In previous research, ranitidine has formed high yields of the disinfection by-product N-Nitrosodimethylamine (NDMA) upon chloramination. In the current research, bench-scale experiments were conducted to investigate the impact of cations (i.e., Ca2+, Mg2+, and Na+) on NDMA formation from ranitidine in three water matrices (Milli-Q® water, Lake Ontario water, and Otonabee River water) under practical chloramine disinfection conditions. In Milli-Q® water, excess cations did not change the yields of NDMA. NDMA formation kinetic profiles monitored in the lake and river water also indicated that elevating the cation concentrations did not affect the ultimate NDMA formation from ranitidine, but then did affect the observed rates of NDMA formation; the rates underwent an initial decrease and a subsequent increase as the cation concentrations were increased. The lowest reaction rates were observed in the lake and river water samples when they have a hardness level of 240 and 203 mg/L as CaCO3, respectively.

N-Nitrosodimethylamine (NDMA), which is a carcinogenic and toxic N-nitrosamine, can be found in water resources associated with a multitude of processes in various industrial facilities or merely as a by-product of water or wastewater treatment. Therefore, the removal of NDMA from drinking water represents an important human safety and public health concern. The present paper presents a density functional theory study of NDMA adsorption in all-silica MFI, Na-ZSM-5 and H-ZSM-5 zeolites. The stability of NDMA inside the zeolite pores was investigated by calculating the amount of energy released during adsorption. Various configurations of adsorbed NDMA to the zeolites were investigated, predominantly at the intersection of straight and sinusoidal channels. The strength of the adsorption energies followed the order H-ZSM5 > Na-ZSM-5 > all-silica MFI. NDMA has a dipole moment and the strongest binding of NDMA occurred through the interactions of the negatively charged O atom of the molecule to positive atoms of the zeolite. Similar calculations were performed for water adsorption in these three zeolites. The adsorption energy of water to these three structures followed the order Na-ZSM5 > H-ZSM-5 > all-silica MFI. We also incorporated van der Waals corrections in the simulations, which had the effect of stabilizing NDMA within the zeolite channels, but did not significantly change the relative stability of the different adsorption geometries. It was concluded that H-ZSM-5 is the best choice to remove NDMA because it is strong enough to adsorb NDMA and it is not too strong in adsorption of water molecules.

abstract: Advanced oxidation processes (AOP’s) are water/wastewater treatment processes simultaneously providing disinfection and potential oxidation of contaminants that may cause long-term adverse health effects in humans. One AOP involves injecting peracetic acid (PAA) upstream of an ultraviolet (UV) irradiation reactor. Two studies were conducted, one in pilot-scale field conditions and another under laboratory conditions. A pilot-scale NeoTech UV reactor (rated for 375 GPM) was used in the pilot study, where a smaller version of this unit was used in the laboratory study (20 to 35 GPM). The pilot study analyzed coliform disinfection and also monitored water quality parameters including UV transmittance (UVT), pH and chlorine residual. Pilot study UV experiments indicate the unit is effectively treating flow streams (>6 logs total coliforms) twice the 95% UVT unit capacity (750 GPM or 17 mJ/cm2 UV Dose). The results were inconclusive on PAA/UV inactivation due to high data variability and field operation conditions creating low inlet concentrations.Escherichia coli (E. coli) bacteria and the enterobacteria phage P22—a surrogate for enteric viruses—were analyzed. UV inactivated >7.9 and 4 logs of E. coli and P22 respectively at a 16.8 mJ/cm2 UV dose in test water containing a significant organics concentration. When PAA doses of 0.25 and 0.5 mg/L were injected upstream of UV at approximately the same UV Dose, the average E.coli log inactivation increased to >8.9 and >9 logs respectively, but P22 inactivation decreased to 2.9 and 3.0 logs, respectively. A bench-scale study with PAA was also conducted for 5, 10 and 30 minutes of contact time, where 0.25 and 0.5 mg/L had <1 log inactivation of E. coli and P22 after 30 minutes of contact time. In addition, degradation of the chemical N-Nitrosodimethylamine (NDMA) in tap water was analyzed, where UV degraded NDMA by 48 to 97% for 4 and 0.5 GPM flowrates, respectively. Adding 0.5 mg/L PAA upstream of UV did not significantly improve NDMA degradation. The results under laboratory conditions indicate that PAA/UV have synergy in the inactivation of bacteria, but decrease virus inactivation. In addition, the pilot study demonstrates the applicability of the technology for full scale operation. / Dissertation/Thesis / Masters Thesis Civil and Environmental Engineering 2017

No description available.

