Watersheds within northwestern Mississippi, a productive agricultural region referred to as the Delta, were recently identified as contributors of total nitrogen and phosphorus fluxes to the Gulf of Mexico. Water withdrawals for irrigation in the Delta have altered flow paths between surface-water and groundwater systems, allowing for more surface-water losses to the underlying alluvial aquifer. In order to understand how to manage nitrogen in a watershed, it is necessary to identify and quantify hydrologic flow paths and biogeochemical conditions along these flow paths, which ultimately combine to determine transport and fate. In order to evaluate the extent and role of surface-water losses to the alluvial aquifer on the transport of nitrate, a two-dimensional groundwater/surface-water exchange model was developed for a site within the Delta. Results from this model determined that groundwater/surface-water exchange at the site occurred regularly and recharge was laterally extensive into the alluvial aquifer. Nitrate was consistently reported in surface-water samples (n= 52, median concentration = 39.8 micromol/L), although never detected in samples collected from instream or near stream piezometers (n=46). Coupled model and water-quality results support the case for denitrification/ nitrate loss from surface water moving through an anoxic streambed. At larger scale, recent results from two Spatially Referenced Regressions on Watershed attributes (SPARROW) models imply that nitrogen is transported relatively conservatively once it enters the main channel of the Big Sunflower River Basin, which contributes much of the water discharging from the Yazoo River Basin to the Mississippi River. Net loss of nitrogen was assessed by comparing total nitrogen data from Lagrangian sampling events to chloride, drainage area, and predicted total nitrogen flux results from the SPARROW models. Results indicated relatively conservative instream transport of nitrogen at the scale of the Big Sunflower River Basin; however, two potential nitrogen loss mechanisms were identified: (1) transport and transformation of nitrogen through the streambed, and (2) sequestration and transformation of nitrogen above the drainage control structures downstream of Anguilla.

The production of methyl mercury, an acute neurotoxin which readily accumulates in the tissue of organisms, is a biologically mediated process facilitated by sulfate reducing bacteria in aquatic sediments. In-situ capping is a frequently considered risk management strategy for contaminated sediments. Since placement of an in-situ cap will induce anaerobic conditions that are known to be favorable for the growth of sulfate reducing bacteria, there is justifiable concern that capping could increase mercury methylation in underlying sediments. This research builds an understanding of the effects of in-situ capping on underlying biogeochemical processes and elucidates their importance in controlling methyl mercury production. Laboratory experiments and mathematical models were implemented to simulate mercury methylation in redox conditions likely to be induced by capping using sediment from different environments. Mathematical descriptions of processes known to be involved in methylation were incorporated into the model to quantify the effects of these processes. Observations in both well-mixed slurry conditions and intact sediment columns showed that methyl mercury concentrations are strongly dependent upon biogeochemical conditions. Results from experiments with sediment spanning a range of redox conditions and organic contents suggested that sulfate reduction rates, aqueous speciation, and solid phase partitioning are involved in limiting methylation depending on bulk geochemical characteristics. A model with a mechanistic basis that incorporates the effects of these processes provides a useful means of qualitatively and quantitatively considering their cumulative impact in limiting methyl mercury production. High methyl mercury concentrations observed in some lab experiments suggest that there is reason to be concerned about anoxic conditions induced by