of oxidized humic quinones in reductive dissolution of Fe-As minerals and subsequent arsenic mobilization via electron shuttling, 2) to quantify the rate of microbially mediated reductive dissolution in the presence of oxidized humic quinones, 3) to evaluate DOM-Fe-As ternary complex formation and its influence on arsenic mobility and 4) to characterize DOM in the arsenic-contaminated aquifers of West Bengal, India and evaluate its role in arsenic mobilization using groundwater flow and contaminant transport modeling approach. Results of this study revealed that oxidized quinone like moieties (such as fulvic acids) serve as an electron shuttle and enhance the reductive dissolution process under reducing conditions, hence mobilize the arsenic in groundwater. Another key result from this study suggested that arsenic binds with non-aromatic portion of the humic-like DOM under reducing conditions and increases its solution concentration. A field study conducted in West Bengal, India revealed that the mechanisms studied in the laboratory exists in reducing aquifer. A groundwater flow and reactive transport model was created to explain multiple interactions of DOM and arsenic spatial scales. Broader impacts of this study include significant addition to scientific knowledge about subsurface biogeochemistry and the role of DOM in biogeochemical reactions in the subsurface.

Litter decomposition is a key ecosystem service within aquatic ecosystems and is a complex process that is sensitive to environmental factors. The role of microbial and macrofaunal decomposers, and how it changes across environmental gradients is not yet fully understood. Decomposition was assessed across 6 biogeographical regions to determine the role of macroinvertebrates in this ecosystem service. Decomposition was estimated using standardized cotton strips, which were deployed in the mesocosms of each region. The role of macroinvertebrates was tested with an exclusion experiment which allowed or prevented the access of macroinvertebrates to cotton strips, a similar experiment was also conducted in natural ponds. After 64 days the cotton strips were collected, and mass loss and tensile strength were measured. There were significant differences in the rate of decomposition across different regions and no differences were found between systems. Macroinvertebrates played an important role, with gatherers being major players; Resumo: A decomposição é um serviço de ecossistema chave e um processo complexo sensível a factores ambientais. O papel de decompositores microbianos e da macrofauna, e como este papel muda num gradiente ambiental não é completamente entendido. A decomposição foi avaliada em 6 zonas biogeográficas para determinar o papel de macroinvertebrados neste serviço de ecossistema. A decomposição foi estimada utilizando tiras de algodão, colocadas em mesocosmos nas diferentes regiões. O papel dos macroinvertebrados foi testado através de uma experiência de exclusão que permitia ou impedia o acesso de macroinvertebrados às tiras, uma experiência semelhante foi realizada em charcos naturais. Ao fim de 64 dias, as tiras de algodão foram recolhidas e a perda de massa e tensão foram quantificadas. Encontraram-se diferenças significativas na decomposição entre as diferentes regiões, mas não se observaram diferenças entre sistemas. Os macroinvertebrados têm um papel importante neste serviço de ecossistema, sendo as espécies colectoras as mais importantes

Thesis (Ph. D)--Ohio State University, 2002.
Title from first page of PDF file. Document formatted into pages; contains xxii, 119 p.: ill. Includes abstract and vita. Advisor: Harold W. Walker, Civil Engineering Program. Includes bibliographical references (p. 115-119).

Orientador: Wilson de Figueiredo Jardim
Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica
Made available in DSpace on 2018-08-04T20:31:57Z (GMT). No. of bitstreams: 1 Bisinoti_MarciaCristina_D.pdf: 1949476 bytes, checksum: a702f967a817c83e250f6e74b334ddd3 (MD5) Previous issue date: 2005
Doutorado
Quimica Analitica
Doutor em Ciências

Thesis (Ph. D.)--Earth and Atmospheric Sciences, Georgia Institute of Technology, 2006.
Taillefert, Martial, Committee Member ; Weber, Rodney, Committee Member ; Stack, Andrew, Committee Member ; Benner, Ronald, Committee Member ; Ingall, Ellery, Committee Chair. Includes bibliographical references.

Granular activated carbon (GAC) is used in municipal drinking water treatment plants for the removal of organic compounds (natural and synthetic), taste and odour compounds, as well as for the removal of disinfection by-products (DBPs). Many alternative technologies for GAC regeneration, such as bioregeneration, chemical regeneration, chemical desorption regeneration, and steam regeneration, have been tested in attempts to overcome the shortcomings of thermal regeneration. In this study, the suitability of electrochemical regeneration for municipal drinking water systems was investigated. Three different sample types were obtained; virgin, field spent and field-thermally reactivated GAC. The field spent samples were electrochemically regenerated at 10, 50, 100 and 200mA in a divided cell electrochemical reactor for 5 h. The virgin, the thermal and the electrochemical regenerated samples were analysed for aqueous NOM adsorption, iodine number, surface chemistry, pore size distribution and surface area to evaluate the regeneration efficiency and to characterize the regeneration. The electrochemical reactor was able to regenerate 8--15% of the adsorption capacity of the field spent GAC compared to approximately 100% regeneration efficiency for the thermally regenerated samples. (Abstract shortened by UMI.)

Natural Organic Matter (NOM), a pervasive component of natural waters, presents many challenges for water treatment systems. Its complex and heterogeneous nature makes NOM difficult to characterize and highly variable in its effect in water treatment. Two specific water treatment challenges caused by NOM and dependent on its character are disinfection by-product (DBP) formation and organic fouling in pressure-driven membranes. Many NOM characterization methods exist and have shown success in highly controlled laboratory settings; however, evaluating their effectiveness in full-scale systems to predict DBP formation and membrane fouling remains an ongoing challenge. Fluorescence NOM Excitation Emission Matrices (EEM) are hypothesized to be effective in NOM characterization because they capture the complexity and heterogeneity of the NOM in data-rich measurements that are unique to each individual sample. The objective of this work was to assess the utility of fluorescence EEM and other NOM characterization techniques for predicting DBP formation and membrane fouling in full-scale treatment systems. The review of current literature on NOM characterization and use in predicting water treatment challenges revealed patterns among NOM characterizations and water treatment outcomes – namely, high molecular weight, hydrophobic, aromatic NOM leads to increased DBP formation, while hydrophilic NOM with low aromaticity leads to increased organic fouling. Multiple reports from laboratory studies indicating the success of fluorescence measurements in characterizing DBP formation and membrane fouling suggest evaluation at full-scale treatment plants is warranted. The two field studies presented in this dissertation each address one of the major treatment challenges outlined – DBP formation and membrane fouling. The DBP formation field study incorporated source water and finished water samples from six treatment plants along the Monongahela River in southwestern Pennsylvania to create a regional watershed model. Fluorescence measurements of the source water were used successfully to classify finished water DBPs according to various targets using classification trees. The membrane fouling study incorporated samples of the raw source water and treated water at various treatment stages within a full-scale two-pass (two-stage) reverse osmosis membrane treatment plant. Fluorescence measurements were successful in distinguishing between high fouling and low fouling periods within the plant, however, they were not capable of tracking treatability of source water throughout the pre-treatment steps. The results of the two field studies indicate that fluorescence measurements have utility in NOM characterization for full-scale treatment plant operations, but more research is needed in determining which specific signals are useful in online fluorescence detection and in assessing the broader applicability of these techniques to other geographical regions with different water qualities.

Natural biogeochemical cycles of the macronutrient elements carbon (C), nitrogen (N) and phosphorus (P) have been transformed by food and fuel production, through atmospheric pollution and climate change. Further, land disturbance has led to considerable losses of nutrients from terrestrial ecosystems. This investigation aims to explore and address several barriers to understanding natural organic matter cycling across terrestrial and aquatic ecosystems. Soil organic matter (SOM) turnover models are often constrained by C and N, while data on organic P is lacking. Twenty UK soils were used to provide the first investigation of organic P in density fractionated SOM pools. Organic matter in the mineral fraction was considerably more enriched in oP. Stoichiometric ratios agreed with a new classification model, which provides important constraints for models of nutrient cycles. Radiocarbon (14C) measurements of aquatic OM indicates sources and turnover on different timescales. Here, the first analysis of particulate O14C in UK rivers suggested topsoil was the major source. Significantly depleted material was found in a catchment with historical mining activity. Global, temporal analysis of dissolved O14C enabled quantification of different OM sources, and highlighted the importance of assessing the data against the changing atmospheric 14C signal. New dissolved O14C data for rural, arable and urban catchments were more depleted than the global averages. In industry, there is a growing need to manage aquatic nutrient enrichment through rapid and reliable monitoring. A model of UV absorbance was tested against freshwaters that were biased towards eutrophic conditions. The results demonstrated the weak absorbing components of algal DOM, and new variable model parameters were introduced, which quantified the contribution of algal DOM. This could have implications on model predictions of DOC concentration, and a generally applicable spectroscopic model is questionable. This investigation considerably expands the dataset available for modelling large scale biogeochemical cycles, highlights the importance of an integrated approach, and considers the implications involved with applied modelled predictions of aquatic DOC.

