Disinfectants, such as chlorine, are widely used in water treatment plants to ensure the safety and quality of drinking water. However, these disinfectants easily react with some natural or man-made organic compounds in raw water and then form disinfection by-products (DBPs). For example, halogenated acetic acid (HAAs) and trihalomethanes (THMs) are two main components of DBPs. The purposes of this study are to analyze the concentration of DBPs including HAAs and THMs in drinking water and investigate the distribution of DBPs in the processes of three advanced water treatment plants in southern Taiwan. The analytical method of HAAs is based on the USEPA Method 552.3 and THMs is analyzed by headspace solid-phase microextraction(HS-SPME). Moreover, some factors which may influence the formation of DBPs such as dissolved organic carbon (DOC) and water temperature are also analyzed to further discuss the relation to the generation of DBPs. Through this study, the results could be the reference for operation control in water treatment plants and regulation setting in Taiwan. The samples of drinking water were collected in three advanced water treatment plants in southern Taiwan from June 2007 to April 2008. The analyzed HAA9 results were 28.71 ¡Ó 14.77£g g / L in Plant A, 24.43 ¡Ó 15.70 £g g / L in Plant B, 28.91 ¡Ó 14.38 £g g / L in Plant C. Comparing the HAA5 results with the maximum contaminant level (MCL) in USEPA, it was clearly found that all the values were under the standard of 60 £g g / L. As to THMs, the results were 9.99 ¡Ó 3.39£g g / L in Plant A, 0.94 ¡Ó 2.12 £g g / L in Plant B, 28.91 ¡Ó 14.38 £g g / L in Plant C and greatly under the EPA standard of 80 £g g / L in Taiwan. Furthermore, the major species of HAA9 in order were BCAA and TCAA while THMs was trichloromethane (CHCl3). In the relation between DOC and DBPs, the results demonstrated that DOC was more relative to DBPs in raw water; meanwhile, the water temperature did not show great relation. In general, despite the poor correlation, it was still could conclude that the concentration of DBPs increases with the increase of DOC and temperature. In conclusion, the research results showed that the removal efficiency of DBPs in Plant A and B (UF/RO system) is greater than Plant C (Biological Activated Carbon system, BAC system ), and all three advanced water treatment plants could show greatly effectiveness in drinking water quality improvement. However, higher concentration of bromine products in HAAs was discovered in this research. It was suggested that the phenomenon should be further discussed and controlled.

ABSTRACT Being a densely populated and heavily industrialized harbor, the emissions of air pollutants in the Kaohsiung area are very huge. There is substantial amount of VOCs (volatile organic compounds) present in the ambient air. Furthermore, relative high temperature and strong sunlight tend to transform these VOCs to oznone, causing high ozone episodes. This study aimed to determine the VOCs source profiles (or fingerprints) from 20 stationary sources, 10 from each of Kaohsiung City and Kaohsiung County. These include flue gas emission from incineration plants, sewage treatment plants, petroleum plants, and others. The samples was collected using a stainless-steel thermal desorption tube, then analyzed a Hewlett-Packard 58900-II gas chromatograph, fitted with a flame ionization detector and desk-top personel computer. The OFP (ozone formation potential) of VOCs from individual sources were evaluated based on MIR (maximum incremental reactivities). The results show that the speciations of VOCs depend on the raw material and air pollution control equipments used in the processes. The major VOCs in the petro-chemical industries are benzene, toluene, xylene, and 1,3,5-trimethylbenzene. The major VOCs in the PVC processes and surface-painting industries are 2-methylbutane, 2-methylpentane, and ethylbenzene. The major VOCs in the sewage treatment plants are ethylene, hexane, benzene, toluene, and m-xylene. The highest average reaction of the samples is 27.94 g-O3/g-VOCs from intermediary process, the next are from lubrication oil distillation tower, TPE process, ABS process, and maleic anhydride process, ranging from 3 ~ 5 g-O3/g-VOCs. Thus, the reactivity of aromatic-related process is highest, the next are aldehydes - and ketones -related processes. Keywords: Volatile Organic Compounds, Fingerprints, Ozone Formation Potential

Kaohsiung is a densely populated harbor city, in which the density of motor vehicles is also high. Since the temperature and sunlight is also relatively high in Southern Taiwan, tending to transform ambient volatile organic compounds to ozone thus causes high ozone events. This study measured the concentrations of 63 hydrocarbon (HC) species from C2 to C15 simultaneously at the Nan-Chie and Hsiung-Kong sites in Kaohsiung city during the morning (07-10), the afternoon (13-16), and the evening (18-21) periods on three successive days in winter 2004. Results show that the most abundant species of Kaohsiung¡¦s air is toluene (43.01-60.95 £gg/m3), followed by i-pentane, 1,2,4-trimethylbenzene, benzene, n-butane, propane, and acetylene, in the range 9.55-16.93 £gg/m3, while the concentrations of halocarbons is 0.17-4.12 £gg/m3. Alkanes (44.7-45.9%) represent the largest proportion of the total HC, followed by aromatics (35.4-36.8%), alkenes (10.5-10.9%) and halocarbons (3.6-3.9 %). The OFP (ozone formation potential) of HC species were evaluated based on the MIR (maximum incremental reactivity). Results show that aromatics (45.9-54.3%) represent the largest proportion of the OFP, followed by alkenes (17.7-37.5%), and alkanes (16.5-23.6%). The results from the factor analyses show the major sources of ambient HC in Kaohsiung city are the vehicle exhausts, industrial processes, solvent evaporations, combustion exhausts, and petrochemical processes.