capping; however, not all anoxic conditions led to equivalent increases in methyl mercury. Experimental and modeling results suggest that in a high organic environment, in-situ capping may produce conditions which accelerate methylation in (formerly) surficial sediment while in a low organic environment, with an overall lower potential for methylation, capping can be expected to have a less dramatic effect. Over time, two processes will temper capinduced increases in methyl mercury. Increases will only last until sulfide builds up to inhibitory levels in underlying sediment or until organic carbon is depleted and overall bacterial activity slows. By providing a more fundamental understanding of the effects of capping on mercury methylation, the results of this research will aid in identifying situations and conditions in which cap-induced increases in methyl mercury have the potential to limit the effectiveness of the management strategy. / text

Before January 2003, the Dapeng Bay lagoon was occupied by oyster culture racks and fish farming cages. Along with the development of the Dapeng Bay National Scenic Area Administration, the government has started taking actions on removing oyster culture racks, and has kept improving the quality of lagoon water. Nowadays, the government is implementing sediment dredging plan. As to discuss the change of biogeochemical processes, this study is divided by three parts, including the first stage, before the removal of oyster culture rafts; second stage, after the removal of oyster culture rafts, and the third stage, after implementation of sediment dredging. At the first stage, the annual mean of water exchange time at the Dapeng Bay was approximately 10 days. At the second and third stage, the annual mean of water exchange time were 6.2 days and 8.3 days, respectively. The difference is not significant between the second stage and third stage. The trend of water exchange time is similar to the seawater exchange rate. Distributions of chlorophyll a were controlled by temperature and solar radiation, rather than by nutrient concentration throughout three-stage periods. Although the change tendency between chlorophyll a, DIN, and DIP at the third stage is similar, chlorophyll a correlated positively with DIN and DIP only in fall. The net ecosystem production (NEP) was positive (p¡Ðr > 0) at all three stages, so the Dapeng Bay was always an autotrophic system throughout the study period. Before the removal of the oyster culture racks, the NEP was 5.64 mole C m-2 yr-1, after that, it increase to 11.64 mole C m-2 yr-1. During the sediment dredging period, the NEP was 14.31 mole C m-2 yr-1. The NEP increases 106 % from the first stage to the second stage, and increases 23% from the second stage to the third stage. The environmental remediation appears to produce significant influence on NEP. The concentration of DIN¡BDSi¡BDIP decreases by removing the oyster culture of racks. But the concentrations of particulate and dissolved organic carbon and nitrogen increase sharply after removing the oyster culture racks. Nevertheless, the concentration of dissolved organic carbon, nitrogen and the phosphorus decreases during the third stage, resulted mainly from the improvement of water quality. The system changed from the condition of phosphorus surplus (Si/N=1.8¡Ó1.2 and N/P=7.4¡Ó5.2) during the first and second stage to the condition of phosphorus limitation (Si/N=1.0¡Ó1.2 and N/P=22.2¡Ó18.7) during the third stage. The ratios of particulate organic carbon and nitrogen (POC/PN) are 7.7¡Ó1.1, 8.0¡Ó1.0, 6.5¡Ó1.3, respectively. The ratio at the third stage is very close to the Redfield ratio (C/N=6.6), which may result from the improvement of water quality. In terms of temporal and spatial variation of various parameters, DO variability was strong in the time scale than in the spatial scale, but nutrients and POC show a decrease of spatial variability from the first stage to the third stage. The removal of oyster culture racks, and the implementation of sediment dredging plan at the Dapeng Bay have significant influence on the improvement of lagoon environment for the past ten years.