The association between natural organic matter (NOM) and iron (Fe) minerals was widely found in soil and sediments and has been shown to impact the fate of Fe minerals and NOM. Ferrihydrite, a ubiquitous Fe mineral, serves as important sink for NOM and rapidly transforms to secondary Fe minerals in the presence of Fe(II). The associated NOM has been found to influence the Fe(II)-catalyzed ferrihydrite transformation pathway, but it remains unclear how various NOM affects this transformation and the implication. This study specifically investigates how different species of NOM affect Fe(II)-catalyzed ferrihydrite transformation under different C/Fe ratios. A series of Fe isotope tracer experiments were conducted to measure Fe atom exchange and electron transfer between aqueous Fe(II) and ferrihydrite in the presence of diverse NOM species. The fate of Ni during Fe(II)-catalyzed transformation of NOM-Fh coprecipitate was also investigated. Ferrihydrite was found less susceptible to Fe(II)-catalyzed transformation with increasing C/Fe ratio and fulvic acids and Suwannee River NOM (SRNOM) in the coprecipitates need lower C/Fe ratio than humic acids to completely inhibit formation of secondary Fe minerals. At C/Fe ratios where ferrihydrite transformed to secondary minerals, goethite was dominant in ferrihydrite coprecipitated with humic acids, whereas lepidocrocite was favored in ferrihydrite coprecipitated with fulvic acids and SRNOM. Adsorbed SRNOM may be more inhibitive than coprecipitated SRNOM on Fe(II)-catalyzed ferrihydrite transformation under similar C/Fe ratios. Despite no secondary mineral transformation at high C/Fe ratios, Mössbauer spectra indicated electron transfer still occurred between Fe(II) and ferrihydrite coprecipitated with fulvic acid and SRNOM. In addition, isotope tracer experiments revealed that a significant fraction of structural Fe(III) in the ferrihydrite mixed with the aqueous phase Fe(II) (~85%). After reaction with Fe(II), Mössbauer spectroscopy indicated some subtle changes in the crystallinity, particle size or particle interactions in the coprecipitate. The effect of coprecipitated SRNOM on Ni(II) distribution during Fe(II)-catalyzed ferrihydrite transformation was investigated with adsorbed Ni(II) and coprecipitated Ni(II). Ni(II) adsorbed on ferrihydrite was more resistant to acid extraction after Fe(II)-catalyzed transformation and suggested that structural incorporation of Ni into secondary Fe minerals occurred. With coprecipitated SRNOM, ferrihydrite did not transform to secondary minerals in the presence of Fe(II) but extensive Fe atom exchange between aqueous Fe(II) and structural Fe(III) still occurred. Limited change in Ni stability was observed, suggesting there was only small portion of Ni redistributed in the presence of Fe(II). Pre-incorporated Ni(II) in Ni-SRNOM-Fh coprecipitate was partially released (6-8 %) in the presence of Fe(II), but the distribution of remaining Ni(II) in the solid did not change measurably. Our observation suggests that the presence of SRNOM limited the redistribution of Ni most likely because of limited transformation of ferrihydrite to secondary minerals.

The objective of this thesis was to study the adsorption and desorption characteristics of natural organic matter (NOM) adsorbed on granular activated carbon (GAC). Five different natural waters (Ottawa River, ON; St. Lawrence River, ON; Vars Ground Water, ON; Buffalo Pound Lake, SK; Ohio River, OH) were studied to see if the characteristic of irreversible adsorption was a universal phenomenon. This was studied by comparing desorption isotherms to adsorption isotherms. Preliminary long-term kinetic studies were used to ensure that the contact time was sufficient for equilibrium. The waters were also fractionated to further study the differences in adsorption and desorption properties of various surface waters. The fractionation techniques used were; ultrafiltration by membrane separation, extraction of humic acids using a methylmethacrylate resin (XAD8) and size exclusion chromatography using a sephadex gel in a glass column. (Abstract shortened by UMI.)

Polycyclic aromatic hydrocarbon (PAH) bioavailability does not correlate directly with total PAH sediment concentration because PAHs strongly sorb to organic matter. Many current toxicological models assume that PAHs present in the dissolved phase reflect actual PAH bioavailability to organisms. Plants can release significant amounts of plant organic matter (POM) to soils and sediments; however, the mechanisms by which POM may affect PAH bioavailability in sediments are unclear. The rhizosphere may increase PAH bioavailability by destabilizing soil organic matter (SOM) and enhancing PAH desorption, or the rhizosphere may alter SOM composition and provide new carbon matrices to sorb/sequester PAHs and reduce PAH desorption. Desorption studies were conducted to determine if vegetation decreased or increased the rate and mass amounts of desorbable PAHs. Replicate desorption studies were conducted using vegetated and non-vegetated bulk sediment and HF/HCl humin fractions; sediments were collected from a coastal refinery distillate waste pit (RP) and refinery-impacted sediments from a freshwater canal (IH). Desorption isotherms for four PAHs were determined by two methods, aqueous and TenaxTM bead extractions. PAHs were quantified by gas chromatography/mass spectrometry selected ion monitoring (GC/MS SIM). Results showed differences in PAH desorption based on the amount of time vegetation had been present in sediments. Vegetated sediments with 30+ years of vegetative growth (RP) desorbed more PAHs than non-vegetated sediments by TenaxTM extraction in both bulk and humin sediment fractions. Recently vegetated, IH freshwater sediments desorbed fewer PAHs than non-vegetated IH sediments by aqueous and TenaxTM extractions in bulk and humin sediment fractions. These findings suggest that initial exposure of sediment to vegetation slows PAH desorption and that extensive exposure to vegetation enhances PAH desorption from both labile and refractory SOM.

