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Landfill leachates are often treated on-site before disposal to municipal wastewater treatment plants, although variations in leachate composition and organic loading continue to have negative impacts on downstream treatment processes.  Leachate samples were collected from four landfills both before and after on-site treatment to evaluate the extent of biological treatment. The samples vary in age, location, and on-site treatment processes.  Size fractionation utilizing microfiltration (MF) and ultrafiltration (UF) was conducted in conjunction with TOC, nitrogen species, and UV254 absorbance analysis to determine the characteristics of organic constituents present in landfill leachate.  The size fraction less than 1thousand Daltons (1 kDa) was responsible for a predominant portion of the organic fraction of the landfill leachates studied.  Humic substances are refractory components present in landfill leachates that are resistant to biological treatment and responsible for a portion of the UV quenching ability of leachates.  Humic substances were also fractionated to humic acid (HA), fulvic acid (FA), and hydrophilic (Hpi) components before being subjected to size fractionation to determine UV254 absorbance and organic fractions.  Particle size and hydrophobic-hydrophilic fractionation were conducted in series to evaluate the potential for membrane treatment after biological treatment as a cost effective alternative to reverse osmosis processes currently used to decrease the organic fractions present in landfill leachate.  The organic nitrogen fraction was predominately in the hydrophilic fraction smaller than 1 kDa. / Master of Science

Dissolved organic nitrogen (DON) represents a major pool of fixed, reactive nitrogen in marine systems. It is now recognized that this pool can support primary production and the ability of some algal species to exploit DON compounds as sources of Nitrogen (N) may indicate that specific DON components can exert selective pressure on the composition of the phytoplankton community. In this study the ability of monocultures of ecologically-relevant algal species from the English Channel (Emiliania huxleyi, Micromonas pusilla, Alexandrium minutum and Chaetoceros peruvianus) to grow with DON as the only N source was examined using different artificial media. Among the two tested artificial seawater recipes, Aquil* was preferred as it contained lower micronutrient concentrations, and gave better growth results for all used species. In order to constrain the DON uptake to algae alone, a method for bacterial removal was tested using antibiotic additions. Both Slocombe antibiotic mixture (Cefotaxime-Carbenicillin-Kanamycin-AugmentinTM) and Penicillin-Streptomycin-Neomycin used were effective and not toxic to the algae. Incubation with the antibiotic up to 48 hours and a transfer period into antibiotic-free medium after 72 hours proved to be effective. However, the treatment removed bacteria in A. minutum cultures only; further treatment would be required for the other species to be cultured axenically. The ability to use DON was tested for the above mentioned species using the amino acid L-Arginine (ARG) as the sole N source, and growth was compared with nitrate-containing cultures of the same species. All the selected species grew in both NOᴈ‾ and in ARG, reaching lower final densities when incubated with ARG, although these were not significant. This study has shown that E. huxleyi, A. minutum, M. pusilla and C. peruvianus can grow on organic N, either by direct or indirect uptake, and develop comparable biomasses to species using inorganic N. Both C. peruvianus and M. pusilla cultures contained dissolved ammonium at the end of the experimental period, indicating potential indirect use by the algae of organic N converted to inorganic N by bacteria. A. minutum grew in the presence of ARG along with the cosmopolitan E. huxleyi; N-demand estimates, based on the molar concentration of N-ARG consumed, correlated with the final cell density, indicating that the species did not develop on inorganic N produced from ARG mineralisation, but directly on the ON substrate. Since A. minimum has been linked to harmful algal blooms, and E. huxleyi contributes significantly to oceanic CaCOᴈ deposition, their ability to utilise DON has environmental consequences in addition to the oceanic N-budget. Climate change scenarios predict both episodic conditions of elevated rainfall and extended periods of dry conditions leading to variable riverine inputs to coastal areas, altered nitrogen to phosphorus (N:P) ratios, and changes in the inorganic to organic balance of the nutrient pools. Organic N can constitute up to 69 % of the total N pools, respectively, making it crucial, to understand the cycling of this fraction in coastal waters, and how changes in the composition of nutrient pools could impact on marine ecosystem function and health.

Dissolved organic nitrogen (DON) represents a significant portion (25-80%) of total dissolved nitrogen in the final effluent of wastewater treatment plants (WWTPs). DON in treated wastewater, once degraded, causes oxygen depletion and/or eutrophication in receiving waters and should be reduced prior to discharge. Biodegradability, bioavailability, and photodegradability are important characteristics of wastewater derived DON and are subjects of research in this dissertation. Four research tasks were performed. In the first task, laboratory-scale chemostat experiments were conducted to examine whether solids retention time (SRT) could be used to control DON and biodegradable DON (BDON) in treated wastewater. Nine different SRTs from 0.3 to 13 were studied. There was no correlation between effluent DON and SRTs. However, BDONs at SRTs of 0.3 to 4 days were comparable and had a decreasing trend with SRTs after that. These results indicate the benefit of high SRTs in term of producing effluent with less BDON. The second task was a comprehensive year-round data collection to study the fate of DON and BDON through the treatment train of a trickling filter (TF) WWTP. The plant removed substantial amounts of DON (62%) and BDON (76%) mainly through the biological process. However, the discharged concentrations in the effluent were still high enough to be critical for a stringent total nitrogen discharge limit (below 5 mg-N/L). Evolution of bioavailable DON (ABDON) along the treatment trains of activated sludge (AS) and TF WWTPs and relationship between ABDON and BDON were examined in the third task. ABDON exerted from a combination of bacteria and algae inocula was higher than algae inoculated ABDON and bacteria inoculated BDON suggesting the use of algae as a treatment organism along with bacteria to minimize effluent DON. The TF and AS WWTPs removed 88% and 64% of ABDON, respectively. In the last task, photodegradable DON (PDON) in primary wastewater and final effluent from TF and AS WWTPs was studied. PDON and BDON fractions of DON data in the final effluent of TF and AS WWTP samples elucidate that photodegradation is as critically important as biodegradation when mineralization of effluent DON is a concern in receiving waters.

