Atmospheric deposition of nitrogen species represents an additional nutrient source to natural environments, and can alter the nitrogen cycle by increasing nutrient levels beyond the requirements of organisms. In Tampa Bay, atmospheric deposition of dissolved inorganic nitrogen species (DIN) has been found to be the second largest nitrogen source, but little is known about dissolved organic nitrogen species (DON). The research goal was to improve the dry and wet deposition estimates by inclusion of the DON contribution. In the atmospheric chemistry field a standard method to measure DON in atmospheric samples has not been agreed upon. This research proposes the use of the ultraviolet (UV)-photolysis method and presents the optimal settings for its application on atmospheric samples. Using a factorial design scheme, experiments on surrogate nitrogen compounds, typically found in the atmosphere, indicated that DON can be xviii measured with no biases if optimal settings are fixed to be solution pH 2 with a 24-hr irradiance period. DIN species (NH4 +, NO2 -, NO3 -) and DON concentrations were determined in fine (PM2.5) and coarse particles (PM10-2.5) as well as in rainwater samples collected at Tampa Bay. The estimates of wet deposition fluxes for NH4 +, NO3 - and DON were 1.40, 3.18 and 0.34 kg-N ha-1yr-1, respectively. Hourly-measured gas concentrations and 24-hr integrated PM10 concentrations were used in conjunction with a below-cloud scavenging model to explain DIN and DON concentration in rainwater samples. Scavenging of aerosol-phase DON contributed only 0.9 ± 0.2% to rainwater DON concentrations, and therefore gas scavenging should be responsible for 99%. These results confirmed the existence of negative biases in the dry and wet deposition fluxes over Tampa Bay. There is increasing interest in simulating wet deposition fluxes, and the proposed below-cloud scavenging model offers a new computational approach to the problem. It integrates the typical gas and particle collection functions and the concept of the deposition-weighted average concentrations. The model uses mass balance to describe the time-dependent cumulative contribution of all droplets in the rain spectrum to the rainwater concentration, giving predictions closer to experimental values and better estimations than those reported in the literature for similar cases.

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

Neste trabalho, estudou-se a degradação do bisfenol A (BPA) em solução aquosa através da fotólise direta sob radiação UV em 254 nm. Os experimentos foram realizados um reator fotoquímico tubular de vidro de 3,9 L, equipado com uma lâmpada de vapor de mercúrio de baixa pressão tubular concêntrica (36 W). Avaliaram-se os efeitos da taxa específica de emissão de fótons (0,87×10 18 ; 1,4×1018 e 3,6×1018 fótons L-1 s-1 ) e da concentração inicial de BPA (10 a 50 mg L-1 ), conforme um projeto experimental Doehlert. Os resultados dos experimentos indicaram que a degradação do BPA diminui com o aumento de sua concentração inicial, seguindo decaimento de pseudo primeira-ordem. A constante cinética de velocidade de degradação do BPA variou de 0,001 a 0,0066 min-1 , enquanto a porcentagem de degradação de BPA ao final de 120 minutos variou de 14 a 55%; já a remoção do carbono orgânico total variou entre 1,5 e 12,5%. Houve a formação de produtos persistentes e as espécies reativas de oxigênio (1 O2 oOH ) mostraram-se muito importantes durante a degradação do BPA. O rendimento quântico para fotólise de BPA foi de 0,0075 mol BPA mol fótons-1, determinado a partir dos dados experimentais através de um modelo matemático para degradação fotolítica do BPA em função do tempo. Para tanto, considerou-se um sistema de tratamento formado por um reator tubular e um tanque de mistura com recirculação entre eles, sendo o reator tubular tratado como uma série de três reatores contínuos de mistura perfeita (CSTR) associados entre si. Através da análise estatística dos dados experimentais para duas respostas (constante específica de degradação do BPA e porcentagem de degradação do BPA ao final de 120 minutos) avaliaram-se os efeitos das variáveis envolvidas (concentração inicial de BPA e taxa específica de emissão de fótons). / The aim of this study was to evaluate bisphenol A (BPA) degradation in aqueous solution by direct photolysis under UV radiation at 254 nm, considering the effects of the specific rate of photon emission (0.87×1018; 1.4×1018 and 3.6×1018 fótons L-1 s-1) and the initial BPA concentration (10-50 mg L-1), according to a Doehlert experimental design. The experiments were performed in a glass tubular photochemical reactor of 3.9 L equipped with a concentric low pressure mercury vapor lamp of 36 W. The experimental results indicated that BPA degradation decreases