学位授与年月日: 2007-07-23 ; 学位の種類: 新制・課程博士 ; 学位記番号: 工博第2837号 / Perfluorochemicals (PFCs) were produced by industries and consumed “safely” as surfactants, repellents, additives, fire-fighting foams, polymer emulsifiers and insecticides for almost fifty years. However they are now considered as persistent, bioaccumulated and toxic (PBT) chemicals, and ubiquitously distributed in waster, air, human body and biota. Although some efforts were contributed to reduce PFCs in environment, such as development of alternatives and recycling processes, huge amount of persisted PFCs have already been discharged in environment and accumulated in biota including humans. In some industrialized areas, such as Yodo river basin in Japan, water environment and human blood were polluted by some PFCs, and thus reduction and control of PFCs were urgently required for the purpose of environmental safety and human health in these areas. Unfortunately, some studies implied that current water and wastewater treatment processes seemed ineffective to remove PFCs in trace levels. Therefore, this study will try to develop some proper technologies to treat trace level of PFCs in wastewater. In order to achieve this main objective, several works have been accomplished as follows. 　Current available literature has been reviewed to obtain a solid background for this study. Basic information of PFCs was summarized in physiochemical properties, PBT properties, productions and applications, regulations and etc.. Analytical methods for PFCs, especially of LC-ESI-MS/MS, were reviewed including pretreatment processes in diverse matrices, which derived objectives of chapter III. Distributions and behavior of PFCs were briefly discussed in water environments, biota sphere and human bloods. Available control strategies were shown in detail about alternatives, industrial recycling processes, and newly developed treatment processes. Current wastewater treatment processes showed inefficient removal for some PFCs, deriving objectives of chapter IV on the PFC behavior in treatment process. Newly developed treatment technologies seemed able to decompose PFCs completely but unsuitable for application in WWTP. Therefore, granular activated carbon (GAC) adsorption and ultra violet (UV) photolysis were developed in chapter V and VI as removal and degradation processes respectively. 　Fifteen kinds of PFCs were included in this study, consisting of twelve kinds of perfluorocarboxylic acids (PFCAs) with 4~18 carbons and three kinds of perfluoroalkyl sulfonates (PFASs) with 4~8 carbons. An integral procedure was developed in chapter III to pretreat wastewater samples. LC-ESI-MS/MS was applied to quantify all PFCs in trace level. Pretreatment methods were optimized between C18 and WAX-SPE processes for aqueous samples, and between IPE, AD-WAX and ASE-WAX processes for particulate samples. Standard spiking experiments were regularly conducted for each wastewater sample to calculate recovery rate and control analytical quality. As the result, WAX-SPE showed better performance on samples with very high organics concentrations, and C18-SPE performed better for long-chained PFCs. ASE-WAX was proposed as the optimum method to pretreat particulate samples because of the simple and time saving operations. 9H-PFNA was used as internal standard to estimate matrix effect in wastewater. 　Behavior of PFCs in a municipal WWTP has been studied in chapter IV by periodical surveys for six times in half a year. All PFCs used in this study were detected in WWTP influent and effluent. According to their carbon chain lengths, all PFCs can be classified into “Medium”, “Long” and “Short” patterns to simplify behavior analysis. PFCs in same pattern showed similar properties and behavior in wastewater treatment facilities. Very high concentrations of PFCs existed in WWTP influent, indicating some point sources of industrial discharge in this area. “Medium” PFCs, such as PFOA(8), PFNA(9) and PFOS(8), were primary contaminants in the WWTP and poorly removed by overall process. Performances of individual facilities were estimated for removal of each PFC. Primary clarification and secondary clarification were helpful to remove all PFCs in both aqueous phase and particulate phase. “Medium” PFCs in aqueous phase were increased after activated sludge process, but other PFCs can be effectively removed. Ozone seemed ineffective to decompose PFCs because of the strong stability of PFC molecules. Sand filtration and biological activated carbon (BAC) filtration in this WWTP can not remove PFCs effectively too, which required further studies. Performances of combined processes were estimated by integrating individual facilities along the wastewater flow. Activated sludge process coupled with clarifiers showed satisfied removal of most PFCs in the investigated WWTP except “Medium” PFCs. 　Adsorption characteristics of PFCs onto GAC have been studied by batch experiments in chapter V. Freundlich equation and homogenous surface diffusion model (HSDM) were applied to interpret experimental data. Isothermal and kinetics experiments implied that PFC adsorption on GAC was directly related with their carbon chain lengths. By ascendant carbon chain length, adsorption capacity for specific PFC was increased, and diffusion coefficient (Ds) was decreased. Ds of GAC adsorption was also decreased gradually in smaller GAC diameters. Coexisted natural organic matters (NOMs) reduced adsorption capacities by mechanism of competition and carbon fouling. Carbon fouling was found reducing adsorption capacity much more intensively than competition by organics. Acidic bulk solution was slightly helpful for adsorption of PFCs. However adsorption velocity or kinetics was not affected by NOM and pH significantly. GAC from Wako Company showed the best performance among four kinds of GACs, and Filtra 400 from Calgon Company was considered more suitable to removal all PFCs among the commercial GACs. Preliminary RSSCT and SBA results implied that background organics broke through fixed GAC bed much earlier than trace level of PFCs. Medium-chained PFCs can be effectively removed by fixed bed filtration without concerning biological processes. 　Direct photolysis process has been developed in chapter VI to decompose PFCAs in river water. Irradiation at UV254 nm and UV254+185 nm can both degrade PFCAs. Stepwise decomposition mechanism of PFCAs was confirmed by mass spectra analysis, and consecutive kinetics was proposed to simulate experimental data. PFASs can also be degraded by UV254+185 photolysis, although the products have not been identified yet. Coexisted NOMs reduced performance of UV photolysis for PFCAs by competition for UV photons. Sample volume or irradiation intensity showed significant influence on degradation of PFCAs. Local river water polluted by PFOA can be cleaned up by UV254+185 photolysis effectively. Ozone-related processes were also studied but ineffective to degrade PFC molecules. However, PFCs could be removed in aeration flow by another mechanism. / 京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第13340号 / 工博第2837号 / 新制||工||1417(附属図書館) / UT51-2007-M963 / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 田中 宏明, 教授 藤井 滋穂, 教授 伊藤 禎彦 / 学位規則第4条第1項該当 / Doctor of Engineering / Kyoto University / DFAM

