Metro Kaohsiung with high percentage (6-10 %) of poor air quality (PSI>100) has been announced officially by Taiwan Environmental Protection Administration (TEPA) as the worst air quality region among seven Air Quality Zones (AQZ) in Taiwan. Ozone is one of two major air pollutants that are responsible for the poor air quality. In this study, the vertical concentration profiles of ozone and its precursors (NOX and VOCs) at eight sites were measured by tethered balloons with air pumps and tedlar sampling bags. This method was used to investigate the vertical profile and the tempospatial distribution of ozone and its precursors in offshore/inland regions. This study further investigated ozone formation mechanism and air mass trajectory via simultaneous air quality sampling around the coastal region of metro Kaohsiung. This study sampled the vertical concentration profiles of ozone and its precursors at both inland and offshore sites during eight intensive sampling periods on August 16-17 and November 2-3, 2006, January 24-25, March 6-7 and May 2-3, 2007, October 30-31, 2008, and March 11-12 and July 15-16, 2009. Eight sampling periods were divided into the sea-land breeze period, the northeast monsoon period, and the mixing wind field period. During the sea-land breeze period, the wind direction changed 90˚ and more between daytime and nighttime, and the wind speeds of the sea breezes varied significantly than those of the land breezes. During the northeast monsoon period, prevailing wind blew from the north (300~60˚) with the average wind speeds of 1~4 m/s. During the mixing wind field period, the wind direction varied significantly from 270˚ to 90˚ with the average wind speeds of 1~3 m/s. Results obtained from the vertical profiles showed that O3 concentration appeared stratification phenomenon at 40 out of 64 sampling sites, in which its precursors (NOX or VOCs) demonstrated stratification phenomenon at 30 sampling sites, accounting for 75 % of total O3 stratification. It suggested that ozone and its precursors had strong correlation with each other. The linear slope of the titration effect showed that the intensity of titration effect at night during the northeast monsoon period was larger and had higher correlation (R> 0.7), and followed by the mixing wind field period and the sea-land breeze period. This phenomenon correlated closely with meteorological conditions, the concentrations of O3 precursors, and solar radiation intensity. Therefore, O3 concentration at night during the northeast monsoon period was lower than those of the sea-land breeze period. Results obtained from VOCs measurement indicated that the major species of VOCs was acetone which accounted for 16.25~64.05 % of total TVOCs-C2 in the offshore region. High concentration of TVOCs-C2 was affected by the usage of organic solvents. While, the major species of VOCs in the inland region was toluene which accounted for 6.41~43.77 % of total TVOCs-C2. Furthermore, results obtained from backward trajectory showed that air pollutants emited from land sources could transport to the offshore region, resulting in high concentration of oversea NOX and VOCs. Major species of VOCs for high O3 formation potential were aromatics and vinyls at the height of 0~500 m around the coastal region of metro Kaohsiung. The control of O3 precursors concentration showed that the ratio of [TVOCs-C2]/[NOX] in the offshore region was higher, indicating that O3 formation was NOX-limited. Therefore, NOX must be controlled for reducing O3 formation. However, the ratio of [TVOCs-C2]/[NOX] in the inland region was lower, some cases even below 4, showing that O3 formation was VOCs-limited. Thus, VOCs must be controlled for reducing O3 formation.