with increasing initial concentration, following pseudo first-order decay, and increases with increasing specific rate of photon emission. The values of the specific BPA degradation rate varied in the range 0.001-0.0066 min-1, while BPA percent degradation at 120 minutes of irradiation varied from 14 to 55%; TOC removal varied from 1.5 to 12.5%. Persistent degradation products were formed, and oxygen reactive species (1O2, oHO) showed to exhibit an important role during BPA degradation. The obtained quantum yield of BPA photolysis was 0.0075 mol BPA mol photons-1, determined from the experimental data through a mathematical model for BPA photolytic degradation versus time. With that aim a treatment system formed by a tubular reactor connected with a mixing tank with recirculation between them was considered; the tubular reactor was treated as a series of three associated continuous perfect mixing reactors (CSTR). Through statistical analysis of the experimental data for two responses (specific BPA degradation rate and BPA percent degradation at 120 minutes), the effects of the variables involved in BPA degradation (initial BPA concentration and specific rate of photon emission) were discussed.

Neste trabalho, estudou-se a degradação do bisfenol A (BPA) em solução aquosa através da fotólise direta sob radiação UV em 254 nm. Os experimentos foram realizados um reator fotoquímico tubular de vidro de 3,9 L, equipado com uma lâmpada de vapor de mercúrio de baixa pressão tubular concêntrica (36 W). Avaliaram-se os efeitos da taxa específica de emissão de fótons (0,87×10 18 ; 1,4×1018 e 3,6×1018 fótons L-1 s-1 ) e da concentração inicial de BPA (10 a 50 mg L-1 ), conforme um projeto experimental Doehlert. Os resultados dos experimentos indicaram que a degradação do BPA diminui com o aumento de sua concentração inicial, seguindo decaimento de pseudo primeira-ordem. A constante cinética de velocidade de degradação do BPA variou de 0,001 a 0,0066 min-1 , enquanto a porcentagem de degradação de BPA ao final de 120 minutos variou de 14 a 55%; já a remoção do carbono orgânico total variou entre 1,5 e 12,5%. Houve a formação de produtos persistentes e as espécies reativas de oxigênio (1 O2 oOH ) mostraram-se muito importantes durante a degradação do BPA. O rendimento quântico para fotólise de BPA foi de 0,0075 mol BPA mol fótons-1, determinado a partir dos dados experimentais através de um modelo matemático para degradação fotolítica do BPA em função do tempo. Para tanto, considerou-se um sistema de tratamento formado por um reator tubular e um tanque de mistura com recirculação entre eles, sendo o reator tubular tratado como uma série de três reatores contínuos de mistura perfeita (CSTR) associados entre si. Através da análise estatística dos dados experimentais para duas respostas (constante específica de degradação do BPA e porcentagem de degradação do BPA ao final de 120 minutos) avaliaram-se os efeitos das variáveis envolvidas (concentração inicial de BPA e taxa específica de emissão de fótons). / The aim of this study was to evaluate bisphenol A (BPA) degradation in aqueous solution by direct photolysis under UV radiation at 254 nm, considering the effects of the specific rate of photon emission (0.87×1018; 1.4×1018 and 3.6×1018 fótons L-1 s-1) and the initial BPA concentration (10-50 mg L-1), according to a Doehlert experimental design. The experiments were performed in a glass tubular photochemical reactor of 3.9 L equipped with a concentric low pressure mercury vapor lamp of 36 W. The experimental results indicated that BPA degradation decreases with increasing initial concentration, following pseudo first-order decay, and increases with increasing specific rate of photon emission. The values of the specific BPA degradation rate varied in the range 0.001-0.0066 min-1, while BPA percent degradation at 120 minutes of irradiation varied from 14 to 55%; TOC removal varied from 1.5 to 12.5%. Persistent degradation products were formed, and oxygen reactive species (1O2, oHO) showed to exhibit an important role during BPA degradation. The obtained quantum yield of BPA photolysis was 0.0075 mol BPA mol photons-1, determined from the experimental data through a mathematical model for BPA photolytic degradation versus time. With that aim a treatment system formed by a tubular reactor connected with a mixing tank with recirculation between them was considered; the tubular reactor was treated as a series of three associated continuous perfect mixing reactors (CSTR). Through statistical analysis of the experimental data for two responses (specific BPA degradation rate and BPA percent degradation at 120 minutes), the effects of the variables involved in BPA degradation (initial BPA concentration and specific rate of photon emission) were discussed.