Natural organic matter (NOM), ubiquitous in natural water sources, is generated by biogeochemical processes in both the water body and in the surrounding watershed, as well as from the contribution of organic compounds that enter the water as a result of human activity. NOM significantly affects the properties of the water source, including the ability to transport metals, influence the aggregation kinetics of colloidal particles, serve as a food source for microorganisms and act as a precursor in the formation of disinfection by-products (DBPs), as well as imparting a brown colour to the water. The reactivity of NOM is closely tied to its physicochemical properties, such as aromaticity, elemental composition, functional group content and molecular weight (MW) distribution. The MW distribution is an important consideration from a water treatment perspective for several reasons. For example, low MW NOM decreases the efficiency of treatment with activated carbon, and this fraction is thought to be the portion most difficult to remove using coagulation. The efficiency of membranes in the treatment of drinking water is also influenced by the MW distribution of NOM, while some studies have shown that the low MW fraction contributes disproportionately to the formation of bioavailable organic matter, therefore promoting the formation of biofilms in the distribution system. For these reasons, understanding the MW distribution of NOM is important for the treatment of natural waters for use as drinking waters. Optimisation of a high pressure size exclusion chromatography (HPSEC) method for analysis of the MW distribution of NOM in natural waters is described (Chapter 2). Several parameters influencing the performance of HPSEC are tested and an optimised set of conditions illustrated.These parameters included eluent composition, ionic strength of the sample, flow rate and injection volume. Firstly, it was found that increasing the ionic strength of the HPSEC eluent resulted in less exclusion of NOM from the stationary phase. Stationary phases used in HPSEC contain a residual negative charge that can repel the negatively charged regions of NOM, effectively reducing the accessible pore volume. By increasing the ionic strength, interactions between the stationary phase and eluent enabled a larger effective pore size for the NOM analytes. However, increasing ionic strength of the eluent also resulted in a loss of peak resolution for the NOM portion able to access the pore volume of the stationary phase. Determining the ideal eluent composition required the balancing of these two outcomes. Matching of the ionic strength of the sample with the eluent was also an important consideration. Retention times were slightly lower when the sample ionic strength was not matched with the eluent, especially for the lowest MW material, although the effect on chromatography was minimal. Flow rate had no effect on the resolution of the HPSEC chromatogram for the portion of material able to permeate the pore space of the stationary phase. Changes in the volume of sample injected had a marked effect on the elution profile of the NOM sample. Besides the obvious limitation of detection limit, only minor changes in elution profile were obtained up to an injection volume of 100 µL. Volumes above this value, however, resulted in significant peak broadening issues, as well as an undesirable effect on the low MW portion of detected DOC.In Chapter 3, high pressure size exclusion chromatography with UV254 [subscript] and on-line detection of organic carbon (HPSEC-UV254[subscript]-OCD) was used to compare the removal of different apparent MW fractions of DOC by two process streams operating in parallel at the local Wanneroo groundwater treatment plant (GWTP). One of these two process streams included alum coagulation (operating in an enhanced coagulation mode (EC) for increased DOC removal) and the other stream included a magnetic ion exchange (MIEX®) process followed by alum coagulation (MIEX®-C). The MIEX® process is based on a micro-sized, macroporous, strong base anion exchange resin with magnetic properties, which has been designed to remove NOM through ion exchange of the anionic sites in NOM. Water was sampled from five key locations within these process streams, and the DOC at each location was characterised in terms of its MW distribution. HPSEC was carried out using three different on-line detector systems, namely OCD, UV absorbance detection at 254 nm, and fluorescence detection (λex[subscript]= 282 nm; λim[subscript] = 353 nm). This approach provided significant information on the chemical nature of the DOC in the various MW fractions. The MIEX®-C process was found to outperform the EC process: these two processes removed similar amounts of high and low MW DOC, but the MIEX®-C process showed greater removal of DOC from the intermediate MW fractions. The two coagulation processes (EC and coagulation following MIEX®) showed good removal of the fractions of highest MW, while the MIEX® process alone was found to remove DOC across all MW fractions.These results seem to indicate that anionic groups, particularly susceptible to removal with MIEX® treatment, are well distributed across all MW fractions of NOM. In agreement with previous studies, MIEX®-C outperformed EC in the overall removal of DOC (MIEX®-C removed 25 % more DOC than EC). However, 70% of the additional DOC removed by MIEX®-C was comprised of a surprisingly narrow range of medium-high MW fractions. The development of a novel online organic carbon detector (OCD) for use with HPSEC for determining the MW distribution of NOM is described in Chapter 4. With UV absorbance detection, the magnitude of the signal is based on the extinction coefficient of the chromophores in the analytes being investigated; whereas the signal from an OCD is proportional to the actual organic carbon concentrations, providing significantly more information. The development of an online OCD involved the separation of analytes using HPSEC, removal of inorganic carbon species which may interfere with organic carbon determination, oxidation of the organic carbon to carbon dioxide, separation of the produced carbon dioxide from the aqueous phase and subsequent detection of the gaseous carbon dioxide. In the new instrument, following separation of components by HPSEC, the sample stream was acidified with orthophosphoric acid to a concentration of 20 mmol L-1[superscript], resulting in a pH of ≤ 2, in order to convert inorganic carbon to carbon dioxide. This acid dose was found to remove greater than 99 % of inorganic carbon once the acidified sample was passed through a hydrophobic polytetrafluoroethylene (PTFE) membrane allowing the passage of dissolved gases (under negative pressure from a vacuum pump) but restricting the flow of the mobile phase.Several factors influenced the oxidation of the organic carbon in the next step, including the dose of persulfate, the type and intensity of UV radiation and the composition of the capillary through which the sample stream passes. Through optimisation of this process, it was found that a persulfate dose of 0.84 mmol L-1[superscript] in the sample stream was required for optimum oxidation efficiency. A medium pressure UV lamp was compared to a vacuum UV lamp for its efficiency in oxidation of organic carbon to carbon dioxide. While the medium pressure lamp produced a far smaller percentage of its total radiation at the optimum wavelength for oxidation of organic compounds, the greater overall intensity of the medium pressure lamp was shown to be superior for this application. The composition of the capillary was shown to have a considerable effect on the oxidation efficiency. A quartz capillary, internal diameter 0.6 mm, was compared with a PTFE capillary, internal diameter 0.5 mm, for the oxidation of organic carbon by external UV treatment. While peak width, an important consideration in chromatographic resolution, was greater for the larger internal diameter quartz capillary, the lower UV transparency of PTFE combined with the shorter contact time, due to the reduced internal diameter of the capillary, resulted in a less efficient oxidation step using the PTFE capillary. The quartz capillary was therefore chosen for use in the UV/persulfate oxidation step for oxidation of organic carbon to carbon dioxide. Separation of the produced carbon dioxide from the sample stream was achieved by sparging with nitrogen and contacting the gas/liquid mixture with a hydrophobic PTFE membrane, restricting the passage of the liquid while allowing the nitrogen and carbon dioxide gases to pass to the detection system.The only factor influencing this separation was the flow of the nitrogen sparge gas, with a flow of 2 mL min-1[superscript] found to be optimum. Detection of produced carbon dioxide was via a Fourier transform infrared (FTIR) spectrometer with a Iightpipe accessory. The Iightpipe accessory was designed for use as a detector for gas chromatography and the small size of the detector cell was ideal for use with this application. Using the new system described, concentrations of a single peak could be determined with a detection limit of 31 ng and a determination limit of 68 ng. The development of the new OCD allowed characterisation of NOM in terms of its MW distribution and the UV and fluorescence spectral properties of each MW fraction. Further characterisation of MW fractions of NOM from a local groundwater bore was carried out by separation of the fractions by preparative HPSEC, followed by off-line analysis. Preparative HPSEC involved the injection of a pre-concentrated groundwater sample multiple times, using a large scale HPSEC column, then collecting and combining material of identical MW. This allowed each MW fraction of the sample to be further characterised as described in Chapter 5. Preparative HPSEC has only previously been applied to a small number of samples for the concentration and fractionation of NOM, where the structural features of the various MW fractions were studied. In the current research, more extensive studies of not only the chemical characteristics, but also the disinfection behaviour, of the MW fractions were conducted. Separation of the sample was conducted on a large diameter silica-based HPSEC column, with fraction collection based on semi-resolved peaks of the HPSEC chromatogram. Nine MW fractions were collected by this method.After concentration and dialysis to remove the buffer salts in the HPSEC mobile phase, each fraction was re-analysed by analytical HPSEC-UV254[subscript] and showed a single Gaussian shaped peak, indicating discrete MW fractions had successfully been collected. Analysis of the collected MW fractions indicated that 57 % of the organic carbon was in Fractions 3 and 4, with 41 % in Fractions 5-9, leaving only 2 % in Fractions 1 (highest MW) and 2. For each of the nine MW fractions, chorine demand and 7 day trihalomethane formation potential (THMFP) were measured on dilute solutions of the same DOC concentration, and solid state 13[superscript]C NMR spectra were recorded on some of the solid isolates obtained after Iyophilisation of the separate or combined dialysis retentates. The larger MW Fractions 3 and 4 were found to contain a greater proportion of aromatic and carbonyl carbon, and the lower MW Fractions 5 and 6 and Fractions 7-9 contained greater proportions of aliphatic and O-aliphatic carbon, by this technique. Chlorine demand experiments on each individual fraction with a normalised DOC concentration indicated that the largest MW fraction (Fraction 1) had the lowest chlorine demand. It was concluded that material in this fraction may be associated with inorganic colloids and unavailable for reaction with chlorine. Fraction 3 had the highest chlorine demand, just over two times more than the next highest chlorine demand (Fraction 4) and approximately three times the chlorine demand of Fraction 2. The organic material in Fraction 2 was postulated to contain a mixture of the reactive material present in Fraction 3 and the colloidal associated material present in Fraction 1.NMR analysis indicated that the difference between Fraction 3 and Fraction 4 was a reduction in reactive aromatic carbon and hence the lower chlorine demand in the latter fraction. Fractions 5-8 had similar chlorine demands, lower than Fraction 4, while Fraction 9 had a very low chlorine demand similar to that of Fraction 1. For Fractions 5-9, the lower aromatic carbon content most likely resulted in the lower chlorine demand. The 7 day THMFP experiments showed some clear trends, with Fraction 1 and Fraction 2 producing the least amounts of THMs but having the greatest incorporation of bromine. Fractions 3 and 4 produced the greatest concentration of THMs with the lowest bromine incorporation, perhaps as they contained fast reacting THM precursors and the higher chlorine concentrations resulted in greater amounts of chlorinated THMs. Fraction 5 and Fraction 6 produced similar levels of THMs over 7 days to Fractions 7-9 (approximately 75% of the amount formed by Fractions 3 and 4), however, Fractions 7-9 formed these THMs more quickly than Fractions 5 and 6, with slightly greater amounts of bromine incorporation. It was thought that the increased speed of formation was due to the smaller MW of these fractions and a simpler reaction pathway from starting material to formation of THMs, as well as some structural differences. This research marks the first report of significantly resolved MW fractions being isolated and their behaviour in the presence of a disinfectant being determined. While the high MW fractions had the greatest chlorine demands and THMFPs, these fractions are also the easiest to remove during coagulation water treatment processes, as shown in Chapter 3. The lowest MW material formed significant amounts of THMs, and also formed THMs more quickly than other MW fractions.This has important implications from a water treatment perspective, as the lowest MW material is also the most difficult to remove during conventional treatment processes. Solid samples of NOM were isolated from water samples taken from four points at the Wanneroo GWTP using ultrafiltration and subsequent Iyophilisation of the retained fractions, as described in Chapter 6. The sampling points were following aeration (Raw), following treatment by MIEX®, following treatment by MIEX®-C and following treatment by EC. Elemental analysis, FTIR spectroscopy, solid state 13[superscript]C NMR spectroscopy and HPSEC-UV254[subscript]-0CD analysis were used to compare the four isolates. Treatment with MIEX®-C was found to remove the greatest amount of NOM. Additionally, treatment with MIEX®-C was able to remove the largest MW range of NOM, with the remaining material being depleted in aromatic species and having a greater proportion of aliphatic and O-aliphatic carbon. EC treatment completely removed the NOM components above 5000 Da, but NOM below this was not well removed. NOM remaining after the EC train had a lower aromatic content and more aliphatic oxygenated organic matter than the RW. The remaining organic matter after MIEX® treatment contained less aromatic material compared to the RW, but had a greater aromatic content than either of the EC or MIEX®-C samples. HPSEC was a significant analytical technique used throughout this research. Initial optimisation of an HPSEC method was an important development which allowed improved resolution of various MW fractions. The application of this technique and comparison of three detection systems for the study of DOC removal showed, for the first time, the performance of MIEX® treatment at a full scale groundwater treatment facility.The use of various HPSEC detection systems allowed significant characterisation of the MW fractions, more information than had previously been gathered from such a sample set. This work demonstrated the need for OCD when applying HPSEC to the study of NOM. As such, a system was constructed that built on previously developed systems, with the use of a small detector cell enabling detection limits capable of measuring even the most dilute natural and treated water samples. To study the individual MW fractions in detail, preparative HPSEC was applied and, for the first time, the disinfection behaviour of various MW fractions was examined. Interestingly, the lowest MW fractions, acknowledged to be the most recalcitrant to conventional water treatment processes, produced significant quantities of THMs. Also the formation kinetics of THMs from the low MW fractions indicated that THMs were formed as quickly as, or perhaps even at faster rates than from the larger MW fractions. Finally, structural characterisation of NOM at four stages of the Wanneroo GWTP indicated MIEX®-C treatment was superior to EC, of significant interest for the water industry.