This thesis assesses the possible photochemical transformations of nitrogen fixed in organic compounds. The aim of this study was to monitor the kinetics and seasonal trends in photochemical degradation of dissolved organic matter and nitrogen in the first order stream.

Previous studies on the effects of land cover influence on stream nitrogen have focused on base flow conditions or were conducted specifically within urbanized or primarily agricultural watersheds. While these studies have shown relationships between land cover and nitrogen, this relationship and the scale of influence could change during storms. The purpose of my study was to understand how land cover influences nitrogen in streams during storms. This was address using nine watersheds within the Little Tennessee Basin in North Carolina. While this basin is primarily forested, the nine watersheds have mixed agricultural, built, and forest land cover. Land cover influences were addressed through nitrogen concentration/discharge patterns, nitrogen concentration relationship to land cover, and comparison of storm and base flow nitrogen concentrations over time. Weekly base flow samples and samples from six storm were collected in 2010-2011. Total dissolved nitrogen (TDN), nitrate (NO??), dissolved organic nitrogen (DON), and ammonium (NH?⁺) concentrations were compared among sites. During most storms, DON peaked before the peak of the discharge while NO?? peaked after the peak of the storm. This suggest that DON could be coming from a near stream source or surface runoff while NO?? could be from longer pathways such as subsurface flow or from sources further away on the watershed. NO?? concentration varied among sites, while DON concentration varied more between base flow and storm samples. Examining the different landscape scales from 200-m local corridor, 200-m stream corridor, and entire watershed, watershed land cover was the best predictor for all the nitrogen concentrations. Agricultural and built combined best predicted TDN and NO??, while agricultural land cover was a better predictor of DON. For storms, nitrogen concentrations did not show seasonal patterns but was more related to discharge. Nitrogen concentration increased with discharge during storms and the more intense and longer storms had higher TDN and NO?? concentrations. However, conflicting seasonal trends were seen in monthly base flow. The more forested watersheds had high NO?? during the summer and low NO?? in the winter. For sites with higher NO??, the seasonality was reversed, with higher winter NO?? concentration. The least forested site had relatively constant nitrogen through the year at base flow and concentration decreased for most storms. Further studies on storms and nitrogen transport are needed to understand better the seasonal patterns of nitrogen input during storms. / Master of Science

Abstract The South China Sea (SCS) is the largest marginal sea in the world and connects with the East China Sea (ECS) through the Taiwan Strait (TS). This study investigates the distribution and biogeochemical behavior of both particulate and dissolved organic matter in the SCS and the TS based on samples collected on several cruises of the R/V Ocean Researchers I and III. Dissolved inorganic nitrogen and phosphorus (DIN and DIP), particulate organic carbon and nitrogen (POC and PON) as well as dissolved organic nitrogen and phosphorus (DON and DOP) concentrations were determined. Concentrations of DON and DOP in the SCS are in the range of 1.2-9.9 mMN and 0.04-0.21 mMP, respectively. The surface DON concentration is the highest in the northern SCS, whereas it is the lowest in the southern part. The DOP does not show a similar trend. DON and DOP concentrations all decrease with depth but increase slightly near the bottom, perhaps on account of sediment resuspension. Because of the preferential degradation of DOP over DON, the maximum concentration of DOP appears at a shallower depth than that of DON. Approximately 11 % and 2 % of DIN and DIP respectively are attributed to the degradation of DON and DOP above 500 m in the SCS. Concentrations of POC and PON in the SCS are in the range of 1.06-2.84 mMC and 0.07-0.36 mMN, respectively. The distributions of POC and PON show similar patterns with a correlation coefficient of 0.97. The concentrations of these are the highest at the surface layer, decrease with depth, but then increase slightly near the bottom, perhaps again because of resuspension of the bottom sediments. The ratio of PON/POC is 0.138 in the euphotic zone, a value close to the Redfield ratio of 0.15. In the TS and the adjacent coastal zones, the effect of terrestrial input is obvious and results in higher POC, PON, DON and DOP nearshore. Ranges of these concentrations are 0.06-59.6 mMN, 0.01-1.29 mMP, 3.80-57.1 mMC and 0.19-3.4 mMN, respectively. There was an attempt to use the one-dimensional diffusion-advection model to estimate the DIN and DIP production rates and the DON and DOP consumption rates over the depth range of 900-2500 m. These values are, respectively, 0.036, 0.006, 0.021 and 0.002 mmol/kg/yr.