N-Nitrosodimethylamine (commonly known as NDMA) is a probable human carcinogen that has been recognized as an emerging drinking water contaminant in recent years. Previous studies have shown that certain N-containing organic compounds may form NDMA in reaction with chlorine or monochloramine and the NDMA yield is affected by the structure of the organic-N compounds, water conditions and treatment parameters. Many amine-based water treatment polymers contain organic-N functional groups and thus have been suspected as potential NDMA precursors in water treatment systems. The purpose of this research was to systematically assess the potential NDMA formation from different structural types of water treatment polymers in reactions with various oxidants and probe the possible factors that influence the NDMA formation. Robust analytical methods for detection of NDMA and the well-known NDMA precursor dimethylamine (DMA) in the reaction samples were established. The cationic polyacrylamide (cationic PAMS), aminomethylated polyacrylamide (Mannich), poly-diallyldimethylammonium chloride (polyDADMAC) and polyamine polymers were evaluated in reactions with nitrite, free chlorine, monochloramine or chlorine dioxide in aqueous solutions at circumneutral pH and room temperature conditions. This study employed high dosages of polymer and oxidant and long reaction time in order to assess the maximum potential to form NDMA. A range of operational parameters that may affect the above reactions were also evaluated.

abstract: N-Nitrosodimethylamine (NDMA), a probable human carcinogen, has been found in clouds and fogs at concentration up to 500 ng/L and in drinking water as disinfection by-product. NDMA exposure to the general public is not well understood because of knowledge gaps in terms of occurrence, formation and fate both in air and water. The goal of this dissertation was to contribute to closing these knowledge gaps on potential human NDMA exposure through contributions to atmospheric measurements and fate as well as aqueous formation processes. Novel, sensitive methods of measuring NDMA in air were developed based on Solid Phase Extraction (SPE) and Solid Phase Microextraction (SPME) coupled to Gas Chromatography-Mass Spectrometry (GC-MS). The two measuring techniques were evaluated in laboratory experiments. SPE-GC-MS was applicable in ambient air sampling and NDMA in ambient air was found in the 0.1-13.0 ng/m3 range. NDMA photolysis, the main degradation atmospheric pathway, was studied in the atmospheric aqueous phase. Water soluble organic carbon (WSOC) was found to have more impact than inorganic species on NDMA photolysis by competing with NDMA for photons and therefore could substantially increase the NDMA lifetime in the atmosphere. The optical properties of atmospheric WSOC were investigated in aerosol, fog and cloud samples and showed WSOC from atmospheric aerosols has a higher mass absorption efficiency (MAE) than organic matter in fog and cloud water, resulting from a different composition, especially in regards of volatile species, that are not very absorbing but abundant in fogs and clouds. NDMA formation kinetics during chloramination were studied in aqueous samples including wastewater, surface water and ground water, at two monochloramine concentrations. A simple second order NDMA formation model was developed using measured NDMA and monochloramine concentrations at select reaction times. The model fitted the NDMA formation well (R2 >0.88) in all water matrices. The proposed model was then optimized and applied to fit the data of NDMA formation from natural organic matter (NOM) and model precursors in previously studies. By determining the rate constants, the model was able to describe the effect of water conditions such as DOC and pH on NDMA formation. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2016