Natural organic matter (NOM) occurs ubiquitously in drinking water supplies and is problematic since it serves as a precursor to disinfection by-products (DBPs) formation. Stricter DBP regulations will drive utilities to consider advanced treatment processes for DBP control through NOM removal. Herein, the transformation of NOM in homogeneous (UVA/H2O2 and UVA/Fe/H2O2) and heterogeneous (UVA/TiO2) Advanced Oxidation Processes (AOPs) were studied. Organic matter from three different sources was investigated in this work, specifically a commercial humic acid, and two Australian surface water sources. The transformation of the organic matter as a result of oxidation was investigated through multiple analytical techniques, such as UV-Vis spectroscopy, DOC analysis, high performance size exclusion chromatography (HPSEC), resin fractionation, liquid chromatography with organic carbon detection (LC-OCD) and disinfection byproducts formation potential. The multi-analysis approach is required due to the complex and heterogeneous nature of NOM. Each analytical technique provides complementary information on different properties of NOM, leading to a comprehensive understanding on how AOPs transform the chemical and physical properties of NOM. Both homogeneous and heterogeneous AOPs were found to be effective for NOM removal. However, complete mineralisation was not achieved, even under prolonged irradiation. Large aromatic and hydrophobic organics were degraded into lower molecular weight hydrophilic compounds, which had weak UV absorbance at 254 nm. In the UVA/TiO2 treatment, multi-wavelength HPSEC analysis demonstrated the formation of low molecular weight compounds with strong absorbance at wavelength lower than 230 nm. These residual organic compounds, though recalcitrant, had a low reactivity to chlorine to form THMs, and were identified to be low molecular weight acids and neutral compounds from LC-OCD analysis. Finally, the current work reports the novel synthesis of magnetic photocatalyst for NOM oxidation from low cost precursors to solve the separation problem of nano-sized particles. Magnetite particles were coated with a layer of protective silica from sodium silicate precursor. Photoactive titanium dioxide was then deposited onto the silica coated particles using titanium tetrachloride precursor. The as-prepared magnetic photocatalyst exhibited excellent stability and durability. Although the photoactivity of the magnetic photocatalyst is lower than commercial TiO2 photocatalyst, it can be easily recovered by magnetic field.

Industrial activities and accidental releases often introduce a large amount of inorganic and organic contaminants to the environment. Humic substances interact strongly with metals and organic pollutants. In this study, this property was exploited in order to establish new remediation materials in two environmental applications and in one pharmaceutical application. The two remediation materials under investigation were sludge and sediment, ST sludge and CE sludge, respectively. The first application aimed at investigating the use of the remediation materials to remove arsenic, iron, and uranium from the industrial effluents. The main results were the release of iron from ST sludge inhibited its usage as remediation material whereas CE sludge showed excellent performance. The extractions were both rapid and efficient. The second application studied the extraction of organic contaminants. The objective of this study was to find a new remediation material for removal of organic contaminants. The remediation materials showed similar and excellent performance on extraction of chlorinated anilines, phenols and benzenes. The third application investigated the extraction of iodine species from urine. It aimed at determining whether the radioactive iodine can be extracted from the urine and thereby concentrated into a smaller volume of solid. Even though the extraction percentages from urine were not as promising as from deionised water and synthetic urine, scientific interest was raised and further investigations on the effect of the composition of urine and solubility of sludges for the extraction of iodine species were recommended. The outcome of the presented study was interesting both scientifically and economically. The promising extraction results for arsenic, iron and uranium indicate that the CE sludge is ready to be tested in a field study. The extraction of organic compounds by both remediation materials was also promising. However, further studies on permeability and solubility were recommended.