This study measured Ambient concentrations of air pollutants and Volatile Organic Compounds (VOCs) in industrial park in Kaohsiung City. The spatial distribution was investigated during different time periods and seasons. The ozone formation potential (OFP) of VOCs species were evaluated based on the maximum incremental reactivity (MIR). Also, this study using factor analysis to estimate the polluted source. The season distribution of air pollutants showed concentration in spring higher than summer, owing to air activities of summer are acute include wet precipitation, photochemical reaction, and convection. The time period distribution showed the results which NOx and O3 concentration occurred peaks at 7:00 − 8:00, 18:00 − 19:00 and 13:00 − 16:00, respectively. The reason is photochemical reaction, lead to concentration trend with time of NOx inversely to O3. The concentration trend with time of CO and PM10 similar to NOx. The polluted sources were estimated mobile. By the way, O3 is proportional to temperature, but it is Inversely proportional to humility. The seasons distribution of VOCs showed most abundant species included 2-butanone, toluene, and n-pentane in spring, while included toluene, acetone, m,p-xylene, and methyl methacrylate in summer. According to percent composition, most abundant categories in spring and summer were both aromatics, ketones, and alkanes. The TVOC concentration was spring (164.6 £gg/m3) higher than summer (116.4 £gg/m3). The time periods distribution of VOCs showed most abundant categories included aromatics and ketones in morning and evening, while included aromatics and alkanes in night. The TVOC concentration of evening (163.2 ¡Ó 62.7 £gg/m3) was highest, followed by night (159.9 ¡Ó 87.4 £gg/m3), Lowest was morning (98.4 ¡Ó 32.3 £gg/m3). Results showed alkanes and alkenes own higher concentration in night, ketones and esters in evening, and aromatics in evening and night. The reason is related with sunshine, inversion layer, and lower wind speed. By the way, TVOC is proportional to temperature. In spring, the OFP was 566.0 £gg-O3/m3, OFP/TVOC was 3.44. In summer the OFP was 629.3 £gg-O3/m3, OFP/TVOC was 5.41. It was worth mentioning highest OFP categories in spring and summer was both aromatics (332.2 £gg-O3/m3, 380.3 £gg-O3/m3), and highest OFP species was toluene (138.8 £gg-O3/m3) and methyl methacrylate (171.7 £gg-O3/m3) , respectively. The results from factor analyses showed the predominant source included mobile polluted source, petrol evaporation, related electronic industry, metallurgy industry, refinery, and architectural coatings escape in spring. The predominant source included mobile polluted source, petrol evaporation, plastic industry, steel industry, and related electronic industry in summer.

The emission of volatile organic compounds (VOCs) and odors from petrochemical industrial complex, including China Petroleum company (CPC),Renwu and Dazher petrochemical industrial parks, causes poor air quality of northern Kaohsiung. The removal efficiencies of elevated stacks and flares might play important roles on ambient air quality in metro Kaohsiung. Consequently, this study applied a tethered balloon technology to measure the vertical profile of VOCs, and ascertained their three dimensional dispersion in the atmosphere. The vertical profile of VOCs in ambient atmosphere surrounding the petrochemical industrial complex was measured during the intensive sampling periods (September 17-18th and December 20-21st, 2009 and April 8-9th and July 7-8th, 2010). Moreover, this study was designed to sample and analyze VOCs emitted from elevated stacks and flares, and estimate their emission factors. Finally, the source identification and ozone formation were further determined by principal component analysis (PCA) and ozone formation potential (OFP). This study found that some regions had relatively poorer air quality than other regions surrounding the petrochemical industrial complex. Most sampling sites with poor air quality were located at the downwind region of the petrochemical industrial complex, particularly with the prevailing winds blown from the northwest. Moreover, stratification phenomena were frequently observed at most sampling sites, indicating that high-altitude VOCs pollution should be considered for ambient air quality. This study revealed that the indicators of VOCs in northern Kaohsiung were toluene, C2 (ethylene+acetylene+ethane), and acetone. Vertical sampling of VOCs showed that the species of VOCs at the ground and high altitude were different, suggesting that ambient air quality at high altitude might be affected by the emission of VOCs from elevated stacks and flares at the petrochemical industrial complex. Results obtained from PCA showed that the major sources of VOCs in the ambient atmosphere of the petrochemical industrial complex were similar to the characteristics of VOCs emitted from the petrochemical industrial complex. The characteristics of VOCs at high altitude had strong correlation with petrochemical industry, indicating that the ambient air quality of northern Kaohsiung was highly influenced by the emission of VOCs from high stacks and flares. In addition, major VOCs for O3 formation potential at northern Kaohsiung were aromatics and vinyls, with particular species of toluene and C2. Moreover, air pollution episodes resulting from high O3 concentration was usually observed in early winter. Flare sampling results indicated that major VOCs emitted from the ground flare of CPC were alkanes and vinyls. The average removal efficiency of TVOCs was 98.2%. The average emission factor of VOCs was 0.0186 kg NMHC/kg flare gas. In addition, stack sampling results indicated that the emission factors of crude oil distillation process (P105), mixing process (P060), and rubber manufacturing process (P408) were 0.105, 1.11, and 61.97 g/Kl, respectively. The emission factor of P105 was lower than AP-42, while that of P408 was higher than AP-42.