No description available.

No description available.

No description available.

Continuous increases in the interest and implementation of wastewater reuse due to intensified water stress has escalated the concerns of emerging contaminants. Among emerging contaminants there are microbial (antibiotic resistance) and chemical (pharmaceuticals) elements which have been shown to survive wastewater treatment. This dissertation aims to mitigate emerging contaminants by means of understanding and/or developing the appropriate disinfection strategies, with the intention to provide knowledge that would facilitate towards safe and sustainable water reuse. The first part of this thesis explored microbial risk component of antibiotic resistance. Antibiotic resistance genes are abundant in treated wastewater, and only pose a risk if taken up by potential pathogens through natural transformation. Our results showed that solar irradiation can double natural transformation rates, mediated by reactive oxygen species generation, which led to upregulation in DNA repair and competence genes in Acinetobacter baylyi ADP1. Treatment with UV-C254 nm irradiation also resulted in upregulation in DNA repair genes, nevertheless we observed a decrease in natural transformation rates. These results imply that direct damage of antibiotic resistance genes (ARG) could inhibit their spread and therefore risk, despite other factors contributing to the contrary. The next chapter in this dissertation postulated that the UV/H2O2 combination would be ideal to treat microbial and chemical emerging contaminants in effluent generated from an anaerobic membrane bioreactor. We demonstrated that at an optimal UV intensity and H2O2 concentration, we were able to achieve a 2 and 6-log reduction of the two antibiotic resistance genes and bacteria and used in this study, respectively, and more than 90% removal of the three pharmaceutical compounds. These observations suggest that UV/H2O2 has great potential in treating effluent with high nitrogen concentrations, preserving the fertilization benefit of AnMBR effluent. Overall, this dissertation revealed the potential of UV-based treatments for treated wastewater intended for reuse. Post-membrane processes effluent allows one to deploy UV-C254 nm to selectively target DNA and therefore ARB and ARG that may be still present in the treated wastewater. At the same time, coupling chemical oxidants with UV-C (i.e., UV AOP) would further enhance the means to simultaneously oxidize and degrade potentially harmful chemical contaminants.