The analytical capacity of MSSV pyrolysis has been used to extend the structural characterisation of aquatic natural organic matter (NOM). NOM can contribute to various potable water issues and is present in high concentrations (> 5 mg L-1) in many Australian source supplies. NOM can also impede the filtration performance of ultrafiltration or other membranes used in the increasingly popular practices of desalination and wastewater treatment. Characterisation studies that provide a detailed understanding of the origins, structural features and reactivity of NOM in source waters will help predict its impact on potable supplies and allow targeted treatment.MSSV pyrolysis GC-MS analyses were conducted on XAD fractions of NOM from selected rivers, reservoirs, ground waters and biologically treated waste waters. The analytical sensitivity of the MSSV Py approach was demonstrated by the detection of high concentrations and complex distributions of pyrolysates. These included many additional products to those detected by corresponding flash pyrolysis GC-MS analysis, which is often limited by excessive degradation or poor chromatographic resolution of pyrolysates of high structural polarity. Nevertheless, flash pyrolysis did lead to several unique products from some samples, reflecting the complementary nature of the two methods.Despite the high product concentrations detected by MSSV pyrolysis of NOM, primary structural fragments are prone to further alteration due to the confined nature and extended (e.g. 72 hr) application of the moderate thermal conditions (e.g. 300°C). This approach has not been widely applied to the characterisation of recent or immature OM. Consequently, the mechanistic formation of many NOM pyrolysates is poorly understood, seriously limiting interpretation of their source and significance. As articulated in CHAPTER 1, these issues are specifically addressed by the present research, which aims to extend the application of MSSV pyrolysis to the characterisation of NOM and related environmental organic materials rich in intact biochemical inputs. To gain a better understanding of product formation pathways, several samples, including soil leachates, the organic foulant of ultra filtration membranes and a suite of standards representing potential biochemical precursors of NOM were separately analysed by MSSV Py. The effect of thermal conditions on product distributions was also addressed by analysis of a small sub-set of the samples at several different temperatures (260 – 330°C for 72 hours).The capacity of MSSV Py to convert functionalised biochemical precursors into hydrocarbon products more amenable to GC resolution was initially demonstrated by the conversion of bacterial hopanepolyols of several surface and ground water NOM fractions, a bacterial isolate and biomass growth from an ultrafiltration membrane into corresponding hopane biomarkers as described in CHAPTER 2. The significance and integrity of the hopane distribution of the MSSV data was assessed by analyses of the same samples by flash pyrolysis and the advanced analytical techniques of hydropyrolysis (HyPy) GC-MS and liquid chromatography (LC)-MS with atmospheric pressure chemical ionisation. Flash pyrolysis showed no evidence of hopanes.In comparison to the distributions of intact biohopanoids detected by LC-MS, the microbial hopane biomarker signatures detected by MSSV Py and HyPy were generally consistent, although HyPy did produce higher concentrations of ββ−diastereoisomers and higher MW fragments indicating a lower degree of structural alteration. Hopane products were detected in very low concentrations in the NOM samples, hence bacterial contribution may be more conveniently detected with biological methods (e.g., microbial arrays, bacterial counts). Nevertheless, MSSV pyrolysis represents a simple, low cost analytical method able to confirm the occurrence of diagnostic bacterial biomarkers in complex environmental settings, such as source waters and surrounding catchments, and may be a useful screening method prior to more involved characterisation possible with LC-MS. Moreover, this application represents an elegant demonstration of the capacity of MSSV pyrolysis to provide new information concerning functionalised biological precursors which have historically proved difficult to analyse by GC(MS).Additional source diagnostic molecular features detected by MSSV Py of the membrane biofoulant included sterane biomarkers of eukaryote triterpenoids (i.e. steroids), n-alkanes of fatty acids and C16-C19 phenylalkanes indicative of common surfactants used to clean the membranes. The vastly improved molecular characterisation of the polar lipid constituents of membrane foulants, including the identification of industrial chemicals used in cleaning processes, suggests that this analytical capacity might also be applicable to monitoring the fate of organic constituents through the entire potable water system, from source through treatment and distribution to tap.Unlike the established bacterial hopanoid source of hopane biomarkers, the origins of most of the major products from MSSV pyrolysis of the NOM samples are not clear. Subsequent chapters were separately dedicated to a detailed investigation of several of the major product classes.CHAPTER 3 focused on the alkyl aromatic pyrolysates of NOM. The multitude of potential precursors of alkyl substituted benzenes and polycyclic aromatics (e.g. naphthalenes, phenanthrenes) significantly limits their diagnostic potential, nevertheless they represented a major proportion (20 – 50 % of total GC amenable pyrolysate signal) of the MSSV, and to a lesser degree, the flash pyrolysates of the HPO fractions of several NOM samples. The more highly substituted alkyl aromatics (and heteroatom products) of potentially greater source diagnostic value were better preserved by MSSV Py. Distinctive distributions of alkyl aromatics were detected by MSSV Py of the HPO fractions of several surface waters and a lysimetric plate collected ground water. All samples showed high alkyl benzene (AB) concentrations, whilst the ground water showed higher alkyl naphthalene (AN) concentrations than the surface waters. Correlation of several isopropyl substituted benzenes indicative of plant resin terpenoids in a bark sample, suggested these may be a significant source of the alkyl aromatics products of NOM. Furthermore, several higher plant derived polycyclic aromatic terpenoid biomarkers (e.g. cadalene, eudalene, retene and dehydroabietins) were also identified in the NOM fractions. Allochthonous and autochthonous sourced terpenoids have been proposed to be significant precursors of aquatic NOM; however diagnostic flash pyrolysis information about these types of contributors is typically limited.HPO fractions of two waste waters also showed consistently high concentration of alkyl aromatics, reflecting the general recalcitrance of their precursors to biological treatment. The distributions of these products differed from the natural surface and ground waters. Resistant aliphatic biomolecules derived from algal and bacterial biomass, susceptible to cyclisation and aromatization during MSSV Py, were tentatively assigned as the source of these distinctive pyrolysates.MSSV pyrolysis proved particularly sensitive to detection of heteroatom containing products of the NOM samples, and O products (25 – 50 %) and S products (1 – 5 %) were the focus of CHAPTER 4. The alkyl (≤ C4) phenols (APs) of the HPO fractions of the humic rich Gartempe and Uruguay rivers accounted for ca. 40 % of the total product signal. Similarly high concentrations of APs were detected by MSSV Py of a lignin standard, demonstrating the laboratory simulated thermal transformation of methoxy phenolic structures into alkyl phenols. The high concentrations of APs and low concentrations of methoxyphenol biomarkers of lignin typically detected in NOM (e.g. by flash pyrolysis, 13C NMR) suggests that a similar structural change may also be diagenetically mediated. The detection of APs, therefore, may be a more sensitive indicator of lignin input than guiaicyl or syringyl based biomarkers. The polyphenol structural units of selected tannin standards did not survive MSSV Py treatment, so are not likely responsible for the AP MSSV pyrolysates of the NOM samples. The HPO fraction of the waste waters showed similarly high concentrations of APs and alkyl aromatics (as discussed in Chapter 3), suggesting these products are recalcitrant to biological treatment. The Naintré waste waters also contained additional higher MW C4-10 alkyl substituted phenols not detectable by flash pyrolysis. Several of these products were indicative of industrial chemicals of potential health concern.The TPI and COL fractions showed significant concentrations of alkyl furans which along with cyclic ketones were present in much lower abundance than APs in the HPO fractions. These products were attributed to carbohydrate sources following correlation with mono- and polysaccharide standards including glucose, cellulose and chitin. Trace or low relative abundances of these products in the biologically treated wastewaters reflects their vulnerability to mineralization. The HPO fractions of the NOM samples also showed low concentrations of alkyl benzofurans, similar distributions of which were detected in the SRFA standard, suggesting these are more stable polysaccharide metabolites, but still prone to further biodegradation as evident by only trace concentrations detected in the waste waters.Whilst MSSV provided increased access to several S-structural constituents of NOM, their relatively low concentrations and as yet undefined structural origins remain a challenge to source characterisation. Nevertheless, similar alkyl thiophene (AT) distributions were also generated from an S-containing amino acid standard. Notably higher concentrations of S-products in the waste waters may reflect additional anthropogenic sources (e.g. sewerage, industrial chemicals), which may also involve thermally catalysed reaction between H2S and humic substances, analogous to the interaction of inorganic S and functionalised lipids during sedimentary diagenesis.CHAPTER 5 was concerned with the notably high concentrations of N products (3 - 50 %) detected by MSSV Py GC-MS of the NOM samples. These products included a large range of alkyl- pyrroles, pyridines, pyrazines and pyridinamines, as well as amine substituted mono-aromatics and condensed N-heterocyclics. They were consistently detected over a broader range of MSSV Py conditions. Many of these products, particularly those with increased alkyl substitution were not detected by flash pyrolysis; leading to an historic underestimation of their contribution to NOM. Highest concentrations of N-products were detected in the COL fraction of NOM. Similarly high concentrations and distributions were also detected from the organic material prone to foul ultrafiltration membranes, confirming the colloid rich nature of this material. The distinctive low MW N-heterocyclic products of the COL fractions were correlated with the N-products of the amino sugar standard, and to a lesser extent the protein standards. The occurrence in high concentrations of low MW heterocyclics also provides potentially rare evidence for the environmental occurrence of Maillard reactions. The interaction of sugars and amino acids via Maillard processes may be an important contributor to humic substances, although there is much doubt about whether this process is supported by ambient or near surface temperatures. As these reactions are more favourable at high temperatures they may be artefacts of the MSSV Py process. However, MSSV Py of mixtures of carbohydrate and amino acid standards showed no evidence for the production of additional low MW heterocyclics. The waste waters showed relatively high concentrations of alkyl carbazoles and β-carbolines, potentially derived from alkaloid precursors of plants, algae and bacteria, which have been implicated in toxic N-DBPs from potable water treatment.To practically assess the analytical benefits of MSSV pyrolysis for NOM characterisation, it was used in combination with other established analytical methods to holistically characterise the NOM of the North Pine (NP) reservoir, a major source of the potable water supplies of Brisbane and SE Queensland. The NP water is of low colour and has moderate dissolved organic carbon (DOC; 5 mg L-1) levels, but is impacted by algae which periodically occur in bloom proportions. The hydrophobic (HPO; 65 % initial DOC) and transphilic (TPI; 12 %) fractions from XAD resin separation of the DOC both showed high (>1) H/C values, low UVabs characteristics and low aromatic-C measured by NMR, which are all indicative of a relatively low degree of aromaticity. However, MSSV Py of both fractions, in particular the HPO fraction, yielded prolific distributions of alkyl substituted aromatic hydrocarbon (i.e., benzenes, naphthalenes) and hydroaromatic (e.g. tetralins) products. These were attributed to aromatisation of aliphatic structural precursors, including terpenoids of algae and plants, which are usually difficult to detect by analytical pyrolysis. MSSV Py of both fractions also yielded high concentrations of alkyl phenols, which likely reflect contribution from non-methoxylated lignin units of catchment grasses, consistent with the vast forest cleared grassland regions of the NP catchment, but may also derive from algal biopolymers. None of the analytical methods used showed any significant evidence of dihydroxy or methoxy aromatic structures of wood lignin or tannin inputs.MSSVpy of the TPI fraction showed very high abundances of N-products (e.g., alkyl pyrroles, pyridines, indoles) reflecting the structural significance of diagenetically altered proteins, most likely derived from algal biomass. In contrast, much fewer Nproducts were detected by flash Py. This demonstrates the analytical capacity of MSSV to access the significant N content of this fraction, which was quantitatively indicated by low C/N ratio, measured by elemental analysis, and high amide and amine signals by 13C NMR and FTIR spectroscopy.Whilst MSSV generated much higher product concentrations than flash Py or TMAH thermochemolysis, the latter methods did include unique product information demonstrating the complementary nature of different pyrolysis methods. Overall, this case study demonstrates the significant contribution MSSV Py has made to characterising the structure and sources of the Brisbane source water, clearly distinguishing it from humic black waters such as the Gartempe, Arroyo Sanchez and Suwannee Rivers studied in preceding chapters.This PhD project represents the first detailed study of the potential of using MSSV Py to assist the organic speciation and molecular characterisation of biochemically rich NOM. Important additional pyrolysis information can be released with this analytical method which represents an obvious complement to conventional flash pyrolysis techniques where chromatographic resolution of polar biochemicals can be limited. The full realization of this approach, however, will need much further development as briefly alluded to in the closing comments of CHAPTER 7. It is hoped that the present project makes a significant early step in the realization of this potential.

Membrane processes are increasingly used in water treatment. Experiments were performed using stirred cell equipment, polymeric membranes and synthetic surface water containing natural organics, inorganic colloids and their aggregates, and cations. All processes could remove a significant amount of natural organics. Pretreatment with ferric chloride was required to achieve significant organic removal with MF and high MWCO UF. Additionally, fouling mechanisms for the three processes were investigated. Crucial parameters were aggregate characteristics (fractal structure, stability, organic-colloid interactions), solubility of organics and calcium, and hydrodynamics. In MF, fouling by pore plugging was most severe. Variations in solution chemistry changed the aggregation state of the colloids and/or natural organic matter and dramatically affected rejection and fouling behaviour. UF membrane fouling was mainly influenced by pore adsorption and could improve natural organics rejection significantly. Coagulant addition shifted fouling mechanism from pore adsorption to cake formation. Aggregate structure was most significant for flux decline. In NF, rejection of natural organics involved both size and charge exclusion. Fouling was caused by precipitation of a calcium-organic complex. Fouling could be avoided by pretreatment with metal salt coagulants. Thorough chemical characterisation of the organics used demonstrated that only size and aromaticity can be related to fouling. The study is concluded with a process comparison based on a water quality parameter and a cost comparison. Treatment cost of microfiltration with chemical pretreatment was similar to that of nanofiltration at a comparable natural organics rejection.