The concentrations of seventy-one hydrocarbons (HC) from C2 to C15 were measured simultaneously at two sites in Kaohsiung city in the morning (07-10), the afternoon (13-16), and the evening (18-21) on 14 days in spring 2003. Results show that the most abundant species of Kaohsiung¡¦s air is toluene (43.36-54.49 £gg m-3), followed by i-pentane, 1,2,4-trimethylbenzene, benzene, n-butane, propane and acetylene, in the range 10.36¡V17.11 £gg m-3. The concentrations of 14 halocarbons are in the range 0.25¡V4.57 £gg m-3. Alkanes (around 44.8%) represent the largest proportion of the total HC, followed by aromatics (35.1%), alkenes (15.5%) and halocarbons (5.4%). The afternoon HC concentrations are much lower than those in the morning and at night, due to relatively intense photochemical reaction and favorable dispersion conditions from noon to afternoon. Notable increases in daily HC concentrations are consistent with high temperature, and low HC concentrations on Sunday coincide with low traffic volume. Photochemical activity is investigated, and HC concentrations are found to decline as the NO2/NOx ratio increases. Correlation analyses imply that vehicle exhaust is the dominant source of atmospheric hydrocarbons in Kaohsiung. The profiles of traffic exhausts were also measured for 25 HC species during the morning and afternoon rush hours on four different days in all three traffic tunnels in Kaohsiung City. Results show that VOC concentrations increase with traffic flow rate, and emission profiles in the three tunnels are mostly in the range C2 ¡V C6. Besides the traffic conditions and vehicle type, the pattern of emissions in each tunnel was also influenced by other factors, such as vehicle age, nearby pollution sources, and the spatial or temporal variation of HC in the urban atmosphere. The ozone formation potential (OFP) in each tunnel was assessed based on the maximum incremental reactivities of the organic species, demonstrating that OFP increases with traffic flow rate. Vehicle distribution influences the contributions of organic group to OFP in a tunnel. Meanwhile, when ranked in descending order of contribution to OFP in all tunnels, the organic groups followed the sequence alkenes, aromatics, and alkanes. The possible source categories affecting the atmospheric HC species were further analyzed using factor analysis. Results showed that the major sources of ambient HC at the Nan-Chie and Hsiung-Kong sites are: vehicle exhaust, petrol/diesel exhaust, industrial processes (for example, plastic/rubber process), combustion exhaust, solvent fugitive or business/consume exhaust. Based on the results of factor analysis, source profiles (or fingerprints) were selected and receptor modeling was conducted based on chemical mass balance (CMB). Results of receptor modeling indicated that, at Nan-Chie site, vehicle exhaust (46.33% and 56.36%) represent the largest proportion of total HC, followed by industrial processes (29.63% and 22.37%) in the morning (07-10) and the evening (18-21), respectively; but were industrial process (40.39%) and solvent fugitive exhaust (30.61%) in the afternoon (13-16). Similarly at Hsiung-Kong site, vehicle exhaust (around 46.19% and 49.29%) represent the largest proportion of total HC, followed by industrial processes (23.19% and 26.11%) in the morning and evening, respectively; but were solvent fugitive exhaust (38.85%), vehicle exhaust (28.95%) and industrial process (25.19%) in the afternoon. It is evident that relatively low traffic volumes in the afternoon at both sites reduce the contribution of traffic exhaust to ambient HC.