This study aims to understand the role of the Tapong Bay on carbon biogeochemical cycle in the coastal zone and the influence of terrigenous inputs on ecosystem functioning in the Tapong Bay. The Tapong Bay is a semi-enclosed lagoon, occupied largely by fish farming cages and oyster culture racks. There is only one tidal inlet for exchanging water between the Tapong Bay and Taiwan Strait, which results in a low water exchange rate and oxygen deficient condition in the bottom water of the inner bay. The annual mean of water exchange time is about 10.6 days that is much longer than that in the Chiku Lagoon (5.8 days). Experimental results show that biological activity and variations of hydrochemistry primarily control the distributions of carbon and nutrients. Excess of DIP likely occurred in the Tapong Bay. Seasonal variations of primary productivity are apparently controlled by temperature, solar radiation and turbidity. The regression slope between particulate organic carbon and nitrogen approaches the Redfield ratio, indicating that organic carbon is derived primarily from biological production. The stratification of water column in the Tapong Bay was observed throughout the year. Diffusion from sediment may thus contribute significantly to nutrient distributions in bottom water. Diffusion flux estimated from porewater to bottom water is about 7.6% of annual mean input for DIN and is about 1.0% for DIP. Calcification process was observed in the Tapong Bay indicating that the oyster culture would affect the carbon budget in the bay. The annual mean production rate of organic carbon estimated from the biogeochemical model is about 5.80 mole C m-2 yr-1, implying that the Tapong Bay is an autotrophic system. The net ecosystem production (NEP) derived from diel observation is about 6.29 mmole C m-2 d-1 that is closed to 6.65 mmole C m-2 d-1 estimated from the biogeochemical modeling. The annual nitrogen fixation exceeds the annual denitrification [(nfix-denit)¡×1.30 mole m-2 yr-1] in the Tapong Bay. Carbon biogeochemical fluxes and budgets differ significantly between the Tapong Bay and the Chiku Lagoon, which may be arisen from pronounced difference in terrigenous inputs and seawater exchange rates.

Contaminated sediments are periodically subjected to resuspension processes during either storm events or due to dredging. In sediments, metals are often contained in insoluble low bioavailability forms. Upon resuspension, however, biogeochemical processes associated with the exposure to more oxic conditions may lead to transformation and release of the metals, giving rise to exposure and risk in the water column. Batch experiments suggested that oxidation of reduced species and corresponding pH decrease were the most importance processes controlling metals release upon sediment resuspension. A mathematical model was implemented to better understand the complex underlying biogeochemical reactions that affect metals release. The model described the metals dynamics and other inter-related important biogeochemical factors well and was successful at predicting the metals release from different sediment reported in the literature. Tidal and other cyclic variations in oxygen, pH and other relevant parameters in the overlying water may also lead to cyclic transformations and release of metals from surficial sediments. In simulated estuarine microcosm experiments, cyclic variations in pH and salinity due to freshwater/saltwater exchange were shown to lead to cyclic variations in metal release. Both pH and salinity were important factors controlling interstitial dissolved metals concentrations, however, in terms of freely dissolved metals concentrations, which have been considered to be more related with toxicity and bioavailability, pH was the single most important parameter. The mathematical model was extended to the conditions of the cyclic behavior in an estuary and successfully described metals release under such conditions. It is believed that the model can be used to predict the metals behavior in other sediments and conditions by model calibration with a similar experimental approach to that used in this study. / text

This dissertation focuses on understanding the complex interactions between hydrological and geochemical processes, and specifically how these interactions are affected by subsurface heterogeneity across scales. Heterogeneity in the form of macropores and fractures provide preferential flowpaths and affect contaminant transport. Biogeochemical processes are also strongly affected by such heterogeneities. Any lithological layering or interface (e.g. plume fringe, wetland-aquifer boundary, etc.) increases biogeochemical activity around that interface. Hydrologic conditions, rainfall events, drainage patterns, and pH variations are also dominant controls on redox processes and thereby affect contaminant distribution and migration. An inherent limitation of modeling fate and transport of contaminants in the subsurface is that the interactions among biogeochemical processes are complex and non-linear. Therefore, this research investigates the effect of hydrological variations and physical heterogeneity on coupled biogeochemical processes across column and landfill scales. Structural heterogeneity in the form of macropore distributions (no macropore, single macropore, and multiple macropores) in experimental soil columns is investigated to accurately model preferential flow and tracer transport. This research is crucial to agricultural systems where soil and crop management practices modify soil structure and alter macropore densities. The comparison between deterministic and stochastic approaches for simulating preferential flow improved the characterization of interface parameters of the dual permeability model, and outlined the need for efficient sampling algorithms or additional datasets to yield unique (equifinal) soil hydraulic parameters. To evaluate the effect of heterogeneity on redox processes, repacked soil columns with homogeneous and heterogeneous (layered) profiles from soil cores collected at the Norman Landfill site, Oklahoma, USA were employed. Results indicate that heterogeneity in the form of textural layering is paramount in controlling redox processes in the layered column. To evaluate the effect of hydrologic conditions on redox processes, temporal data at the Norman landfill site was used. Results indicate that seasonal hydrologic variations exert dominant control over redox-sensitive concentrations. An integrated MCMC algorithm was devised to upscale linked biogeochemical processes from the column to the field scale. Results indicate that heterogeneity and hydrologic processes are paramount in controlling effective redox concentrations at the Norman landfill site.