É grande a preocupação quanto à presença de poluentes persistentes (POP) no ambiente aquático, devido ao potencial destes micropoluentes em afetar organismos aquáticos e a saúde humana. Dentre os POP estão os herbicidas atrazina (ATZ) e amicarbazona (AMZ), empregados no controle de ervas daninhas no cultivo de cana-de-açúcar, responsável por grande parte do consumo de herbicidas no país. O conhecimento do destino desses compostos no meio ambiente é essencial para avaliar seus potenciais impactos, embora não haja na literatura estudos detalhados relacionados a esse tema. No presente trabalho, através da combinação de resultados de experimentos realizados em simulador solar empregando matéria orgânica natural isolada, dados da literatura e simulações matemáticas, foi investigado o destino ambiental fotoquímico da AMZ, considerando as características de corpos d\'águas brasileiros. Analogamente e para fins de comparação, simulou-se o destino ambiental fotoquímico da ATZ com base em informações da literatura. Os resultados das simulações indicaram que a matéria orgânica dissolvida e a profundidade da coluna d\'água são as variáveis que mais influenciam na persistência dos dois herbicidas. O tempo de meiavida pode chegar a aproximadamente 2 meses e 1 ano, para AMZ e ATZ, respectivamente. Assim como é importante o entendimento do destino ambiental dos POP, também é essencial a investigação de processos avançados de oxidação desses poluentes, muitos dos quais são fotoirradiados. Procurando contribuir nesse sentido, neste trabalho estudou-se a fotólise da ATZ sob radiação UV em 254 nm, considerando os efeitos da taxa específica de emissão de fótons e da concentração inicial do herbicida. Procurou-se investigar detalhadamente o papel de espécies reativas de oxigênio (ROS) neste processo, resultados até então não discutidos na literatura. Além disso, os resultados obtidos para ATZ foram comparados aos disponíveis na literatura para AMZ. A degradação dos dois herbicidas diminui com o aumento da concentração inicial dos herbicidas, seguindo decaimento de pseudo primeira-ordem e aumentando com a taxa de emissão de fótons. Os resultados sugerem a formação de produtos persistentes e as ROS foram apontadas como atores importantes durante a degradação fotolítica dos herbicidas. / The presence of Persistent Organic Pollutants (POP) in aquatic environment is a subject of great concern, especially due to their capacity to affect not only aquatic organisms but also the human health. Herbicides as atrazine (ATZ) and amicarbazone (AMZ) are also classified as POP and are widely applied to control weeds on sugarcane cultivations, which are responsible for the increased consumption of herbicides in Brazil. The knowledge regarding the fate of these compounds once released into the environment represents an important issue and is also a type of information usually lacking in the available literature. Through the use of results obtained in experiments performed with a solar simulator, literature data, and mathematical simulations, the photochemical destination of AMZ in the environment was studied considering the characteristics of Brazilian surface water bodies. For purposes of comparison, the environmental destination of ATZ was also simulated. The results indicate that the dissolved organic matter and the depth of the water column are the most influential variables in the environmental persistence of these pesticides. Their half-life may extend up to 2 months to a year, for AMZ and ATZ, respectively. Besides the environmental fate, this investigation also aims to shine a light on the degradation of these contaminants in irradiated advanced oxidation processes. Accordingly, ATZ photolysis through the use of UV radiation (254 nm) was studied, whilst taking into consideration both the herbicide initial concentration and the specific photon emission rate. Another important contribution of this study is the investigation of the role of reactive oxygen species (ROS) in photolytic processes, a subject not usually discussed in the literature. In addition, a crossed-reference analysis between the results obtained for ATZ and those available in the literature for AMZ is presented. The degradation of both herbicides diminishes with the increase in their initial concentration and follows a pseudo first-order decay, increasing with the photon emission rate. Moreover, the results indicate that the formation of persistent degradation products does occur and that ROS play a crucial role in photolytic herbicide degradation.