A dissertation submitted to the Faculty of Engineering, University of the Witwatersrand, in fulfillment of the requirements for the degree of Master of Science in Engineering / South Africa, like many other developing countries, is faced with rapid urbanisation with the associated increase in the pollution load. Much of this pollution is destined for our watercourses, that eventually run into storage reservoirs which may be used for drinking water or recreational purposes. This pollution is usually attributed to human waste products which include nitrogenous wastes, phosphates, microorganisms, organic material and litter, A 6km stretch of the Jukskei river just downstream of Alexandra Township, was used to determine the different biological, physical and chemical processes that pollutants undergo during natural assimilation, their rates and efficiencies of assimilation in rivers and their impact Oil the environment downstream of the urban area. "Grab" samples were taken over a period which included both low-flow and storm events. Due to the high concentration of nutrients in the run-off from Alexandra Township, the major changes seen were in the biological conversion of organic nitrogen compounds and ammonia to nitrates, in the BOD and in the concentration of dissolved oxygen in the river, with lows of 1.1 to 1.5 mg/l 02 being recorded at Alexandra. A rapid rise in the concentration of faecal coliforms has been seen with a high of 31 million/100 ml being recorded at Alexandra in September, 1994. Sedimentation at the Alexandra site is also a common occurrence with a lot of adsorbed pollutants being effectively removed from the water column with the suspended solids. The QUAL2E water quality model, used by the EPA in the United States, was used to model the reactions that the nutrients, BOD and DO undergo. BOD and DO were modelled very well with r of 0.98 and 0.94 being calculated respectively. QUAL2E did not model tile dissolved potlutants, dissolved phosphorus and ammonia very well with the observed results showing a greater reduction ill these pollutants. A method by which these pollutants adhere to SS and settle out was / AC2017

<p>Organic nitrogen compounds are important in environmental systems because they are prevalent in natural waters but are also components of polymers within membrane filters that are used for water treatment. In both of these cases, these compounds can be exposed to free chlorine during disinfection, which can trigger a set of reactions that can form a host of different halogenated by-products. When such by-products form during water treatment disinfection, these by-products, known as nitrogen-based disinfection by-products (N-DBPs), can be highly toxic and affect human and ecosystem health. Alternatively, when such reactions occur during membrane filtration, the organic nitrogen compounds, which are embedded within the upper layer polymer structure of the membrane filter, can degrade when free chlorine is applied. Therefore, this research was aimed at exploring the chemistry behind how specific types of organic nitrogen compounds which are found in these applications, such as tertiary amines and amides, react with free chlorine. It particularly focused on assessing the kinetics and by-product formation of these reactions under variable water quality conditions (e.g., pH, halide concentrations, and precursor doses).</p> <p> </p> <p>More specifically, in the first phase of this work, the roles of tertiary amines in enhancing disinfection by-product (DBP) formation, such as trihalomethanes (THMs) and haloacetic acids (HAAs), during chlorination of aromatic compounds were studied. The results indicated that in synthetic solutions, chloroform (CHCl₃) and trichloroacetic acid (TCAA) were enhanced by up to 20× with tertiary amines at low dose ([tertiary amine]₀ = 0.5×[aromatic compound]₀). The enhancement effect was also dependent on the aromatic compound type, tertiary amine type and dose, and water conditions such as pH and bromide concentrations. Thus, THMs and HAAs were predicted to be enhanced when the aromatic compound reacted with R₃N-X⁺ (X=Br or Cl) and was not outcompeted by aromatic compound or tertiary amine reaction with free chlorine or bromine alone. In the second phase of this work, the reaction kinetics, by-product formation, and overall mechanisms of a polyamide-based monomer with chlorine were evaluated under varying water conditions. The current known mechanism, Orton Rearrangement, was reevaluated, and new mechanisms were proposed, where it was found that N-halogenation and ring halogenation were two independent pathways. The ability to choose either pathway was highly dependent on the water quality condition of the aqueous solution. The roles of different chlorinating/brominating agents were also investigated where certain species-specific rate constants were obtained. For the N-halogenation pathway, only chlorination and no bromination occurred in which the reactivity of the chlorinating agents likely decreased such that ClO^->HOCl. However, for the ring halogenation pathway, both chlorination and bromination occurred in which the reactivity of the chlorinating and brominating agents decreased such that Cl₂ >HOCl, and BrCl > BrOCl > Br₂ > Br₂O > HOBr, respectively. Overall, this study suggests that a number of unique reactions can occur for various types of organic nitrogen compounds which: (i) allow them to affect water quality by enhancing DBP formation, (ii) but, when integrated into a polymer matrix used for water treatment, can induce reactions that lead to permanent structural damage of the polymer. In all cases, the extent of these reactions is strongly governed by the surrounding water matrix.</p>