A qualidade da matéria orgânica e a magnitude de suas deposições estão entre os principais fatores que controlam as respostas dos organismos bênticos marinhos. Uma vez depositada nos sedimentos, a matéria orgânica é degradada por processos biogeoquímicos microbianos, que podem ser acelerados mediante a bioturbação da macrofauna. Entretanto, em regiões costeiras, a dinâmica das forçantes ambientais influencia tanto a qualidade dos recursos alimentares, quanto os mecanismos de utilização pelos organismos, implicando em alterações na remineralização da matéria orgânica. Este estudo visou investigar o sistema bêntico da área costeira de Ubatuba frente às variações da qualidade e quantidade da matéria orgânica, incluindo os impactos da bioturbação na diagênese recente e regeneração de nutrientes. Observou-se que os processos físicos da região atuaram na variação da qualidade da matéria orgânica e na estruturação dos organismos bênticos. Os microorganismos exploraram matéria orgânica de diferentes composições, exercendo também importante papel para a comunidade macrobêntica, enriquecendo os detritos orgânicos disponíveis como alimento. A meiofauna não apresentou relação direta com alta qualidade da matéria orgânica, já a macrofauna foi estruturalmente modificada pela passagem de frentes frias e pela presença de compostos lábeis, quando os mesmos apareceram em maiores concentrações. Experimentalmente, verificou-se que a mistura de partículas foi significativa somente quando altas densidades da macrofauna estiveram presentes na superfície do sedimento. Além disso, foi demonstrado em laboratório que a macrofauna exerceu pouca influência nos fluxos de oxigênio e nutrientes do sedimento para a água, porém suficiente para estimular a decomposição de material orgânico verticalmente na coluna sedimentar. Portanto, a dinâmica dos processos físicos e as variações estruturais da macrofauna são importantes fatores ecológicos na modulação de funções fundamentais do ecossistema costeiro de Ubatuba, como produtividade, metabolismo bêntico, degradação da matéria orgânica e fluxos de energia. / The magnitude and quality of organic matter inputs to the seafloor are among the main factors regulating the responses of marine benthic communities. Once deposited on the sediments, the organic matter is degraded by several microbial biogeochemical processes that may be stimulated through macrofauna bioturbation. However, in coastal regions the dynamics of environmental forcing not only influences the quality of food sources, but the food uptake by organisms, resulting in changes on remineralization rates of organic material. This study aimed to investigate the benthic system of Ubatuba coastal area in relation to quality and quantity of organic matter as well as bioturbation impacts on early diagenesis and nutrient regeneration. Data suggests that physical stresses influenced the quality of organic matter and the structure of benthic organisms. Different compositions of organic matter were assimilated by microorganisms, which in turn played an important role to the macrobenthic community, enriching the organic detritus available as food. The meiofaunal organisms did not numerically respond to the deposition of high quality organic matter, while macrofauna community structure was modified by the incidence of cold fronts and by the presence of labile compounds, whenever available. Experimentally, sediment reworking was only significant at higher levels of macrofaunal density on the sediment surface. In addition, it was demonstrated in laboratory that macrofauna imposed weak effects on the fluxes of oxygen and nutrients from sediments to the water column, but those changes were enough to stimulate vertically in the sediments, the decomposition of organic matter. Therefore, the dynamics of physical processes and the variability on macrofaunal structure are both important ecological factors modulating fundamental functions of the coastal ecosystem in Ubatuba, including productivity, benthic metabolism, degradation of organic matter and energy flow.