Many Canadian water treatment plants supplied by surface waters of the Canadian Prairie and Shield have elevated concentrations of trihalomethanes (THMs), which exceed the provincial standards. These water sources are characterized by elevated levels of dissolved organic carbon (DOC) and varying levels of calcium hardness, which causes a challenge for the removal of THMs precursors. The objective of this study was to investigate the effect of two treatment methods: chemical coagulation and pre-ozonation-coagulation on the removal of DOC as the main THMs precursor. Surface waters typical for the Canadian Prairie and Canadian Shield were used in the experiments which includes Assiniboine River, Red River, and Rainy River. The effects of different experimental conditions such as coagulant dose, coagulant type, and solution pH as well as ozone dosage on THMs removal were investigated. The structural and chemical characteristics of natural organic matter and isolated humic substances, before and after the reaction with ozone, were studied using spectroscopic techniques. The results illustrated that the quality of source water (DOC characteristics, concentration of water DOC and Calcium) has a significant impact on THMs reduction by chemical coagulation and ozonation. Coagulation results showed that reduction of total DOC does not guarantee THMFP reduction and chemical coagulation should be optimized to remove the hydrophobic acid fraction which forms most THMs. The removal of DOC by aluminum-based coagulants was affected more by the concentration of polymeric and colloidal aluminum speciation. This finding is especially important for plants supplied by high alkalinity waters where pH adjustment is a serious challenge. The effect of pre-ozonation on coagulation varies depending on the concentration of calcium, which has the ability to form complexes with DOC compounds promoting their removal in coagulation. For the surface water with high levels of organic carbon and calcium hardness, ozonation prior to coagulation was beneficial in terms of DOC reduction. However, it showed the opposite effect on water with high levels of DOC accompanied with low level of calcium hardness. Spectroscopic results showed that ozonation of NOM and humic substances cause a significant reduction of aromatic and highly conjugated compounds (constituting primarily the hydrophobic acid fraction). / February 2016

Disinfection is an essential process in the treatment of municipal wastewater before the treated wastewater can be discharged to the environment. Hillsborough County's Northwest Regional Water Reclamation Facility (NWRWRF) in Tampa, Florida, currently uses ultraviolet (UV) light for disinfection. However, this method has proven expensive to implement and maintain, and may not be effective if the light transmission is poor. For these reasons, Hillsborough County is considering switching from UV light to sodium hypochlorite for disinfection. However, hypochlorite (chlorine) disinfection has disadvantages as well, such as the production of disinfection by-products (DBPs) such as trihalomethanes (THM) and haloacetic acids (HAAs), which may have adverse impacts on the quality of surface waters that receive the treated wastewater. Therefore, the objectives of this research are (1) to compare NWRWRF typical operating conditions and water quality to those of two nearby facilities (River Oaks and Dale Mabry Advanced Wastewater Treatment Plants) that currently employ chlorine disinfection, (2) to determine the chlorine demand of treated effluent from NWRWRF, (3) to quantify the DBP formation potential of treated effluent from NWRWRF, and (4) to determine the effects of temperature, reaction time, and chlorine dose on chlorine demand and THM formation. To inform laboratory experiments, the quality of final effluent was monitored at NWRWRF and at two nearby wastewater treatment plants that currently use hypochlorite for disinfection. At these two facilities, pH of 7.0-8.0, chemical oxygen demand (COD) of 12-26 mg/L, alkalinity of 200-250 mg/L as CaCO3, chlorine residual of 1.5-6.0 mg/L, and total trihalomethanes of 100-190 ix μg/L (mostly chloroform) were observed. Conditions at NWRWRF were similar to those at Dale Mabry and River Oaks AWWTP, suggesting that chlorine demand and THM formation at NWRWRF would be similar to those at the two AWWTP, if chlorination is to be used. THM experimental results agreed with this suggestion. Chlorine dose and temperature effects on the free chlorine residual and THMs production in NWRWRF filtered wastewater effluent were determined. Filtered effluent was collected and transported to USF laboratory where it was tested for 3 different chlorine doses (6 mg/L, 9 mg/L and 12 mg/L as Cl2) and 3 different temperatures (16°C, 23°C, and 30°C) at 7 different contact times (15, 30, 45, 60, 75, 90, and 120 min) in duplicate. The total number of batches prepared was: 3 different chlorine doses × 3 different temperatures × 7 different reaction times = 126 