Natural organic matter (NOM), ubiquitous in natural water sources, is generated by biogeochemical processes in both the water body and in the surrounding watershed, as well as from the contribution of organic compounds that enter the water as a result of human activity. NOM significantly affects the properties of the water source, including the ability to transport metals, influence the aggregation kinetics of colloidal particles, serve as a food source for microorganisms and act as a precursor in the formation of disinfection by-products (DBPs), as well as imparting a brown colour to the water. The reactivity of NOM is closely tied to its physicochemical properties, such as aromaticity, elemental composition, functional group content and molecular weight (MW) distribution. The MW distribution is an important consideration from a water treatment perspective for several reasons. For example, low MW NOM decreases the efficiency of treatment with activated carbon, and this fraction is thought to be the portion most difficult to remove using coagulation. The efficiency of membranes in the treatment of drinking water is also influenced by the MW distribution of NOM, while some studies have shown that the low MW fraction contributes disproportionately to the formation of bioavailable organic matter, therefore promoting the formation of biofilms in the distribution system. For these reasons, understanding the MW distribution of NOM is important for the treatment of natural waters for use as drinking waters. Optimisation of a high pressure size exclusion chromatography (HPSEC) method for analysis of the MW distribution of NOM in natural waters is described (Chapter 2). Several parameters influencing the performance of HPSEC are tested and an optimised set of conditions illustrated.
These parameters included eluent composition, ionic strength of the sample, flow rate and injection volume. Firstly, it was found that increasing the ionic strength of the HPSEC eluent resulted in less exclusion of NOM from the stationary phase. Stationary phases used in HPSEC contain a residual negative charge that can repel the negatively charged regions of NOM, effectively reducing the accessible pore volume. By increasing the ionic strength, interactions between the stationary phase and eluent enabled a larger effective pore size for the NOM analytes. However, increasing ionic strength of the eluent also resulted in a loss of peak resolution for the NOM portion able to access the pore volume of the stationary phase. Determining the ideal eluent composition required the balancing of these two outcomes. Matching of the ionic strength of the sample with the eluent was also an important consideration. Retention times were slightly lower when the sample ionic strength was not matched with the eluent, especially for the lowest MW material, although the effect on chromatography was minimal. Flow rate had no effect on the resolution of the HPSEC chromatogram for the portion of material able to permeate the pore space of the stationary phase. Changes in the volume of sample injected had a marked effect on the elution profile of the NOM sample. Besides the obvious limitation of detection limit, only minor changes in elution profile were obtained up to an injection volume of 100 µL. Volumes above this value, however, resulted in significant peak broadening issues, as well as an undesirable effect on the low MW portion of detected DOC.
In Chapter 3, high pressure size exclusion chromatography with UV254 [subscript] and on-line detection of organic carbon (HPSEC-UV254[subscript]-OCD) was used to compare the removal of different apparent MW fractions of DOC by two process streams operating in parallel at the local Wanneroo groundwater treatment plant (GWTP). One of these two process streams included alum coagulation (operating in an enhanced coagulation mode (EC) for increased DOC removal) and the other stream included a magnetic ion exchange (MIEX®) process followed by alum coagulation (MIEX®-C). The MIEX® process is based on a micro-sized, macroporous, strong base anion exchange resin with magnetic properties, which has been designed to remove NOM through ion exchange of the anionic sites in NOM. Water was sampled from five key locations within these process streams, and the DOC at each location was characterised in terms of its MW distribution. HPSEC was carried out using three different on-line detector systems, namely OCD, UV absorbance detection at 254 nm, and fluorescence detection (λex[subscript]= 282 nm; λim[subscript] = 353 nm). This approach provided significant information on the chemical nature of the DOC in the various MW fractions. The MIEX®-C process was found to outperform the EC process: these two processes removed similar amounts of high and low MW DOC, but the MIEX®-C process showed greater removal of DOC from the intermediate MW fractions. The two coagulation processes (EC and coagulation following MIEX®) showed good removal of the fractions of highest MW, while the MIEX® process alone was found to remove DOC across all MW fractions.
These results seem to indicate that anionic groups, particularly susceptible to removal with MIEX® treatment, are well distributed across all MW fractions of NOM. In agreement with previous studies, MIEX®-C outperformed EC in the overall removal of DOC (MIEX®-C removed 25 % more DOC than EC). However, 70% of the additional DOC removed by MIEX®-C was comprised of a surprisingly narrow range of medium-high MW fractions. The development of a novel online organic carbon detector (OCD) for use with HPSEC for determining the MW distribution of NOM is described in Chapter 4. With UV absorbance detection, the magnitude of the signal is based on the extinction coefficient of the chromophores in the analytes being investigated; whereas the signal from an OCD is proportional to the actual organic carbon concentrations, providing significantly more information. The development of an online OCD involved the separation of analytes using HPSEC, removal of inorganic carbon species which may interfere with organic carbon determination, oxidation of the organic carbon to carbon dioxide, separation of the produced carbon dioxide from the aqueous phase and subsequent detection of the gaseous carbon dioxide. In the new instrument, following separation of components by HPSEC, the sample stream was acidified with orthophosphoric acid to a concentration of 20 mmol L-1[superscript], resulting in a pH of ≤ 2, in order to convert inorganic carbon to carbon dioxide. This acid dose was found to remove greater than 99 % of inorganic carbon once the acidified sample was passed through a hydrophobic polytetrafluoroethylene (PTFE) membrane allowing the passage of dissolved gases (under negative pressure from a vacuum pump) but restricting the flow of the mobile phase.
Several factors influenced the oxidation of the organic carbon in the next step, including the dose of persulfate, the type and intensity of UV radiation and the composition of the capillary through which the sample stream passes. Through optimisation of this process, it was found that a persulfate dose of 0.84 mmol L-1[superscript] in the sample stream was required for optimum oxidation efficiency. A medium pressure UV lamp was compared to a vacuum UV lamp for its efficiency in oxidation of organic carbon to carbon dioxide. While the medium pressure lamp produced a far smaller percentage of its total radiation at the optimum wavelength for oxidation of organic compounds, the greater overall intensity of the medium pressure lamp was shown to be superior for this application. The composition of the capillary was shown to have a considerable effect on the oxidation efficiency. A quartz capillary, internal diameter 0.6 mm, was compared with a PTFE capillary, internal diameter 0.5 mm, for the oxidation of organic carbon by external UV treatment. While peak width, an important consideration in chromatographic resolution, was greater for the larger internal diameter quartz capillary, the lower UV transparency of PTFE combined with the shorter contact time, due to the reduced internal diameter of the capillary, resulted in a less efficient oxidation step using the PTFE capillary. The quartz capillary was therefore chosen for use in the UV/persulfate oxidation step for oxidation of organic carbon to carbon dioxide. Separation of the produced carbon dioxide from the sample stream was achieved by sparging with nitrogen and contacting the gas/liquid mixture with a hydrophobic PTFE membrane, restricting the passage of the liquid while allowing the nitrogen and carbon dioxide gases to pass to the detection system.
The only factor influencing this separation was the flow of the nitrogen sparge gas, with a flow of 2 mL min-1[superscript] found to be optimum. Detection of produced carbon dioxide was via a Fourier transform infrared (FTIR) spectrometer with a Iightpipe accessory. The Iightpipe accessory was designed for use as a detector for gas chromatography and the small size of the detector cell was ideal for use with this application. Using the new system described, concentrations of a single peak could be determined with a detection limit of 31 ng and a determination limit of 68 ng. The development of the new OCD allowed characterisation of NOM in terms of its MW distribution and the UV and fluorescence spectral properties of each MW fraction. Further characterisation of MW fractions of NOM from a local groundwater bore was carried out by separation of the fractions by preparative HPSEC, followed by off-line analysis. Preparative HPSEC involved the injection of a pre-concentrated groundwater sample multiple times, using a large scale HPSEC column, then collecting and combining material of identical MW. This allowed each MW fraction of the sample to be further characterised as described in Chapter 5. Preparative HPSEC has only previously been applied to a small number of samples for the concentration and fractionation of NOM, where the structural features of the various MW fractions were studied. In the current research, more extensive studies of not only the chemical characteristics, but also the disinfection behaviour, of the MW fractions were conducted. Separation of the sample was conducted on a large diameter silica-based HPSEC column, with fraction collection based on semi-resolved peaks of the HPSEC chromatogram. Nine MW fractions were collected by this method.
After concentration and dialysis to remove the buffer salts in the HPSEC mobile phase, each fraction was re-analysed by analytical HPSEC-UV254[subscript] and showed a single Gaussian shaped peak, indicating discrete MW fractions had successfully been collected. Analysis of the collected MW fractions indicated that 57 % of the organic carbon was in Fractions 3 and 4, with 41 % in Fractions 5-9, leaving only 2 % in Fractions 1 (highest MW) and 2. For each of the nine MW fractions, chorine demand and 7 day trihalomethane formation potential (THMFP) were measured on dilute solutions of the same DOC concentration, and solid state 13[superscript]C NMR spectra were recorded on some of the solid isolates obtained after Iyophilisation of the separate or combined dialysis retentates. The larger MW Fractions 3 and 4 were found to contain a greater proportion of aromatic and carbonyl carbon, and the lower MW Fractions 5 and 6 and Fractions 7-9 contained greater proportions of aliphatic and O-aliphatic carbon, by this technique. Chlorine demand experiments on each individual fraction with a normalised DOC concentration indicated that the largest MW fraction (Fraction 1) had the lowest chlorine demand. It was concluded that material in this fraction may be associated with inorganic colloids and unavailable for reaction with chlorine. Fraction 3 had the highest chlorine demand, just over two times more than the next highest chlorine demand (Fraction 4) and approximately three times the chlorine demand of Fraction 2. The organic material in Fraction 2 was postulated to contain a mixture of the reactive material present in Fraction 3 and the colloidal associated material present in Fraction 1.
NMR analysis indicated that the difference between Fraction 3 and Fraction 4 was a reduction in reactive aromatic carbon and hence the lower chlorine demand in the latter fraction. Fractions 5-8 had similar chlorine demands, lower than Fraction 4, while Fraction 9 had a very low chlorine demand similar to that of Fraction 1. For Fractions 5-9, the lower aromatic carbon content most likely resulted in the lower chlorine demand. The 7 day THMFP experiments showed some clear trends, with Fraction 1 and Fraction 2 producing the least amounts of THMs but having the greatest incorporation of bromine. Fractions 3 and 4 produced the greatest concentration of THMs with the lowest bromine incorporation, perhaps as they contained fast reacting THM precursors and the higher chlorine concentrations resulted in greater amounts of chlorinated THMs. Fraction 5 and Fraction 6 produced similar levels of THMs over 7 days to Fractions 7-9 (approximately 75% of the amount formed by Fractions 3 and 4), however, Fractions 7-9 formed these THMs more quickly than Fractions 5 and 6, with slightly greater amounts of bromine incorporation. It was thought that the increased speed of formation was due to the smaller MW of these fractions and a simpler reaction pathway from starting material to formation of THMs, as well as some structural differences. This research marks the first report of significantly resolved MW fractions being isolated and their behaviour in the presence of a disinfectant being determined. While the high MW fractions had the greatest chlorine demands and THMFPs, these fractions are also the easiest to remove during coagulation water treatment processes, as shown in Chapter 3. The lowest MW material formed significant amounts of THMs, and also formed THMs more quickly than other MW fractions.
This has important implications from a water treatment perspective, as the lowest MW material is also the most difficult to remove during conventional treatment processes. Solid samples of NOM were isolated from water samples taken from four points at the Wanneroo GWTP using ultrafiltration and subsequent Iyophilisation of the retained fractions, as described in Chapter 6. The sampling points were following aeration (Raw), following treatment by MIEX®, following treatment by MIEX®-C and following treatment by EC. Elemental analysis, FTIR spectroscopy, solid state 13[superscript]C NMR spectroscopy and HPSEC-UV254[subscript]-0CD analysis were used to compare the four isolates. Treatment with MIEX®-C was found to remove the greatest amount of NOM. Additionally, treatment with MIEX®-C was able to remove the largest MW range of NOM, with the remaining material being depleted in aromatic species and having a greater proportion of aliphatic and O-aliphatic carbon. EC treatment completely removed the NOM components above 5000 Da, but NOM below this was not well removed. NOM remaining after the EC train had a lower aromatic content and more aliphatic oxygenated organic matter than the RW. The remaining organic matter after MIEX® treatment contained less aromatic material compared to the RW, but had a greater aromatic content than either of the EC or MIEX®-C samples. HPSEC was a significant analytical technique used throughout this research. Initial optimisation of an HPSEC method was an important development which allowed improved resolution of various MW fractions. The application of this technique and comparison of three detection systems for the study of DOC removal showed, for the first time, the performance of MIEX® treatment at a full scale groundwater treatment facility.
The use of various HPSEC detection systems allowed significant characterisation of the MW fractions, more information than had previously been gathered from such a sample set. This work demonstrated the need for OCD when applying HPSEC to the study of NOM. As such, a system was constructed that built on previously developed systems, with the use of a small detector cell enabling detection limits capable of measuring even the most dilute natural and treated water samples. To study the individual MW fractions in detail, preparative HPSEC was applied and, for the first time, the disinfection behaviour of various MW fractions was examined. Interestingly, the lowest MW fractions, acknowledged to be the most recalcitrant to conventional water treatment processes, produced significant quantities of THMs. Also the formation kinetics of THMs from the low MW fractions indicated that THMs were formed as quickly as, or perhaps even at faster rates than from the larger MW fractions. Finally, structural characterisation of NOM at four stages of the Wanneroo GWTP indicated MIEX®-C treatment was superior to EC, of significant interest for the water industry.

