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Since the early 70's chemistry and transport models (ChTMs) have been proposed and improved. Tropospheric ChTMs for trace species are detailed numerical formulations intended to represent the atmospheric system as a whole, accounting for all the individual processes and phenomena that influence climate changes. The development of computer resources and the retrieval of emission inventories and observational data of the species of interest have enhanced the model evolution towards three-dimensional global models that account for more complicated chemical mechanisms, wet and dry deposition phenomena, and interactions and feedback mechanisms between meteorology and atmospheric chemistry. The purpose of this study is to ascertain the sensitivity of the solar radiative field in the atmosphere to absorption and scattering by aerosols. This effort is preliminary to the study of feedback mechanisms between photolytic processes that create and destroy aerosols and the radiation field itself. In this study, a cloud of water-soluble aerosols, randomly distributed in space within hypothetical 1-cm cubes of atmosphere, is generated. A random radius is assigned to each aerosol according to a lognormal size distribution function. The radiative field characterization is analyzed using a Mie scattering code to determine the scattering phase function and the absorption and scattering coefficients of sulfate aerosols, and a Monte Carlo ray-trace code is used to evaluate the radiative exchange. The ultimate goal of the effort is to create a tool to analyze the vertical distribution of absorption by aerosols in order to determine whether or not feedback between photolytic processes and the radiation field needs to be included in a Third Generation Chemistry and Transport model. / Master of Science

<p>Many modern products, especially electronic goods, are protected by brominated flame retardants (BFR). Some of the most common flame retardants are polybrominated diphenylethers (PBDE), tetrabromobisphenol-A (TBBP-A) and hexabromocyclododecane (HBCD). These compounds have been found in environmental samples and shown to have physiological effects on experimental animals. This thesis considers end-of-life aspects of brominated flame retardants. When spread in the environment, these compounds may be degraded into other forms. For example, if sludge contaminated with PBDE is used as an agricultural fertilizer, the PBDE could be degraded by sunlight to species of PBDE with lower degree of bromination and, to some extent, also form polybrominated dibenzofurans (PBDF). In addition, PBDF and polybrominated dibenzo-p-dioxins (PBDD) are formed during combustion of brominated flame retardants. When waste products with brominated flame retardants are co-combusted with household waste or other chlorinated fuel, polybrominated- chlorinated dibenzo-p-dioxins (PBCDD) and polybrominated- chlorinated dibenzofurans (PBCDF)will be formed. The bromin/chlorine composition of dioxins and furans is dependent on the bromine/chlorine ratio in the fuel, but the types of brominated flame retardants that are being combusted is less important. In the studies reported here, bromine levels higher than "normal" for household waste has been used. The results show that there is a pronounced increase in total dioxin levels in fluegas when when bromine is present, implying that waste containing brominated flame retardants should only be incinerated at combustion plants with effecient air pollution control devices.</p>

Neurological and neuroendocrine disorders result from signaling dysregulation at the molecular, cellular, and multi-cellular levels. This dissertation presents the development of separation methods, using capillary zone electrophoresis (CZE) and capillary liquid chromatography (CLC), for detecting and quantifying small molecules, peptides, and proteins involved in cellular signaling. CZE is a rapid separation technique, making it ideal for monitoring cellular dynamics with high temporal resolution. An ultraviolet - light emitting diode was used for photolytic optical gating of caged fluorophore-labeled biogenic amines, common functional groups in neurotransmitters. Additionally, a novel caged fluorophore with faster reaction kinetics than commercially available dyes was used to label reduced thiols and primary amines in the presence of o-phthalaldehyde. Together this light source and novel caged dye illustrate the utility of these methods for monitoring chemical dynamics during continuous sampling. Many cellular second messengers, including inositol phosphates, are known to exist within the cell, but their dynamics and intermolecular interactions are poorly understood since they lack chromophores or electroactive functional groups making direct detection difficult. Utilizing CZE with capacitive coupled contactless conductivity detection (C4D), biological phosphates were separated and detected based on their high anionic charge, suggesting the utility of C4D in label-free detection of biological molecules. The techniques described above require higher sensitivity to monitor physiologically relevant analyte concentrations; therefore, Hadamard transform capillary electrophoresis (HTCE) was used as a multiplexing method in which multiple separations were performed simultaneously. HTCE resulted in increased sensitivity by decreasing the random background noise. Peptides and proteins propagate signals within or between cells; yet, they are difficult to separate and detect by CZE since their highly charged surfaces result in non-specific adsorption to the capillary wall. To minimize these interactions, stable hybrid phospholipid bilayers were prepared as capillary coatings for CZE separations of cationic proteins. Additionally, stabilized phospholipid bilayer coatings were formed on silica particles through redox polymerization of synthetic, polymerizable lipids. These bilayers were stable after exposure to surfactant, organic solvents, and after storage for one month, suggesting their value as lipid chromatography stationary phases for future incorporation of transmembrane proteins to analyze binding interactions with small molecules.