An exploratory analysis of the trihalomethane (THM) and haloacetic acid (HAA) formation potential (FP) of Cedar Lake in order to produce formation potential curves for both THM and HAA; determine the THMFP and rate constant and compare to previous studies on Cedar Lake; and develop modeling for the formation potential loss of HAA from laboratory analysis of the raw lake water. While extensive modeling approaches have been explored for THM formation on different water sources, not many have been applied to the reservoir that supplies water to the Carbondale Water Treatment Plant and even fewer have explored the formation and modeling of HAA. Data for this study was obtained through laboratory experiment by applying bleach as a substitute for free chlorine to raw water samples obtained from Cedar Lake and quenching the samples at specific time steps to stop the reaction. Samples were then analyzed for THM content using standard method EPA 524.2R4.1 and HAA content using standard method EPA 552.2. The observed peak formation was 641.2701 µg/L for THM and 426.8 µg/L for HAA, but modeling fitted to the laboratory results indicated that a lower FP provided a better fitting of the data. A detailed analysis of the formed THM and HAA compounds indicated that a model produced for each compound resulted in more appropriate fitting by being able to account for the differing reaction rates and limiting factors of each reaction.

In this research, used dimethyl ether as second fuel blended with diesel (mixed quantity with 10 L/min to 60 L/min, interval 10L/min), which test behavior of diesel engine and carbonyls emission investigated. The engine operated at steady-state condition of 1600 rpm, 145 Nm torque , eight kinds of carbonyls were sampling and analysis, and discuss the performance of the ozone formation potential (OFP). The results of regulated pollutant emissions, CO, THC and PM emission could increasing with the addition of DME, NOX emissions, along with the mixed rate of per minute from 10 L, 20 L, 30 L, 40 L, 50 L and 60 L of its reduction rate was 6.8%¡B8.3%¡B10.0%¡B10.6%¡B13.1% and 15.4%, shows that the DME can reduce NOX emissions. Add a various amount of dimethyl ether , which carbonyl compounds emission from the gas flow 0 L(with neat diesel), 10 L, 20 L, 30 L, 40 L, 50 L and 60 L concentrations were 2507.44 g/m3, 2665.27 g/m3, 2726.67 g/m3, 2958.07 g/m3, 4645.87 g/m3, 5470.20 g/m3 and 7279.91 g/m3; the emission factor of 143.58 mg/bhp-hr, 152.65 mg/bhp-hr, 156.62 mg/bhp-hr, 168.69 mg/bhp-hr, 266.22 mg/bhp-hr, 312.38 mg/bhp-hr and 416.36 mg/bhp-hr, shows the addition of DME will rising the carbonyl compound emissions of diesel engine. Gas of dimethyl ether (10,20,30,40,50 and 60 L/min) into the neat diesel fuel (0 L/min) as a mixture fuel additives, the effect of ozone formation potential as increase in the total ozone formation potential, 21945.93 g-O3/m3, 23698.40 g-O3/m3, 24427.46 g-O3/m3, 26672.98 g-O3/m3, 42683.69 g-O3/m3, 50519.26 g-O3/m3 and 67710.60 g-O3/m3 respectively, and ozone manufacturability will 0 L/min of 8.75 increased to 60 L/min of 9.30.

This research conducted exhaust tests in an HDDE (heavy-duty diesel engine) using pure diesel fuel mixed with 10 to 30% isobutanol under the condition of U.S. Transient Cycle. Characteristics of 18 carbonyls emissions were investigated and compared with those using pure diesel. Results showed that the brake power (BP) and brake thermal efficiency (BTE) were decreased with increasing isobutanol mixtures (10 to 30%). Brake specific fuel consumption (BSFC) was increased for isubutanol ¡Ø 10%, but was decreased for isubutanol above 10%. The regulated emissions of CO, PM and NOx were decreased, but CO2 and THC were increased, due to variations of cetane number and heating value. Total carbonyls emission concentrations with pure diesel fuel were 893.25 £gg/m3, with emission factors being 52.57 mg/bhp-hr or 218.44 mg/L-fuel. When 10 to 30% isobutanol mixture was added, total carbonyls concentrations ranged from 1108.21 to 2622.27 £gg/m3, with emission factors being 268.83 to 610.94 mg/L-fuel, or 68.93 to 175.25 mg/bhp-hr. The ozone formation potential of diesel engine with pure diesel fuel was 7132.72 g-O3/m3.When 10 to 30% isobutanol mixture was used, total ozone formation potential ranged from 8764.39 to 20168.73 g-O3/m3. Total carbonyls emissions were increased with increasing isobutanol contents. In summary, addition 10% isobutanol was an optimal blend, since both fuel saving and reductions of pollutant emissions can be achieved.