A qualidade da matéria orgânica e a magnitude de suas deposições estão entre os principais fatores que controlam as respostas dos organismos bênticos marinhos. Uma vez depositada nos sedimentos, a matéria orgânica é degradada por processos biogeoquímicos microbianos, que podem ser acelerados mediante a bioturbação da macrofauna. Entretanto, em regiões costeiras, a dinâmica das forçantes ambientais influencia tanto a qualidade dos recursos alimentares, quanto os mecanismos de utilização pelos organismos, implicando em alterações na remineralização da matéria orgânica. Este estudo visou investigar o sistema bêntico da área costeira de Ubatuba frente às variações da qualidade e quantidade da matéria orgânica, incluindo os impactos da bioturbação na diagênese recente e regeneração de nutrientes. Observou-se que os processos físicos da região atuaram na variação da qualidade da matéria orgânica e na estruturação dos organismos bênticos. Os microorganismos exploraram matéria orgânica de diferentes composições, exercendo também importante papel para a comunidade macrobêntica, enriquecendo os detritos orgânicos disponíveis como alimento. A meiofauna não apresentou relação direta com alta qualidade da matéria orgânica, já a macrofauna foi estruturalmente modificada pela passagem de frentes frias e pela presença de compostos lábeis, quando os mesmos apareceram em maiores concentrações. Experimentalmente, verificou-se que a mistura de partículas foi significativa somente quando altas densidades da macrofauna estiveram presentes na superfície do sedimento. Além disso, foi demonstrado em laboratório que a macrofauna exerceu pouca influência nos fluxos de oxigênio e nutrientes do sedimento para a água, porém suficiente para estimular a decomposição de material orgânico verticalmente na coluna sedimentar. Portanto, a dinâmica dos processos físicos e as variações estruturais da macrofauna são importantes fatores ecológicos na modulação de funções fundamentais do ecossistema costeiro de Ubatuba, como produtividade, metabolismo bêntico, degradação da matéria orgânica e fluxos de energia. / The magnitude and quality of organic matter inputs to the seafloor are among the main factors regulating the responses of marine benthic communities. Once deposited on the sediments, the organic matter is degraded by several microbial biogeochemical processes that may be stimulated through macrofauna bioturbation. However, in coastal regions the dynamics of environmental forcing not only influences the quality of food sources, but the food uptake by organisms, resulting in changes on remineralization rates of organic material. This study aimed to investigate the benthic system of Ubatuba coastal area in relation to quality and quantity of organic matter as well as bioturbation impacts on early diagenesis and nutrient regeneration. Data suggests that physical stresses influenced the quality of organic matter and the structure of benthic organisms. Different compositions of organic matter were assimilated by microorganisms, which in turn played an important role to the macrobenthic community, enriching the organic detritus available as food. The meiofaunal organisms did not numerically respond to the deposition of high quality organic matter, while macrofauna community structure was modified by the incidence of cold fronts and by the presence of labile compounds, whenever available. Experimentally, sediment reworking was only significant at higher levels of macrofaunal density on the sediment surface. In addition, it was demonstrated in laboratory that macrofauna imposed weak effects on the fluxes of oxygen and nutrients from sediments to the water column, but those changes were enough to stimulate vertically in the sediments, the decomposition of organic matter. Therefore, the dynamics of physical processes and the variability on macrofaunal structure are both important ecological factors modulating fundamental functions of the coastal ecosystem in Ubatuba, including productivity, benthic metabolism, degradation of organic matter and energy flow.

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.