The aim of the investigation described in this work is to gain a better understanding of the processes involved in the oxidation of organic compounds by photolytic ozonation in a laboratory scale reactor. The results and discussions are presented in Chapter III. This chapter contains four parts. In the first part, mass transfer efficiency and the calculation of the mass transfer coefficient, KLa, as well as the ozone decomposition rate constant, KD, are presented and compared with those obtained by other investigators. The second part deals with the kinetics of the photolysis of 2,2',4,4',6,6'-hexachlorobiphenyl both in purified and natural lake water. Mathematical expressions and a discussion of the possible reaction processes involved are given. Kinetic models of ozonation and photolytic ozonation in purified and natural lake water are developed and discussed in part three. Rate constants are calculated from experimental data and used to predict values of substrate destruction with a mathematical model. The fourth part of this chapter deals with the identification of products from the photolysis, ozonation and photolytic ozonation of 2,2'4,4',6,6'-hexachlorobiphenyl. The products are isolated and identified using combined gas chromatography and mass spectroscopy, and reaction mechanisms are suggested.

Many modern products, especially electronic goods, are protected by brominated flame retardants (BFR). Some of the most common flame retardants are polybrominated diphenylethers (PBDE), tetrabromobisphenol-A (TBBP-A) and hexabromocyclododecane (HBCD). These compounds have been found in environmental samples and shown to have physiological effects on experimental animals. This thesis considers end-of-life aspects of brominated flame retardants. When spread in the environment, these compounds may be degraded into other forms. For example, if sludge contaminated with PBDE is used as an agricultural fertilizer, the PBDE could be degraded by sunlight to species of PBDE with lower degree of bromination and, to some extent, also form polybrominated dibenzofurans (PBDF). In addition, PBDF and polybrominated dibenzo-p-dioxins (PBDD) are formed during combustion of brominated flame retardants. When waste products with brominated flame retardants are co-combusted with household waste or other chlorinated fuel, polybrominated- chlorinated dibenzo-p-dioxins (PBCDD) and polybrominated- chlorinated dibenzofurans (PBCDF)will be formed. The bromin/chlorine composition of dioxins and furans is dependent on the bromine/chlorine ratio in the fuel, but the types of brominated flame retardants that are being combusted is less important. In the studies reported here, bromine levels higher than "normal" for household waste has been used. The results show that there is a pronounced increase in total dioxin levels in fluegas when when bromine is present, implying that waste containing brominated flame retardants should only be incinerated at combustion plants with effecient air pollution control devices.