reactors. According to Florida Administrative code 62-600.440, total chlorine residual should be at least 1 mg/L after a contact time of at least 15 min at peak hourly flow. Also, according to Florida Administrative code 62-600.440, if effluent wastewater has a concentration of fecal coliforms greater than 10,000 per 100 mL before disinfection, FDEP requires that the product of the chlorine concentration C (in mg/L as Cl2) and the contact time t (in minutes) be at least 120. Results showed that free chlorine residual was always above 1 mg/L in 15 min contact time for all chlorine doses and temperatures tested in this thesis. However, to be conservative, thesis conclusions and recommendations were based on the more stringent regulation: C*t ≥ 120 mg.min/L, assuming that the number of fecal coliform in NWRWRF wastewater effluent exceeds 10,000 per 100 mL prior to disinfection. The analysis showed that free chlorine residual for 6 mg/L was below the FDEP standard at all temperatures. At 16 °C and 23 °C, chlorine doses of 9 and 12 mg/L resulted in an appropriate free chlorine residual above the FDEP standard. However, a chlorine dose of 12 mg/L was resulting in high residual, which means high THM would be expected. Therefore, at 16 x and 23°C, 9 mg/L would be preferable. At 30 °C, only the chlorine dose of 12 mg/L met the standard at all contact times. As expected, free chlorine residual decreased with an increase in temperature from 23°C to 30°C. Surprisingly, the residual at 16°C was lower than residual at 23°C. The production of THMs increased with higher contact time in all the experiments completed. Chlorine dose didn't have an effect on THM formation at 23°C, but it did at 30°C and 16°C, where THM concentrations were generally higher with the increase of chlorine dose. Temperature effect was noticed in most of the experiments, where THM production was usually higher at higher temperatures, except some cases where formation was similar for different temperatures. Chloroform, dichlorobromomethane, dibromochloromethane production ranges were respectively: 20-127 μg/L, 18-59 μg/L, and 3-7 μg/L. Bromoform concentrations were not observed in this experiment at any temperature or chlorine dose. According to Florida Administrative code 62-302.530, Criteria for Surface Water Quality Classifications, the Florida Department for Environmental Protection (FDEP) set the following limits for THM concentrations in wastewater effluent to be as the following; 470 μg/L for chloroform, 22 μg/L for dichlorobromomethane, 34 μg/L for dibromochloromethane, and 360 μg/L for bromoform. Experimental results on NWRWRF filtered effluent showed that only dichlorobromomethane exceeded the limits set by FDEP at about 30 min contact time for all temperatures and chlorine doses tested. However, according to Florida Administrative code 62- 302-400, proposed changes to the code have set higher DCBM limit of 57 μg/L. Chlorination would be recommended at NWRWRF if the DCBM regulated limit increases to 57 μg/L. The recommended chlorine dose would be 9 mg/L for water temperatures around 16-23 °C and 12 mg/L for water temperatures around 30 °C

O presente trabalho consistiu na realização de um estudo geológico na porção norte da Bacia intracratônica do Paraná. O estudo buscou avaliar o potencial gerador e de exploração de shale gas e shale oil dos folhelhos negros da Formação Irati na região de Goiás e Mato Grosso, Centro-Oeste do Brasil, através da caracterização de geoquímica orgânica dos folhelhos, determinação do potencial gerador e grau de maturação da matéria orgânica dos folhelhos, caracterização das relações geológicas da formação, espessuras, áreas de ocorrência, alternância de camadas com carbonatos, profundidade de ocorrência, padrões de fraturamento, composição mineralógica e estimativa de reservas de shale gas tecnicamente recuperáveis. O trabalho contribui com uma metodologia que permite avaliar o potencial de geração e exploração de recursos de shale gas e shale oil. O estudo na temática de recursos energéticos não convencionais, com destaque para o shale gas, principal fonte de gás natural não convencional explorada no mundo, é de extrema importância, pois o gás natural é considerado um combustível de transição de uma matriz energética baseada em energias fósseis para uma matriz com predominância de energias renováveis, considerando-se os seus benefícios, tanto ambientais quanto em aspectos estratégicos e econômicos. Os valores de COT variam de 0,04 a 3,52% com média de 1,31%, o que lhes confere um bom potencial gerador de hidrocarbonetos na área de estudo. Foram encontrados valores no pico S2 que variam de 5,13 a 63,13 mg HC/g de rocha para a maioria das amostras estudadas pela pirólise Rock-Eval, conferindo-lhes um bom a excelente potencial petrolífero. Os folhelhos apresentam querogênio do tipo I, II e IV, com predomínio do querogênio do tipo II e IV. Estudos de maturidade térmica da matéria orgânica (querogênio) com base nos valores de Tmax, IH, IP e Ro, indicam seu grau