A novel caffeine-degrading bacterium, Pseudomonas putida CBB5 was isolated from the soil by an enrichment procedure using caffeine as the sole source of carbon and nitrogen. CBB5 grew not only on caffeine, theobromine, paraxanthine, and 7-methylxanthine as sole carbon and nitrogen sources, but also on theophylline and 3-methylxanthine. Analyses of metabolites in spent media, resting cell suspensions, and crude cell extracts confirmed that CBB5 degraded caffeine via N-demethylation to theobromine (major metabolite) and paraxanthine (minor metabolite). These dimethylxanthines were further N-demethylated to xanthine via 7-methylxanthine. A previously unreported pathway for N-demethylation of theophylline to 1- and 3-methylxanthines, followed by further N-demethylation to xanthine, was also discovered in CBB5. A 240 kDa, Fe2+-dependent N-demethylase (Ndm) was purified from CBB5 by traditional chromatographic techniques. Ndm was composed of NdmA (40 kDa) and NdmB (35 kDa), which could not be resolved further. Ndm was active only in the presence of a partially purified protein which exhibited cytochrome c reductase activity (Ccr). Ccr transfered reducing equivalents from NAD(P)H to Ndm, which catalyzed an oxygen-dependent N-demethylation of methylxanthines to xanthine, formaldehyde and water. Ndm displayed N-demethylation activity toward all substrates in the caffeine and theophylline metabolic pathways. Ndm was deduced to be a Rieske [2Fe-2S]-domain-containing non-heme iron oxygenase base on its distinct absorption spectrum and significant identity of NdmA and NdmB sequences of other Rieske non-heme iron proteins. The ndmA- and ndmB- gene sequences were determined and cloned individually into the pET32a expression vector as C-terminal His-tagged proteins. Both NdmA-His and NdmB-His proteins were purified using a Ni-NTA column. NdmA-His, in conjunction with Ccr, was capable of N-demethylating caffeine, theophylline, paraxanthine, and 1-methylxanthine to theobromine, 3-methylxanthine, 7-methylxanthine, and xanthine, respectively, suggesting that NdmA-His is a specific N-1-demethylase. Similarly, NdmB-His was determined to be a specific N-3-demethylase, as it was capable of N-demethylating caffeine, theophylline, theobromine, and 3-methylxanthine to paraxanthine, 1-methylxanthine, 7-methylxanthine, and xanthine, respectively. N-demethylation activity of 7-methylxanthine to xanthine (putative NdmC) co-eluted with the partially purified Ccr fraction. This is the first report of multiple, highly positional-specific, Rieske, non-heme iron N-demethylase enzymes for bacterial metabolism of purine alkaloids.

Reverse osmosis (RO) is widely used for water reuse and desalination. Although RO membranes are known for their high salt rejection and practical permeate flux, their performance can be impaired by fouling, and their removal of some disinfection byproducts and their precursors (e.g., bromide, N-Nitrosodimethylamine [NDMA]) does not meet drinking water standards. RO membrane modifications have been widely studied to overcome these limitations. In this research, RO membranes were grafted with cationic polymers to induce a positive charge on the RO membrane surface. This modification aimed at enhancing the rejection of negatively charged bromide ions by removing them from solution by binding them to the membrane surface. The results showed that the modified (positively charged) RO membranes achieved lower rejection (82% rejection) for bromide ions compared to the unmodified ones (94.5% rejection). This behavior was likely a result of increased concentration polarization of the bromide ions at the membrane surface and/or increase in porosity of the modified membranes. Calculations based on the film theory indicate that the concentration of bromide ions at the surface of the modified membrane was 1371 ppm compared to 1307 ppm at the surface of the unmodified membrane. Evidently, the polymer attraction energy was not sufficient to keep the bromide ions attached to the membrane surface and prevent their diffusion across the membrane. Although the goal of the modification in the current study (i.e., enhancing removal of bromide ions) was not met, the permeate flux of the modified membrane was improved compared to the unmodified one. The literature suggests that increasing flux after modification is likely a result of increase in membrane pore size and hydrophilicity. In addition to the experimental work conducted in this study, a multi-criteria decision analysis was performed to prioritize research on surface modifications of reverse osmosis membranes. It was found that surface modifications have been mainly focused on reducing membrane fouling and to a much lower extent on removal of disinfection byproducts and their precursors. The RO membrane modification alternatives for fouling reduction and N-Nitrosodimethylamine (NDMA) removal were ranked based on multiple criteria using the Analytical Hierarchy Process (AHP) and the Technique for Order Preference by Similarity to Ideal Solution (TOPSIS). This multi-criteria decision analysis process resulted in the identification of the top five promising modifications to reduce fouling and improve NDMA rejection. Grafting and coating the RO membranes with complex polymeric salts were the highest ranked modification approaches to reduce fouling. Heat-treatment of RO membranes achieved the highest NDMA rejection (98%); however, this technique was the second highest ranked modification approach for NDMA removal because it scored lower for other evaluation criteria.