Literature reviews and laboratory work were used to examine the phosphorus removal efficiency of the reactive filter material Polonite®. This material is produced from the calcium carbonate and silica based rock Opoka. The thesis mainly focuses on adsorption of phosphorus from wastewater with Polonite® but also discuss the possibilities of recycling the filter and the adsorbed phosphorus back into agriculture. This would be beneficial to the environment and a path to a sustainable use of phosphorus. It is important to reduce the employment of phosphorus because of the upcoming “Peak Phosphorus” and the negative impact that an excess of the nutrient has on water bodies. The two main objectives of this thesis were to evaluate and display the phosphorus sorption capacity of Polonite® in a breakthrough curve and to obtain adsorption isotherms of phosphorus on Polonite®.  To achieve these objectives experiments were performed in a pilot-plant and in a laboratory at Hammarby Sjöstadsverk. A 500 kg Polonite® filter was connected to flow of wastewater of 400 L/hr and samples were collected and analyzed regularly. The filter did not perform as well as expected, having already shown promising results in other experiments. This is most likely due to the high flow of wastewater and to a too short residence time. The phosphorus reduction was down to 60 % after approximately 30 days and a breakthrough was noticed after 53 days. When saturated, the filter contained 0.6 kg of phosphorus, the equivalent of a sorption capacity of 0.12 %. The pH in the effluent from the Polonite® filter was 10.2 at the first measurement but then dropped fast. When the filter was saturated the pH was down to 8.7. The breakthrough curve gave some indications of that the saturated Polonite® filter might be able to release adsorbed phosphorus. It was also concluded that the Polonite® filter was acting mainly by sorption and thus reduced the dissolved, but not much of the particular, phosphorus.Equilibrium experiments were conducted using solutions with different concentrations of phosphorus. 1 g of Polonite® was added to each solution which was then stirred. With the help of adsorption isotherms the maximum loading capacity was estimated at 330 mg of phosphorus per gram of Polonite®. This corresponds to a 33 % capacity and is a very high number.    Recommendations for future studies would be to further examine the wastewater residence time in the Polonite® filter to improve sorption capacity of phosphorus. It could also be interesting to redo the equilibrium experiments to obtain a more probable loading capacity. The possible presence of pharmaceuticals and/or heavy metals in the filter is also important to investigate, as is the economic aspect of the employment of Polonite® filters for removal of phosphorus from wastewater.

ABSTRACT IMPROVED MICROALGAL BIOMASS HARVESTING USING OPTIMIZED ENVIRONMENTAL CONDITIONS AND BACTERIAL BIOFLOCCULANTS DEREK CONTE MANHEIM The cost and energy balance of microalgae biofuel production is sensitive to the algae harvesting method, among many other factors. Bioflocculation and settling of suspended microalgae cultures is a harvesting method with potentially low cost and energy input. However, bioflocculation (the spontaneous flocculation of algal cells without chemical addition) has not been a reliable process with cultures grown in ponds. To provide insights to help improve algae settling, factors affecting the settling of algae were investigated in the laboratory using pure cultures of two common microalgae species: Scenedesmus sp. and Chlorella vulgaris. Bioflocculation of these algae was studied with and without the addition of bioflocculants produced by the bacterium, Burkholderia cepacia, to improve settling efficiencies. The bioflocculant produced by this bacterium was used in two different forms: a cell suspension including capsular and dissolved extracellular polymeric substance (EPS) components of B. cepacia, and dialyzed filtrate of the bacterial culture (only dissolved EPS fraction). The effects of algal growth phase, mixing time, bioflocculant dose, and environmental conditions such as pH and nutrient deprivation of bacterial bioflocculant cultures on settling of the algae species were studied. Settling characteristics were different for the two algae cultures, and their settling was affected differently by the many factors studied. Scenedesmus settling was best in later growth stages, while Chlorella settled much better in early growth phases. Addition of B. cepacia cells as a bioflocculant improved settling of Scenedesmus, with the greatest effect during mid to late exponential growth of the Scenedesmus. In contrast, addition of B. cepacia filtrate as a bioflocculant best improved Chlorella settling during stationary growth of Chlorella. Longer mixing times (contact time between the algae cells and bacterial bioflocculant) improved the settling of Scenedesmus, while Chlorella settled better with a shorter mixing time. Reducing the pH to 3 (a typical isoelectric point for microalgae) improved the settling of both algae cultures, with and without bioflocculant addition. Increasing the pH to 11 autoflocculated Scenedesmus cultures, but not Chlorella cultures, at early growth stages. EPS produced by the algae, bacteria, and wastewater organisms was quantified using dialysis separation followed by total organic carbon (TOC) analysis. Wastewater organisms were included because wastewater is a potential growth medium for biofuel algae. Improved settling of both species of algae depended on both the quantity and type of EPS (dissolved or capsular) produced by both the bacterial bioflocculant, and the algae themselves. Scenedesmus settled the best during late growth phases while its own EPS production was high, and combined EPS (capsular and dissolved) from B. cepacia improved settling at a higher dosage of bacterial cells to algae (1:2 B. cepacia cells to algae cells). Since Chlorella settling was not improved at later growth stages when its own EPS production was greatest, it appears that Chlorella’s settling rate was less affected by the production of its own EPS. For Chlorella, B. cepacia EPS addition (capsular and dissolved) was effective only in low doses (1:6 B. cepacia cells to algae cells). Settling results with the addition of bacterial bioflocculants with the pure algae cultures were compared to settling results of lab experiments with algae pondwater sampled from high-rate algae ponds (HRAPs). These algae samples were used to test the addition of return activated sludge (RAS) to improve settling. RAS addition improved the settling of Chlorella, which was the dominant algae species in the HRAP during the time of this study, at two different doses (a ratio of RAS to algae pond water of 1:3 and 1:6). Nutrient deprivation of B. cepacia cells before use as a bioflucculant was found to improve settling for Scenedesmus, especially during early phases of growth when EPS production of Scenedesmus was low. The EPS produced by the starved bacterial cells was about 30% greater than that produced by cultures which were not nutrient-limited. For the bacterial cultures, EPS production peaked at mid stationary phase for non-starved cultures and during early stationary phase for starved cultures. Chlorella settling improved in early growth with starved bacterial cell addition and in later growth with non-starved bacterial cell addition. These results suggest that the settling of microalgae can vary dramatically by species and that the settling of different species is affected differently by growth phase and environmental conditions. In addition, species of algae respond differently to addition of bacterial bioflocculants. Given the dramatically different settling behavior of the two species of algae used in this research, more research should be directed to studying settling of other microalgal species. Based on this research, the use of bacterial bioflocculants is promising for improving algae settling and may contribute to the development of a reliable, low cost harvesting process for commercial biofuel production from microalgae.