<p>Ispitana je direktna i indirektna fotoliza alprazolama (ALP) i amitriptilina (AMI)<br />primenom UV, vidljivog&nbsp; i simuliranog sunčevog zračenja (SSZ). Takođe, praćena je stabilnost vodenih rastvora ALP i AMI u mraku.&nbsp; U okviru ispitivanja fotokatalitičke&nbsp; razgradnje ALP,ispitana je efikasnost ZnO i TiO_2&nbsp;Degussa P25 primenom UV i SSZ.&nbsp; Takođe, proučavan je&nbsp; utica jmasene koncentracije fotokatalizatora, pH, kao i<br />uticaj hvatača radikala/&scaron;upljina&nbsp; i elektron-akceptora.&nbsp; Praćen je stepen mineralizacije<br />merenjem ukupnog organskog ugljenika i primenom&nbsp; jonske hromatografije. Takođe,<br />detaljno su ispitani reakcioni intermedijeri.&nbsp; Dalje,ispitano&nbsp; je ponovno kori&scaron;ćenje ZnO u tri uzastopna procesa razgradnje ALP. U cilju praćenja citotoksičnosti ALP, ispitan je&nbsp; in vitro rast dve ćelijske linije: Neuro-2a i MRC-5. Zatim,proučavana je efikasnost sintetisanih ZnO (ZnO modifikovani mlevenjem i kalcinacijom, ZnO dopirani jonima Mg(II), ternarni i&nbsp; me&scaron;ani&nbsp; cink-kalaj-oksidi) i TiO₂&nbsp; (anatas&nbsp; TiO₂&nbsp; nedopirani&nbsp; i dopirani La(III)-jonima, brukitni TiO2) nanoprahova u razgradnji ALP primenom UV i SSZ. U okviru fotokatalitičke razgradnje AMI, ispitana&nbsp; je&nbsp; efikasnost&nbsp; razgradnje&nbsp; pri različitim eksperimentalnim uslovima&nbsp; (uticaj vrste fotokatalizatora i zračenja, masene&nbsp; koncentracije fotokatalizatora, početne koncentracije supstrata, uticaj prisustva&nbsp; kako&nbsp; hvatača radikala i &scaron;upljina, tako&nbsp; i elektron-akceptora). Praćen je stepen mineralizacije merenjem ukupnog organskog ugljenika i&nbsp; primenom&nbsp; jonske hromatografije.&nbsp; U cilju praćenja citotoksičnosti&nbsp; AMI, ispitan je&nbsp; in vitro&nbsp; rast četiri ćelijske linije: Neuro-2a, MRC-5, H-4-II-E i HT-29.&nbsp; Zatim, proučavana je efikasnost sintetisanih TiO₂/polianilin nanokompozitnih prahova, kao i&nbsp; prevlaka&nbsp; čistog TiO_2&nbsp;i WO₃/TiO₂&nbsp; u razgradnji AMI primenom UV i SSZ. Takođe, ispitan je uticaj&nbsp; strukture&nbsp; supstrata&nbsp; na efikasnost&nbsp; fotokatalitičke razgradnje kroz ispitivanje&nbsp; efikasnosti sintetisanih TiO₂&nbsp; nanoprahova dopiranih jonima W(VI), zatim me&scaron;anih&nbsp; cink-kalaj-oksid&nbsp; nanoprahova, kao i&nbsp; indijum-cink-oksid nanoprahova primenom UV i SSZ.</p> / <p>Direct and indirect photolysis of alprazolam (ALP) and amitriptyline (AMI) were studied using UV, visible,&nbsp; and simulated solar irradiation (SSI). Also, the stability of the ALP and AMI aqueous solutions in the dark were monitored. Photocatalytic degradation of ALP was studied in&nbsp; the&nbsp; presence of&nbsp; ZnO and TiO₂ Degussa&nbsp; P25&nbsp; using UV and SSI. Also, the influence of the photocatalyst&nbsp; loading, pH, as well as the influence of the radical&nbsp; and&nbsp; holes scavengers&nbsp; and electron acceptors&nbsp; were studied. The&nbsp; degree of mineralization was monitored by measuring&nbsp; of&nbsp; total organic carbon and&nbsp; using&nbsp; ion chromatography. Also, reaction intermediates were examined in detail. Further, reusabillity&nbsp; of ZnO was investigated in three consecutive degradation processes of ALP. In order to&nbsp; get insight into the&nbsp; cytotoxicity of the ALP&nbsp; and intermediates formed during photocatalytic degradation, their influence on the growth of two cell lines: Neuro-2a and MRC-5 were investigated. Then, the efficacy of synthesized ZnO (ZnO modified with milling&nbsp; and calcination, ZnO doped with Mg(II) ions, ternary and coupled binary&nbsp; tin-zinc-oxide) and TiO₂&nbsp; (anatase&nbsp; TiO₂&nbsp; undoped and&nbsp; doped&nbsp; with&nbsp; La(III) ions&nbsp; and&nbsp; brookite TiO₂) nanopowders in ALPdegradation using UV and&nbsp; SSI&nbsp; were investigated. Within the photocatalytic degradation of AMI, the&nbsp; degradation efficiency under different experimental conditions was studies (influence of the photocatalyst and irradiation type, photocatalyst&nbsp; loading, initial&nbsp; substrate concentration, the effect of the presence of radical and&nbsp; holes scavengers, and electron acceptors). The degree of mineralization was monitored by measuring&nbsp; of&nbsp; total organiccarbon and&nbsp; using&nbsp; ion chromatography.