Hsuehshan tunnel which included two bore and three ventilation shaft systems is the longest (12.9 km) freeway tunnel in Taiwan. 56 species volatile organic compounds (VOCs) were sampled in two different locations each bore and three emitted shafts to determine the emission factors (EFs). Each sampling day has three sampling period: morning (8:00-10:00), Noon (12:00-14:00) and afternoon 16:00-18:00). C2 species were analyzed by GC/FID and C3 − C12 species were analyzed by GC/MS. The composition in southern bore was expressed by alkanes (36.69% − 39.20%), aromatics (34.14% − 36.33%), alkenes (20.27% − 21.95%), Alkynes (3.35% − 4.11%) and Naphthenes (1.06% − 1.35%). Northern bore had the similar profile. Ethylene (4.93 ¡Ó 2.21 mg/veh-km), Isopropane (4.85 ¡Ó 2.75 mg/veh-km), toluene (4.55 ¡Ó 1.31 mg/veh-km), m,p-xylene (2.98 ¡Ó 0.90 mg/veh-km) and propylene (2.70 ¡Ó 0.88 mg/veh-km) are the top five abundant VOCs in southern bore ; Isopropane (6.78 ¡Ó 3.33 mg/veh-km), ethylene (5.44 ¡Ó 2.63 mg/veh-km), toluene (5.32 ¡Ó 2.39 mg/veh-km), propylene (3.55 ¡Ó 1.67 mg/veh-km) and m,p-xylene (3.36 ¡Ó 1.45 mg/veh-km) are the top five abundant VOCs in northern bore. The EFs were smaller than other freeway tunnel investigated. Shaft emitted the partial mass of VOCs result in concentration gradient dropped off. The total VOCs EF of shafts during holidays was in the range of 72.24 mg/s − 180.60 mg/s higher than on weekdays in the range of 53.40 mg/s − 82.74 mg/s. The EF of shafts had effected by air-extracting apparatus, so standard deviations (S.D.) varied widely. Combining the EF of shaft with EF of tunnel we obtained the overall vehicle EF which was close to other freeway tunnel results. The proportion of Ozone formation potential (OFP) in both bore were alkenes (47.5% − 48.5%), aromatics (40.2% − 42.3%) and alkanes (9.8% − 10.1%). Note that sum of alkenes and aromatics exceeded 90%.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22057号 / 工博第4638号 / 新制||工||1723(附属図書館) / 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 伊藤 禎彦, 講師 中田 典秀 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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Taiwan Water Supply Cooperation (TWSC) has upgraded traditional purification processes into advanced treatment systems in south Taiwan for many years. The removal efficiency of assimilable organic carbon (AOC) by ultrafiltration (UF) with reverse osmosis (RO) systems was 47% was lower than that of 62% by ozone with biological activated carbon system (BAC). In this work, we investigate the removal of AOC and disinfection by products formation potential (DBPFP) of raw water took from a water treatment plant by using BAC and membrane treatment units. BAC system of granular activated carbon(GAC) and powder activated carbon (PAC) showed two kind carbons have certain efficiency for AOC removal. Results we found could reach above 50% (from 44.28¡Ó9.84£gg acetate-C/L reduce to 20.93¡Ó4.25£gg acetate-C/L for GAC and from 45.92¡Ó17.75£gg acetate-C/L reduce to 21.23¡Ó4.25£gg acetate-C/L for PAC), when hydraulic retention time (HRT) in BAC reactor was at 1 hour. When HRT raised to 6 hours the concentration of AOC in effluent of BAC systems were reduced under 15 £gg/L, and removal efficiency could reach above 70%. The suggested limit level of AOC is 50 £gg/L of drinking water. In removal of DBPFP, BAC of two carbons has showed certain efficiency on trihalomethanes formation potential (THMFP) and haloacetic acids formation potential (HAA5FP). The results were done in removal of THMFP (from 20.54¡Ó6.48£gg/L reduce to 14.21¡Ó4.47£gg/L for GAC and from 24.64¡Ó6.74£gg/L reduce to 14.75¡Ó4.04£gg/L for PAC) and HAA5FP (from 39.64¡Ó10.38£gg/L reduce to 17.35£gg/L for GAC and from 17.86¡Ó5.13£gg/L reduce to 11.76¡Ó3.76£gg/L for PAC) in BAC reactors. They were all lower than national standard of drinking water (THMs 80£gg/L, HAAs 60£gg/L). It is believed that two kind carbons in BAC system could all reduce effectively on AOC and DBPFP to obtain high quality of drinking water with biological stability at HRT of 6 hours.