This research addresses refractory forms of nitrogen that, even with advanced biological nitrification-denitrification systems are not removed completely from domestic wastewater. TKN (Total Kjeldahl Nitrogen), ammonia plus organic nitrogen, is one of the forms to measure the levels of nitrogen present in effluent wastewaters. Ferrate, a strong oxidant, was used for the treatment of these nitrogen forms with the objective of producing nitrogen compounds that can be removed by subsequent biological processes. Bench-scale experiments were performed on effluent samples taken prior to chlorination from an Orlando, FL wastewater treatment facility, using a biological nutrient removal process. The samples were treated with doses of ferrate ranging from 1 to 50 mg/L as FeO4–2 under unbuffered conditions. TKN removal as high as 70% and COD removal greater than 55% was observed. The TSS production after ferrate treatment was in a range of 12 to 200 mg/L for doses between 10 and 50 mg/L FeO4-2. After an optimum dose of ferrate was determined, three bench-scale reactors were operated under anoxic conditions for 10 to 12 days, two as duplicates containing the treated effluent and one as a control with untreated sample. Two different doses of ferrate were used as optimum dose for these experiments, 10 and 25 mg/L as FeO4-2. The purpose of these reactors was to determine the potential for biological removal of remaining nitrogen after ferrate oxidation of refractory nitrogen. Treated and raw samples were analyzed for Total Kjeldahl Nitrogen (TKN) (filtered and unfiltered), chemical oxygen demand (COD) (filtered and unfiltered), total suspended solids (TSS), nitrate (NO3-N), nitrite (NO2-N), and heterotrophic plate count (HPC). As a result, more than 70% of the soluble TKN was removed by chemical and biological oxidation for a sample treated with a dose of 25 mg/L FeO4-2, and less than 50% when treated with 10 mg/L FeO4-2. For the control samples run parallel to the ferrate treated samples, a maximum of 48% of soluble TKN and a minimum of 12% was removed. A three-log increase was observed in heterotrophic bacteria numbers for both doses during the operation of the reactors. Sodium ferrate was found to be an effective oxidant that can enhance the biodegradability of recalcitrant TKN present in municipal wastewaters. As mentioned before this research was develop using batch reactor units at bench-scale, therefore it is recommended to follow the investigation of the biodegradability of recalcitrant TKN of a ferrate treated sample under continuous flow conditions so that results can be extrapolated to a full-scale treatment facility.