Nedbrytning av organiskt material är en nyckelfaktor som påverkar omvandlingar av de många grundämnen som utgör eller är associerade till just organiskt material. En stor del av nedbrytningen av akvatiskt organiskt material (OM) sker i gränsskiktet mellan sediment och vatten. Eftersom så många biogeokemiska cykler styrs av nedbrytningen av OM är det viktigt att ha kunskap om processer och påverkansfaktorer både på mikro- och makronivå. Mineraliseringshastigheten av OM är en vanligt förekommande mätparameter, men vanligtvis inkluderar mätningarna inte de naturliga processer som kan påverka nedbrytnings-hastigheterna, t.ex. fysiska krafter.

Syftet med den här studien är att studera mineraliseringshastigheten av det OM som finns naturligt i ytsediment i söt- och brackvatten när det utsätts för fysiska krafter som orsakar förändringar i redox-förhållanden, resuspension eller advektivt porvattenflöde. Fem

laborativa experiment har utförts för att belysa syftet:

Åldrat ytsediment från en sötvattens å utsattes för olika redox förhållanden där oxisk respiration, sulfatreduktion respektive metanogenes gynnades. Resultaten visade ingen skillnad i mineraliseringshastighet beroende på behandling. Detta motsäger studier utförda i marina miljöer, där anoxiska förhållanden ger en lägre mineraliseringshastighet än oxiska.

Vidare gjordes två studier på brackvattensediment där effekten av resuspension var i centrum. Den ena studien fokuserade på frekvens och varaktighet av resuspensionstiderna, den andra på olika typer av sediment. Studierna visade att väldigt korta resuspensionstider med upp till 48 timmars stillhet mellan varje resuspension ökade mineraliseringstakten med fem gånger jämfört med diffusivt utbyte, och mer än dubblerades i jämförelse med kontinuerlig resuspension eller resuspension i långa perioder. Resuspensionen under kort tid var troligen gynnande då resuspension fysiskt stör bildningen av stabila bakteriesamhällen. Mineraliseringshastigheterna i sediment som domineras av väldigt fin, fin eller medium sand visade lika hastigheter, medan grov sand visade en signifikant lägre mineraliseringshastighet. Likheterna mellan de tre första sedimenttyperna kan dock ha påverkats av tillgång på lättnedbrytbart OM då sediment och vatten hämtades in under en algblomning.

Till sist studerades effekten på mineraliseringshastigheten av advektivt porvattenflöde. Detta gjordes på åldrat sediment dels från en sötvattensbäck dels från en brackvattenstrand. Inget av de två sedimenttyperna visade någon skillnad i mineraliseringshastighet i jämförelse med diffusivt styrda system. Det är i motsats till tidigare marina studier, men är i linje med den första studien, där mineraliseringshastigheten var oberoende av redox-förhållande.

Den generella slutsatsen från den här studien är nödvändigheten att studera samma aspekter i olika typer av akvatiska system, eftersom responsen verkar vara annorlunda beroende på system, t.ex. söt- brack- och saltvatten. Faktorer som kan förklara de här skillnaderna finns ännu inte, vilket gör att småskaliga studier och modeller blir viktiga verktyg för att utreda detta.

Organic matter mineralisation is a key parameter that affects most other element transformations associated with organic matter. A substantial part of aquatic organic matter (OM) mineralisation takes place at the interface between sediment and water. Understanding OM mineralisation is important at both the micro and macro scales, since it drives many biogeochemical cycles. OM mineralisation rates are widely measured, but generally not all the natural factors possibly affecting the rates, such as physical forcing, are considered.

This thesis examines the mineralisation rates of indigenous OM in fresh and brackish surface sediments, subjected to different physical forces inducing changed redox conditions, resuspension, and advective pore water flow. Five experiments were performed to this end.

Aged surface sediment from a freshwater river was subjected to different redox conditions favouring oxic respiration, sulphate reduction, and methanogenesis, respectively. Results indicated no difference in mineralisation rate irrespective of treatment. This contradicts what has been found in marine environments, where anoxic mineralisation rates are lower than oxic ones.