&nbsp; In order to&nbsp; study&nbsp; the cytotoxicity of AMI&nbsp; and degradation intermediates, their influence on the&nbsp; growth of four cell lines: Neuro-2a, MRC-5, H-4-II-E,&nbsp; and HT-29&nbsp; were investigated. Then, the efficacy of synthesized TiO2/polyaniline nanocomposite powders, as well as photocatalysts of pure TiO₂&nbsp; and WO₃/TiO₂&nbsp; in the form&nbsp; of&nbsp; films&nbsp;&nbsp; in AMI degradation using UV and SSI were studied. In addition, the effect of the&nbsp; substrate&nbsp; structure on the efficiency of photocatalytic degradation was studied by testing the activity&nbsp; of synthesized TiO_2&nbsp; nanopowders doped with W(VI)&nbsp; ions, then&nbsp; coupled binary tin-zinc- oxide&nbsp; nanopowders, as well as coupled binary&nbsp; indium-zinc- oxide nanopowders using UV and SSI.</p>

The discovery of antibiotics is considered as one of the most significant scientific achievements of the 20th century – lives of millions of people and animals have been saved. Thenceforth, substantial amounts of administered antibiotics and their metabo-lites have been excreted into waste stream via urine and faeces. In this dissertation, primary focus is the qualitative balance of 14 antibiotics and one metabolite in urban water management and in urban waters, respectively. In particular, antibiotics pre-scribed to human beings are drained in the urban sewer system and finally enter the environment: (i) Continuously via the effluent of the wastewater treatment plant after a partially effective removal or degradation or (ii) Intermittent via combined sewer overflow structures due to capacity limitations of the urban drainage system. The fate and the potential effects and risks of these substances on ecosystems and hu-man health are of major concern – their direct toxic effect to all trophic levels as well as the global spread of antibiotic resistance genes are challenging. Hence, an assessment of microbial community activity due to antibiotic exposure is presented. In particular, systematic work has been carried out to study the presence and character-istics of 14 antibiotics in urban waters. In detail, investigations were conducted to gain scientific knowledge with respect to adsorption, desorption, abiotic, biotic and photolyt-ic degradation as well as activity-inhibition of microorganism communities in sewage and of natural freshwater biofilm communities, respectively, due to inevitable urban drainage overflows. In order to provide information to assist potential management strategies, which miti-gate surface water pollution and minimize the adverse impacts of antibiotics on activity of microorganism communities, the following specific topics were addressed: ⑴ The occurrence of 14 antibiotics and one metabolite were determined in sewag-es at three sampling sites in the city of Dresden, Germany. ⑵ The adsorption affinities of 14 antibiotics and one metabolite to size dependent sewer sediments were determined in experimental investigations, three sam-pling campaigns and subsequently an antibiotic-specific adsorption coefficient, normalized to organic content, was quantified. ⑶ The desorption affinity and -dynamics of 14 antibiotics and one metabolite were quantified in size dependent sewer sediments in experimental investigation and with statistical analysis. ⑷ The abiotic, biotic and photolytic degradation affinity of 14 antibiotics and one metabolite were quantified based on batch experiments with three different sewages at 7°C and 22°C, with artificial irradiation and different dilution ratios of the sewage at 30°C and subsequently a model framework decrypted ranges of abiotic, biotic and photolytic degradation coefficients. ⑸ The occurrence of three antibiotics, namely ciprofloxacin, clarithromycin and