como imaturo (com baixo nível de conversão em hidrocarbonetos) a supermaturo (zona de gás seco). Amostras que alcançaram a janela de geração de gás seco não possuem potencial para geração de hidrocarbonetos, uma vez que apresentam querogênio do tipo IV, que evidencia baixo poder de preservação da matéria orgânica durante o intenso magmatismo ocorrido no Mesozóico (Jurássico/Cretáceo). A maioria das amostras analisadas apresentam bom potencial para shale gas e/ou shale oil, porém as condições de temperatura e pressão durante a diagênese não foram suficientes para a maturação da matéria orgânica nos folhelhos. Os folhelhos possuem altos teores de quartzo e quantidades significativas de outros minerais tais como, o feldspato plagioclásio (albita), mica e carbonatos (calcita e dolomita), podendo responder favoravelmente à fraturamento hidráulico. A estimativa de reservas indica que a área de estudo poderia ter um potencial para cerca de 23 Trilhões de Pés Cúbicos de reservas de gás natural não comprovadas tecnicamente recuperáveis. / The present work consisted in the accomplishment of a geological study in the northern portion of the Intracratonic Basin of Paraná. The study aimed to evaluate the potential for shale gas and shale oil exploitation of the Irati Formation black shales in the region of Goiás and Mato Grosso, Mid-West of Brazil, through the characterization of organic geochemistry of shales, determination of the generating potential and degree of maturation of the organic matter of the shales, characterization of the geological relations of the formation, thicknesses, areas of occurrence, alternation of layers with carbonates, depth of occurrence, fracturing patterns, mineralogical composition and estimation of technically recoverable shale gas reserves. The work contributes with a methodology that allows to evaluate the potential of generation and exploitation of shale gas and shale oil resources. The study on the subject of unconventional energy resources, especially shale gas, the main source of unconventional natural gas explored in the world, is extremely important because natural gas is considered a transition fuel of a energy matrix based on energies fossils for a matrix with predominance of renewable energies, considering its benefits, both environmental and strategic and economic aspects. The TOC values vary from 0.04 to 3.52% with an average of 1.31%, which gives them a good hydrocarbon potential in the study area. S2 peak values ranging from 5.13 to 63.13 mg HC / g of rock were found for most of the samples studied by Rock-Eval pyrolysis, giving them a good excellent oil potential.The shales present type I, II and IV kerogen, with predominance of type II and IV kerogen. Thermal maturity studies of organic matter (kerogen) based on the values of Tmax, HI, PI and Ro, indicate their degree as immature (with low conversion level in hydrocarbons) to supermature (dry gas zone). Samples that reached the window of dry gas generation do not have potential for hydrocarbon generation, since they present type IV kerogen, which evidences low preservation power of organic matter during the intense magmatism occurring in the Mesozoic (Jurassic / Cretaceous). Most of the analyzed samples present good potential for shale gas and / or shale oil, but the conditions of temperature and pressure during diagenesis were not sufficient for the maturation of the organic matter in the shales. The shales have high quartz contents and significant amounts of other minerals such as plagioclase feldspar (albite), mica and carbonates (calcite and dolomite), and can respond favorably to hydraulic fracturing. The reserve estimate indicates that the study area could have a potential for about 23 trillion cubic feet of unproved technically recoverable natural gas reserves.

The main theme of this thesis is the usage of the test investigating the formation potential of trihalogenmethanes (THM FP) and its comparison with conventional indicators of water quality (CODMn, A254 and colours). As for the experimental part of the thesis, rating of the effectiveness of selected technological procedures has been applied (e.g.: coagulation, adsorption and ozonation in the act of treatment of artificially prepared water model with a higher content of humic substances in laboratory conditions). Based on the obtained results, it was found that the common indicators of water quality have very similar attributes and also complete each other. On the contrary, those attributes of indicators may not be sufficient in case of the evaluation of water quality with high content of humic substances. The findings made illustrate that the THM FP test enables the accurate evaluation of water quality, especially in connection with the content of an organic material susceptible to chemical changes. THM formation potential has proved its high value and also has confirmed that it can appropriately complete the other standarts that are being used for assessing the quality of treated water up to nowadays.