É grande a preocupação quanto à presença de poluentes persistentes (POP) no ambiente aquático, devido ao potencial destes micropoluentes em afetar organismos aquáticos e a saúde humana. Dentre os POP estão os herbicidas atrazina (ATZ) e amicarbazona (AMZ), empregados no controle de ervas daninhas no cultivo de cana-de-açúcar, responsável por grande parte do consumo de herbicidas no país. O conhecimento do destino desses compostos no meio ambiente é essencial para avaliar seus potenciais impactos, embora não haja na literatura estudos detalhados relacionados a esse tema. No presente trabalho, através da combinação de resultados de experimentos realizados em simulador solar empregando matéria orgânica natural isolada, dados da literatura e simulações matemáticas, foi investigado o destino ambiental fotoquímico da AMZ, considerando as características de corpos d\'águas brasileiros. Analogamente e para fins de comparação, simulou-se o destino ambiental fotoquímico da ATZ com base em informações da literatura. Os resultados das simulações indicaram que a matéria orgânica dissolvida e a profundidade da coluna d\'água são as variáveis que mais influenciam na persistência dos dois herbicidas. O tempo de meiavida pode chegar a aproximadamente 2 meses e 1 ano, para AMZ e ATZ, respectivamente. Assim como é importante o entendimento do destino ambiental dos POP, também é essencial a investigação de processos avançados de oxidação desses poluentes, muitos dos quais são fotoirradiados. Procurando contribuir nesse sentido, neste trabalho estudou-se a fotólise da ATZ sob radiação UV em 254 nm, considerando os efeitos da taxa específica de emissão de fótons e da concentração inicial do herbicida. Procurou-se investigar detalhadamente o papel de espécies reativas de oxigênio (ROS) neste processo, resultados até então não discutidos na literatura. Além disso, os resultados obtidos para ATZ foram comparados aos disponíveis na literatura para AMZ. A degradação dos dois herbicidas diminui com o aumento da concentração inicial dos herbicidas, seguindo decaimento de pseudo primeira-ordem e aumentando com a taxa de emissão de fótons. Os resultados sugerem a formação de produtos persistentes e as ROS foram apontadas como atores importantes durante a degradação fotolítica dos herbicidas. / The presence of Persistent Organic Pollutants (POP) in aquatic environment is a subject of great concern, especially due to their capacity to affect not only aquatic organisms but also the human health. Herbicides as atrazine (ATZ) and amicarbazone (AMZ) are also classified as POP and are widely applied to control weeds on sugarcane cultivations, which are responsible for the increased consumption of herbicides in Brazil. The knowledge regarding the fate of these compounds once released into the environment represents an important issue and is also a type of information usually lacking in the available literature. Through the use of results obtained in experiments performed with a solar simulator, literature data, and mathematical simulations, the photochemical destination of AMZ in the environment was studied considering the characteristics of Brazilian surface water bodies. For purposes of comparison, the environmental destination of ATZ was also simulated. The results indicate that the dissolved organic matter and the depth of the water column are the most influential variables in the environmental persistence of these pesticides. Their half-life may extend up to 2 months to a year, for AMZ and ATZ, respectively. Besides the environmental fate, this investigation also aims to shine a light on the degradation of these contaminants in irradiated advanced oxidation processes. Accordingly, ATZ photolysis through the use of UV radiation (254 nm) was studied, whilst taking into consideration both the herbicide initial concentration and the specific photon emission rate. Another important contribution of this study is the investigation of the role of reactive oxygen species (ROS) in photolytic processes, a subject not usually discussed in the literature. In addition, a crossed-reference analysis between the results obtained for ATZ and those available in the literature for AMZ is presented. The degradation of both herbicides diminishes with the increase in their initial concentration and follows a pseudo first-order decay, increasing with the photon emission rate. Moreover, the results indicate that the formation of persistent degradation products does occur and that ROS play a crucial role in photolytic herbicide degradation.