doxycycline was determined in sewage sampled during dry weather conditions in a small catchment of Dresden, which spills intermittently combined sewage (a mixture of sewage and storm water) to an adjacent brook in the case of capacity limitations of the urban drainage system during periods of intense rainfall and subsequently the three antibiotics were determined in the adjacent brook water. ⑹ Then, the activity-inhibition of microorganism community in sewage of this small catchment was quantified due to an exposition with three different antibiotics and three different antibiotic concentrations. ⑺ Last but not least, the activity-inhibition of natural freshwater biofilm communities in the adjacent brook was quantified via exposure to three antibiotics, which were individually dosed in three different concentrations, and also in mixture. ⑻ Finally, a two-dimensional hierarchical cluster analysis with dendrogram and heat map based on before mentioned activity inhibition of natural freshwater biofilm communities were conducted to identify hot spots of antibiotic tolerant and resistant bacterial subpopulations due to inevitable urban drainage system overflows.:List of Figures IV List of Tables VIII Symbols and Abbreviations XII List of Publications on the Ph.D. topic XIX 1 General Introduction 2 1.1 Background 2 1.2 Aims and Objectives 3 1.3 Innovation and Contribution to the Knowledge 4 1.4 Outline of this Thesis 4 1.5 References 6 2 Adsorption and Desorption Affinity of 14 Antibiotics and One Metabolite for particulate components in urban drainage systems 10 2.1 Introduction 11 2.2 Materials and Methods 12 2.2.1 Study area 12 2.2.2 Sewer sediment and sewage sample collection 12 2.2.3 Sediment fractionation 13 2.2.4 Antibiotic determination in sewage and sediment 13 2.3 Results and Discussion 18 2.3.1 Antibiotics in composite sewage samples 18 2.3.2 Antibiotics adsorbed to sewer sediments 19 2.3.3 Organic-bound antibiotic load as a linear function of liquid concentration 20 2.3.4 Adsorption dynamics and adsorption coefficient determined by bath experiments 20 2.3.5 Mineral composition of sewer sediment SED#1B 23 2.3.6 Initial characteristics of sediment SED#1B 23 2.3.7 Desorption dynamics and desorption coefficient of SED#1B 24 2.4 Conclusions 25 2.5 References 26 3 Abiotic, Biotic and Photolytic Degradation Coefficients of 14 Antibiotics and One Metabolite 32 3.1 Introduction 34 3.2 Materials and Methods 35 3.2.1 Study area and sample collection 35 3.2.2 Experimental set up 35 3.2.3 Modelling framework 38 3.2.4 Procedure of model calibration 40 3.3 Results and Discussion 43 3.3.1 Primary metabolic parameter 43 3.3.2 Secondary metabolic parameter 44 3.4 Conclusions 50 3.5 References 50 4 Activity-Inhibition of Microorganisms due to an Exposition with different Antibiotics and Concentrations 56 4.1 Assessing Antibiotic Resistance of Microorganisms in Sanitary Sewage 56 4.1.1 Introduction 57 4.1.2 Material and Methods 58 4.1.2.1 Sampling Site and Antibiotic Agents 58 4.1.2.2 Analyzing Antibiotics 60 4.1.2.3 Respiration Rate 60 4.1.3 Results and Discussion 60 4.1.3.1 Concentration Range of Antibiotics and Typical Sewage Parameters 60 4.1.3.2 Oxygen Uptake Rate 62 4.1.4 Summary and Conclusions 63 4.1.5 References 64 4.2 Hot Spots of Antibiotic Tolerant and Resistant Bacterial Subpopulations in Natural Freshwater Biofilm Communities due to Inevitable Urban Drainage System Overflows 66 4.2.1 Introduction 68 4.2.2 Material and Methods 69 4.2.3 Results and Discussion 72 4.2.4 Conclusions 76 4.2.5 References 76 5 Summery and General Coclusions 82 5.1 Adsorption and Desorption Affinity 82 5.2 Abiotic, Biotic and Photolytic Degradation 83 5.3 Activity-Inhibition of Microorganism Communities due to Antibiotic Exposure 84 5.4 Enhancement of the Stockholm County Council (2014) assessment of antibiotics 84 5.5 References 87 6 Proposed Directions of Future Research 90 7 Appendixes 94 7.1 Chapters 94 7.2 Figures 95 7.3 Tables 115 7.4 References 139

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