Increasing freshwater scarcity across the world means that wastewater reclamation is being considered as a key method in which to meet the growing demand. Evolution of water reuse schemes where high quality product is required such as for indirect potable reuse has led to the adoption in recent years of the integrated membrane scheme using a combination of microfiltration or ultrafiltration with reverse osmosis membrane. However, despite technological advancements, these membranes are still prone to fouling resulting in increased costs through cleaning or replacement. This thesis aims to look at pretreatment to reduce the fouling propensity of the microfiltration membranes via a 600m3 /d pilot plant which was commissioned to investigate indirect potable reuse. A range of pretreatments including pre-screening, pre-coagulation, powdered activated carbon and granular activated carbon were assessed based on fouling amelioration, water quality improvement and cost analysis. Results showed that ferric sulphate dosing was the most effective in terms of reducing the reversible fouling rate especially at high turbidity loads enabling higher flux to be realised leading to a small cost benefit. Activated carbon proved the most effective pretreatment in terms of organic removal and a significant reduction in the irreversible fouling rate. However, the cost involved in using this as a pretreatment is significant compared to possible cost savings through reduced requirement for chemical cleaning. This pretreatment is only viable if it obviates the need for a separate organic removal process.

Indirect potable reuse has been practiced with the potential to enhance sustainability of water resources if planned accordingly. Depending on the pretreatment implemented for potable reuse, emerging contaminants; such as pharmaceuticals, personal care products, industrial solvents, bacterial/viral pathogens, and disinfection byproducts, might be present in source water and difficult to remove via various water treatment technologies. Low molecular weight organic compounds are especially challenging to remove and may require treatment optimization. The overarching purpose of this study was to demonstrate the feasibility of a carbon-based advanced treatment train; including ozonation, biological activated carbon (BAC) filtration and granular activated carbon (GAC) adsorption to achieve water quality suitable for potable reuse and assess the impact of a range of operating conditions for emerging contaminant removal at pilot-scale. The results from this study showed that carbon-based treatment train is equally effective as more commonly used, and more costly, membrane-based treatment trains in terms of pathogen and disinfection byproduct removal. A multiple-barrier approach was implemented, with each treatment stage capable of removing total organic carbon (TOC). GAC was responsible for removal of most of the TOC and emerging contaminants and this removal depended on the number of bed volumes of water processed by GAC. Empty bed contact time was another factor that dictated the extent of TOC removal in the BAC and GAC units as the carbon media was exhausted. Among the emerging contaminants detected, sucralose, iohexol and acesulfame-k were present in the highest concentrations in the influent and were detected consistently in the GAC effluent, thus making them good indicators of treatment performance. Apart from organics removal, BAC played an important role in removal of nutrients, such as ammonia via nitrification. N-Nitrosodimethlyamine (NDMA) was formed in the treatment process by ozone, but was shown to be effectively removed by BAC. EBCT, temperature, ozone dose and presence of pre-oxidants, such as monochloramine, played an important role in determining the amount of NDMA removed. These factors can be further optimized to improve NDMA removal. Sodium bisulfite was used for dechlorinating monochloramine residual post ozone. Nitrification in the BAC was shown to be inhibited by excess of sodium bisulfite dose. Thus monochloramine residual needs to be dechlorinated with sodium bisulfite to help with NDMA degradation but at the same time the sodium bisulfite dose needs to be monitored to allow complete nitrification in the BAC. 1,4-dioxane, another contaminant of emerging concern, was monitored in the treatment process. Biodegradation of 1,4-dioxane was enhanced via addition of tetrahydrofuran as a growth substrate. Biodegradation of 1,4-dioxane can help reduce energy and capital costs