Nowadays people are more alert about conservation of water and water scarcity. The amount of usable water is decreasing due to unavailability of pure water for day to day use. Both surface and groundwater is contaminated by untreated wastewater discharged from improper onsite wastewater treatment system, nutrient laden agricultural runoff and increasing use of fertilizer in fields. This elevated nutrient level is increasing the maintenance and operation cost of water treatment plant. So it is an important task to remove those nutrients from wastewater and other water bodies by applying environmental friendly process. In the USA, about 25% homes are still depending on on-site wastewater treatment (OSWT) due to unavailability of centralized treatment process. In Florida, OSWT is managed by the Florida Department of Health (FDOH). By realizing the importance of water conservation, USEPA already determined the maximum contaminant level (MCL) for nitrate and nitrite in water bodies. Many researches are conducted to evaluate the performance of EPA recommended treatment process (i.e. traditional standard drain field) for OSWT. The UCF research group also performed an experiment to understand the efficiency of traditional standard drain field. At the same time the research group developed an innovative wastewater treatment process named B&G treatment bed as a comparison with traditional standard drain field. This paper mainly focuses on performance of these two treatment processes. The B&G is a novel treatment process by its functionality for nutrient removal. The process generally used a media mixture developed by the research group of UCF. This mixture will act as organic carbon source to support denitrification process while nitrification process does not demand such carbon source. Evan it is observed that this mixture can remove nutrient by physical-chemical process. The recirculation sand filter (RSF) of traditional drain field is also filled by another mixture of media. Both media mixtures are developed by batch experiment in UCF laboratory. The performance of the B&G is compared with the traditional treatment process practiced in USA. These media mixtures can be good supporting media for microorganisms' growth and development. All the major nitrogen and phosphorus species removal is observed by collecting sample in a weekly fashion. The pathogens removal efficiency is also observed. The sample is analyzed by a certified laboratory (i.e. Environmental Research and Design, ERD) in Orlando, Florida to maintain the best quality of this research. The presence of microorganisms is identified by using PCR. The B&G drainfield is very effective for removing both nitrogen and phosphorus species from wastewater. It is also very efficient to remove pathogens too. Standard drainfield is very effective for pathogen removal but it cannot remove nutrients effectively. Nitrate removal in B&G drainfield is well compared to standard drainfield.

This thesis discusses the mechanisms associated with the removal of organic matter, nitrogen and phosphorus in wastewater-fed high rate algae ponds (HRAP) designed to operate as triplicates. Research was conducted at the San Luis Obispo Water Reclamation Facility (SLOWRF) as a pilot-scale study of nine 30-square meter ponds one foot in depth. During period of study, triplicates were operated at hydraulic retention times (HRT) of 4, 3 or 2-days. Main objectives for the study were to determine minimum HRTs required to achieve secondary and tertiary treatment. Experimental conditions such as CO2 supplementation, nighttime aeration and operation of ponds in series were employed to evaluate optimal conditions for efficient nutrient removal. Ponds were continuously fed primary effluent with the following water quality characteristics: 5-day total biochemical oxygen demand (TBOD5) of 124mg/L, 5-day soluble carbonaceous biochemical oxygen demand of 67mg/L (scBOD5), total suspended solids (TSS) of 66mg/L, volatile suspended solids (VSS) of 65mg/L, total ammonia nitrogen (TAN) of 34mg/L-N, oxidized nitrogen of 1.1mg/L-N, total K̇jeldahl nitrogen (TKN) of 42mg/L-N and dissolved reactive phosphorus (DRP) of 3.3mg/L-P. Nutrient removal efficiencies were compared between summer months (April – October) and winter months (November – February). Average pond temperatures during summer and winter were 20.4 °C and 14.9 °C, respectively. Average TAN removal efficiencies of 2-day HRT ponds ranged from 62% in winter to 78% in summer. Operation of ponds at an increased 3-day HRTs resulted in corresponding seasonal increases of TAN removal by 14% and 12%. In 4-day HRT ponds operating in series after a 3-day HRT set, TAN removal efficiency was 98% in winter and 99% in summer. Aeration increased nitrification and nitrate concentrations in 2-day HRT ponds to10mg/L-N ± 4.4mg/L-N. DRP concentrations and BOD removal efficiencies within replicate ponds were similar throughout seasonality. DRP was 1.2mg/L-P ± 0.66mg/L-P at a 4-day HRT operating in series, 2.2mg/L-P ± 0.57mg/L-P at a 3-day HRT and 2.6mg/L-P ± 0.58mg/L-P at a 2-day HRT. Aeration had no measureable effect on BOD removal. BOD removal efficiency was 97% at a 4-day HRT in series with a 3-day HRT and 95% at 3-day and 2-day HRTs.