Further, two studies of resuspension of brackish sediments were performed, one addressing the impact of the frequency and duration of the resuspension events, and the other addressing the impact of resuspension on different types of sediments. The studies found that very brief resuspension events followed by calm periods of up to 48 h increased mineralisation rates by five times compared to diffusion, and more than doubled the rate compared to continuous or long-term resuspension. The short-term events were possibly favoured because resuspension physically disturbs the arrangement of a stable bacteria community. Mineralisation rates on sediments dominated by very fine, fine, or medium-grained sand were the same, while coarse sand displayed a significantly lower rate. The similar rates of the three first sediment types could stem from access to labile OM, due to an ongoing algae bloom when the sediment and water samples were collected.

Finally, the effect of advective pore water flow on aged sediment from one fresh and one brackish sediment was studied. Neither of the sediments displayed a mineralisation rate different from those occurring in incubations in which only diffusive exchange occurred. This contradicts the findings of previous marine studies, but is in line with the first study, which did not detect different mineralisation rates irrespective of redox conditions.

The general conclusion is that it is necessary to study the same physical forces in different aquatic environments, since responses appear to differ, for example, between freshwater, brackish, and marine environments. Factors explaining these differences have not yet been expressed, making small-scale studies and modelling a challenge for future research.

Volcanic ash, pumice and Moringa oleifera (M. oleifera) were investigated as indigenous materials for removal of natural organic matter (NOM) at Kampala and Masaka water treatment plants in Uganda. Coagulation and filtration experiments were done using raw water at Kampala (Ggaba) and Masaka (Boma) National Water & Sewerage Corporation water treatment plants. Assessment of the two plants was done and they were found to be faced with differing challenges given the nature of their raw water sources. Therefore, the study was conducted to seek appropriate treatment processes that suite the conditions at the respective plant and avoid or minimize formation of unwanted chlorination by-products. The results from the study indicated that there were both operational and design handicaps at the Ggaba treatment plant with a need to modify the filtration and clarification units. At Masaka, pre-chlorination led to increases in total trihalomethanes as high as 4000%. The characterization studies indicated the major fraction of NOM to be hydrophilic and there was no variation in the character of NOM along the unit treatment processes investigated. On the other hand experiments conducted at both the pilot and laboratory scale gave promising results. Simple horizontal flow roughing filter at Masaka gave rise to dissolved organic carbon (DOC) and ferrous iron removals of 27% and 89% respectively. With a combined use of pumice and hydrogen peroxide in the filter, DOC removals of up to 68% were achieved. The results from jar test experiments also indicated that use of alum with M. oleifera coagulant extracted with sodium chloride solution as coagulant aid is promising as a first stage in the treatment train for waters with a humic materials and high content of iron, typical of swamp water sources. Therefore the findings show that it is possible to avoid the formation of unwanted by-products by application of roughing filtration with hydrogen peroxide in place of the pre-chlorination process. Assessment of the characteristics of the volcanic ash showed that it meets the requirements for a filtration material; and results obtained from the pilot study showed that it was a suitable alternative material for use in a dual media filtration system. There was an increase in the filter run length of about two and half fold in the dual media filtration column compared to the mono medium column.
Vulkanaska, pimpsten och Moringa oleifera (M. oleifera) undersöktes som inhemska material for borttagande av naturligt organiskt material (NOM) i Kampala och Masaka reningsverk i Uganda. Koagulation och filtreringsexperiment gjordes med hjalp av råvatten i Kampala (Ggaba) och Masaka (Boma)reningsverk, som ingår i Nationella Vatten- och avloppsreningsverk, ett företag i Uganda. En bedömning av de två anläggningarna gjordes och det visade sig stå inför olika utmaningar på grund av de olika råvattnens karaktär. Den här studien genomfördes för att söka lämpliga processer för behandling av anpassade till förhållandena vid respektive anläggning samt för att undvika eller minimera uppkomsten av olika klorerade biprodukter. Resultatet från studien visade att det fanns problem både när det gäller design och arbetsrutiner på reningsverket Ggaba med ett behov att ändra filtrerings- och klarningsenheternaI Masaka ökade förkloreringsprocessen den totala mängden trihalometaner med 4000 %. Karakteriseringen av naturligt organiskt material (NOM) visade på en stor andel hydrofilt material och att ingen förändring av det organiska materialets karaktär skedde längs den undersökta processenheten. Å andra sidan visade både laboratorieförsök och experiment i pilotanläggningen att lovande resultat. Ett enkelt horisontellt flöde genom ett grovt filter i pilotanläggningen i Masaka resulterade i 89% mindre järn och 27% mindre NOM. Med en kombination av pimpsten och väteperoxid i filtret var avlägsnandet av löst organiskt material(DOC) från vattnet 68%. Resultaten från batchexperiment (jar test) i laboratoriet visade också lovande resultat för aluminium tillsammans med en koagulant extraherad med natriumklorid från Moringa oleifera (MOC-SC), som ett första steg för vatten från sumpmark med höga halter av järn och organiskt material. Således visar resultaten att det går att undvika bildandet av höga halter av trihalometan (THM) genom genom tillämpning av grovfitrering med väteperoxid i stället för förkloreringsprocessen. Utvärderingen av vulkanaskans egenskaper visade att vulkanaskan uppfyller kraven på ett filtermaterial och resultaten från pilotanläggningen visade att det är ett lämpligt material i ett filtreringssystem med två media. Den utnyttjade delen av filtret var 2,5 gånger längre i körningen med dubbla medier jämfört med ett medium.

QC 20120910

MAKERERE – Sida/SAREC RESEARCH COLLABORATION

Mangroves are the dominant vegetation in Everglades estuarine environment and are known to contain polyphenols such as tannins, which present similar fluorescence properties as some amino acid fluorophores. In the present study, gas chromatography–mass spectrometry (GC/MS) was used to quantify gallic acid, which is a normal monomer of polyphenols. The quantitative GC/MS analytical method was developed using gallic acid and tannic acid standards to quantify the false ‘protein-like’ fluorescence in DOM. The present study also compared the optical properties, reactive species (RS) production and radical scavenging ability of DOM from different regions of the Everglades and a correlation was observed between DOM composition and its photo-productivity. In general, the reactive species quantum yield decreased with increased DOM redox potential. The RS formation rates were controlled by the DOC and CDOM abundace. Normalized RS formation rates were shown to be influenced by DOM aromaticity and molecular weight characteristics

Natural organic matter (NOM) is described as an intricate mixture of organic compounds that occurs universally in ground and surface waters. After treatment for potable use, there is NOM remaining in the water that reacts with the chlorine used for disinfection to form disinfection by-products (DBPs). Some of the DBPs, trihalomethanes (THMs) are regulated. Several water treatment works (WTWs) in the Yorkshire Water and United Utilities (previously North West Water) region in England have recently experienced difficulty in meeting THM limits (100 µg L-1) in their finished drinking water at certain times of the year. An investigation into how NOM changes seasonally, pragmatic methods of NOM analysis and its reactivity with chlorine was undertaken. By separating the NOM using adsorbent resins into fractions, it was possible to gain an insight into the seasonality of NOM. It was observed that a particular, difficult to remove fraction was always more reactive with respect to THM formation in autumn. Some of the methods proposed in the literature were used here with varying successes. It was found that High Performance Size Exclusion Chromatographic methods were most useful to the WTW operators for optimising treatment processes. It is known that the formation of DBPs is very complex. An attempt was made to predict the reactivity of a raw water in terms of THM-FP by looking at the NOM makeup. However, it was found that the fluorescence spectra combined with the fluorescence index of raw water and chlorinated samples gave more insight into the reactivity of the raw water at a particular time than knowing the fraction distribution. The use of fluorescence as a tool for understanding chlorine-NOM reactions is promising.

Removal of organic matter is increasingly important to drinking water utilities and consumers. Organic matter is a significant precursor in the formation of disinfection by-products (DBPs). The maximum contaminant levels for (DBPs) are decreasing and more DBPs are believed carcinogenic. Traditional coagulation focuses on the removal of particulate matter and in the last decade soluble species have also been targeted with high coagulant doses. However, colloidal matter is smaller than particulate matter and therefore not easily removed by conventional drinking water treatment. This research focused on the conversion of soluble organic matter to colloids using relatively low doses of ferric sulfate coagulant and the subsequent removal of the colloids by filtration during drinking water treatment. The goal is to achieve enhanced removal of soluble organic matter with minimal chemical costs and residual formation. This study investigated the effects of pH, iron coagulant dose, turbidity, organic matter concentration, and temperature on colloid formation. Characterization of the colloidal organic matter was attempted using zeta potential and sizing analyses. Cationic low molecular weight, nonionic high molecular weight, and cationic medium molecular weight polymers were evaluated on their removal of colloidal organic matter. Colloidal organic matter formation was affected by changes in coagulation pH, coagulant dose, and organic matter concentration, whereas turbidity and temperature did not significantly impact colloid formation. Decreased coagulation pH caused increased organic carbon removal. As coagulant dose was increased, colloid formation initially increased to maximum and subsequently rapidly decreased. Colloid formation was increased as the organic matter concentration increased. Due to low sample signal, the colloids could not be characterized using zeta potential and sizing analyses. In addition, polymers were ineffective for aggregating colloidal organic matter when used as flocculant aids.
Master of Science