associated with advanced oxidation processes that are currently used for 1,4-dioxane removal. Further, relying on biodegradation for the removal of 1,4-dioxane can help avoid the formation of disinfection byproducts associated with advanced oxidation processes such as ozone with peroxide or ultraviolet disinfection with peroxide. The results from this project can be useful for designing potable reuse treatment trains and provide a baseline for removal of organic carbon and emerging contaminants. The conventionally used reverse osmosis and ultrafiltration approach is useful for organics removal in areas where the rationale behind potable reuse is water scarcity. Operational difficulties encountered during this study can prove to be important as this treatment process is scaled up to treat a total of 120 MGD of water for managed aquifer recharge. Overall the lessons learnt from this study can give a better understanding of a carbon-based treatment and further the advancement of reuse projects that have drivers other than water scarcity. / Doctor of Philosophy / The increased growth in urban areas has been accompanied by an increase in potable water demand, leading to depletion of surface and groundwater. Further, the discharge of nutrients such as nitrogen and phosphorus into some of these water bodies can lead to algal blooms. Water reuse involves treating used water and discharging into either a surface or groundwater body. Water reuse has been sought after as a solution to prevent these nutrients being discharged into surface water and to provide a sustainable solution for depletion of water sources. Direct or indirect potable reuse can include a combination of advanced treatment methods such as membrane filtration using ultrafiltration and reverse osmosis, biological filtration, granular or powdered activated carbon adsorption and disinfection methods such as ozonation and ultraviolet disinfection. This study focused on Hampton Roads Sanitation District's managed aquifer recharge project 'sustainable water initiative for tomorrow' (SWIFT), two different advanced water treatment strategies, namely carbon-based and membrane-based were implemented on a pilot-scale (20,000 L/day). The driver for indirect potable reuse in this study was not related to water shortage but aimed at reducing the nutrients discharged into the Chesapeake Bay. Other reasons for implementing reuse included recharging the depleting groundwater levels, land subsidence, and preventing flooding and seawater intrusion near the coastal areas. Membrane-based treatments, such as reverse osmosis, have been well established and studied for potable reuse. The less frequently used carbon-based treatment, that includes used of activated carbon for adsorption and biodegradation of organics (not involving any membrane barrier), was shown to be cost-effective and provided equal protection as that of the membrane-based system in terms of removal of pathogens. Further, since there is no membrane involved in the carbon-based treatment the energy requirements are less than that of the membrane-based treatment and concentrated brine solution is not produced, which makes it favorable for potable reuse where water scarcity is not an issue. This carbon-based treatment which included ozonation and activated carbon filtration and adsorption was further monitored and optimized for removal of organic contaminants and disinfection byproducts. Emerging contaminants such as pharmaceuticals, industrial solvents and personal care products can be harmful to human health and water ecology even at low concentrations. These contaminants are often present in wastewater effluent and can enter drinking water sources if untreated. These emerging contaminants were shown to be effectively removed by ozonation and granular activated carbon adsorption. The formation of disinfection byproducts such as N-nitrosodimethylamine in the treatment process and its removal in the biological activated carbon filtration was also monitored. The impact of temperature, presence of pre-oxidants and design factors such as ozone dose and empty bed contact time affected the removal of all these contaminants. This study provided an understanding of implementing carbon-based treatment for managed aquifer recharge for optimizing removal of bulk organic carbon and emerging contaminants. The results from this study can be utilized for designing advanced water treatment systems and can prove to be a guideline for monitoring and removing emerging contaminants.