Les déchets sulfurés issus de l’extraction des minerais métalliques génèrent des drainages miniers acides (DMA) contenant des éléments toxiques tels que l’arsenic. Les procédés de traitement passifs basés sur l’oxydation bactérienne du fer et de l’arsenic, en favorisant la précipitation de ces éléments sous une forme stable, pourraient représenter une solution efficace et économique pour traiter cette pollution. Dans ce contexte, l’objectif général de cette thèse était de mieux comprendre les facteurs environnementaux et opérationnels qui contrôlent l’efficacité d’élimination de l’arsenic. Une approche en pilote à flux continu a été mise en oeuvre afin de se rapprocher des conditions réelles d’un traitement. L’étude a été conduite d’abord à l’échelle d’un bioréacteur de paillasse en conditions contrôlées (température, lumière, débit, temps de séjour et hauteur d’eau), puis dans un dispositif de taille supérieure, fonctionnant de manière totalement passive et in situ. Ces dispositifs ont été alimentés avec de l’eau d’un DMA riche en arsenic, issue de l’ancien site minier de Carnoulès, dans le Gard. Les caractéristiques de l’eau et des bioprécipités au sein de ces pilotes, en particulier le rédox du fer et de l’arsenic, ont été suivis dans différentes conditions environnementales et d’opération par des méthodes de spéciation liquide et solide (HPLC-ICP-MS, EXAFS, XANES), des analyses minéralogiques (DRX) et des analyses microbiologiques (ARISA, séquençage haut débit du gène de l'ARNr 16S, quantification du gène aioA). Les résultats issus des expériences en laboratoire ont mis en évidence l’effet de différents paramètres opérationnels (hauteur d’eau, temps de rétention hydraulique, et présence/absence d’une pellicule flottante) sur les performances du traitement, ainsi que sur la microbiologie et la minéralogie des bioprécipités formés. Le dispositif de terrain a permis de tester les performances du procédé dans des conditions environnementales fluctuantes (variabilité de la physico-chimie de l’eau d’entrée et de la température) et d’acquérir des connaissances nouvelles sur l’évolution des bioprécipités au cours de six mois de traitement. Les connaissances acquises dans cette thèse pourront servir de base à la conception d’une étape d’élimination de l’arsenic dans les processus de traitement des DMA. / Acid mine drainage (AMD) are produced by sulfuric tailings from mining of metal ores. They are characterized by high contents of toxic elements like arsenic. One efficient and economical solution for the treatment of As in these tailings could be the use of a passive method based on iron and arsenic bacterial oxidation, and the subsequent precipitation of these elements in a stable form. In this context, the objective of this PhD thesis was to better understand the environmental and operational factors controlling the efficiency of As removal processes. A continuous-flow pilot approach was implemented in order to better reproduce the real treatment conditions. This study was first performed in a bench-scale bioreactor with controlled conditions (temperature, light, flow, residence time and water height). Then, it was performed in a field-scale bioreactor installed in situ, reproducing a passive treatment in real conditions. These devices were fed with As-rich AMD waters from the ancient mine of Carnoulès (Gard, France). Water and bioprecipitate properties were monitored in both devices, specially the redox speciation of iron and arsenic. This monitoring was held for different environmental and operational conditions. Iron and arsenic speciation in liquid and solid phases was measured by different analytical techniques such as HPLC-ICP-MS, EXAFS and XANES. Mineral identification was made by XRD analysis, while microbiological characterization was made by ARISA, high-throughput sequencing of 16S rRNA gene, and aioA gene quantification. Results from the lab-scale experiments evidenced the effects of the different operational parameters (water height, hydraulic retention time and the presence/absence of a floating film) on the treatment performance, as well as on the microbiology and mineralogy of the produced bioprecipitates. The field device was used to test the treatment performance under fluctuating environmental conditions (variability of the physico-chemistry of the feed water and of the temperature) and to gain new knowledge about the evolution of the bioprecipitates during six months of treatment. All the knowledge acquired in this PhD thesis could serve as a basis for the design of an arsenic removal stage in DMA treatment processes.