<p>U okviru ovog istraživanja ispitani su: 1. Optimalni uslovi&nbsp; za<br />eksperimente biodegradacije policikličnih aromatičnih ugljovodonika sa istim i<br />različitim brojem prstenova; 2. Uticaj struture&nbsp; i matriksa na biodegradaciju<br />policikličnih aromatičnih ugljovodonika sa istim brojem prstenova; 3.<br />Fitotoksičnost biljaka&nbsp; (testovi klijavosti i usvajanje policikličnih aromatičnih<br />ugljovodonika); 4. Procena&nbsp; potencijalne&nbsp; biodostupne frakcije primenom<br />različitih hemijskih sorbenata (HPCD, &beta;CD&nbsp; i&nbsp; MCD, XAD4 i TenaxTA)&nbsp; i 5.<br />Korelacija dobijenih rezultata&nbsp; testovima biodegradacije, testovima klijavosti,<br />testovima fitotoksičnosti i rezultata dobijenih iz eksperimenta procene<br />biodostupnosti hemijskim testovima.&nbsp; Rezultati su pokazali da se&nbsp; optimalni<br />uslovi za biodegradaciju&nbsp; postižu dodatkom mineralnih medijuma, inokuluma i<br />surfaktanata.&nbsp; Posmatrajući uticaj sadržaja gline i organske materije i strukture<br />molekula,&nbsp; najveći stepen biorazgradnje ima fluoranten, &scaron;to je u skladu sa<br />njegovim fizičko-hemijskim osobinama, dok se sadržaj pirena i krizena nije<br />mogao jasno korelirati sa sadržajem organske materije i gline.&nbsp; &Scaron;to se tiče<br />testova fitotoksičnosti,&nbsp; sva semena su proklijala, &scaron;to govori u prilog tome&nbsp; da<br />me&scaron;avina ovih kontaminanata&nbsp; pri ispitivanim koncentracijama&nbsp; nije inhibirala<br />klijanje biljaka.&nbsp; Testovi usvojivosti ispitivanih PAH-ova su pokazali da je<br />najmanji procenat usvojivosti semenom dobijen za benzo(a)piren, &scaron;to se može<br />objasniti njegovom kompleksnijom strukturom. Hemijskim testovima za<br />procenu biodostupnosti je sa druge strane pokazano da se desorpcija u prisustvu<br />MCD, XAD4 smole i Tenaxa može koristiti kao jednostavna metoda za procenu<br />potencijalne biodostupne&nbsp; frakcije organskih jedinjenja u sistemima sediment&nbsp; -voda.</p> / <p>The aim of this study was to investigate: 1. The optimal conditions for&nbsp;the biodegradation of polycyclic aromatic hydrocarbons with the same and&nbsp;different numbers of rings; 2. The impact of structure and matrix&nbsp;biodegradation of polycyclic aromatic hydrocarbons with the same number of&nbsp;rings; 3. Phytotoxicity (germination tests and polycyclic aromatic hydrocarbon&nbsp;uptake); 4. The means for assessing the bioavailable fractions using various&nbsp;chemical sorbents (HPCD, &beta;CD, MCD, XAD4 and &nbsp;TenaxTA) and 5. The&nbsp;correlation between the results of the biodegradation tests, germination tests,&nbsp;phytotoxicity tests and the results obtained from the experiments in the&nbsp;assessment of bioavailability and chemical tests. The results showed that the&nbsp;optimal conditions for biodegradation are achieved by the addition of mineral&nbsp;media, inoculum and surfactants. When considering the effect of the contents of&nbsp;clay and organic matter and the structure of the molecules, the highest degree of&nbsp;biodegradation was observed with fluoranthene,&nbsp; which is in line with its&nbsp;physico-chemical properties. The concentrations of pyrene and chrysene were&nbsp;not clearly correlated with the organic matter and clay contents. During thephytotoxicity tests, all seeds sprouted, which speaks in favor of a mixture of&nbsp;these contaminants not inhibiting the germination of the plants. Tests for the&nbsp;uptake of the investigated PAHs showed that the lowest percentage seed uptake&nbsp;was for benzo(a)pyrene, which is explained by its more complex structure.&nbsp;Chemical tests for evaluating bioavailability have shown that desorption in the&nbsp;presence of MCD, XAD4 and Tenax resins can be used as a simple method for&nbsp;the evaluation of a potential bioavailable fraction of organic compounds in&nbsp;water-sediment systems.</p>

Orientador: Fauze Ahmad Aouada / Resumo: Com o objetivo de aplicar agroquímicos de uma forma controlada, e reduzir os danos à saúde e ao meio ambiente causados por estes, foram desenvolvidos neste trabalho, dois novos hidrogéis a partir de dois polissacarídeos diferentes carboximetilcelulose (CMC) e quitosana (Qs), suportados em redes de poli (ácido metacrílico)-co-poliacrilamida (PMAA-co-PAAm). Também foi investigada a influência da zeólita nas principais propriedades agroquímicas desses materiais como sorção e dessorção de herbicidas. A estabilidade da zeólita na solução polimérica foi estudada por meio de medidas de viscosidade. Estes comprovaram que a adição de polissacarídeo na solução formadora dos hidrogéis possibilita a obtenção de um hidrogel nanocompósito homogêneo. A incorporação da zeólita nos hidrogéis foi confirmada pela presença das bandas características da zeólita em 798 cm-1 e 600 cm-1 nos espectros de FTIR dos hidrogéis nanoestruturados. Outros indícios de incorporação foram a redução no volume dos poros e a presença de microporos nas paredes dos poros dos hidrogéis, aumento na massa residual dos hidrogéis nanoestruturados a 800ºC, observados nos resultados obtidos por microscopia eletrônica de varredura (MEV) e análise termogravimétrica (TG), respectivamente. Constatou-se também que a presença da zeólita reduziu o grau de intumescimento desses materiais, devido ao decréscimo na elasticidade das cadeias poliméricas. Entretanto, nos resultados de dessorção observou-se que a presença da zeólita pode... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In order to apply agrochemicals in a controlled manner, and to reduce the damages to the health and environmental caused by these, two new hydrogels based on carboxymethylcellulose (CMC) and chitosan (Qs) polysaccharides supported on poly(methacrylic acid)-co-polyacrylamide (PMAA-co-PAAm) networks were synthesized. The influence of zeolite on the main properties of these materials such as sorption and desorption was also investigated. The stability of zeolite in the polymeric solution was studied by viscosimetry. These results showed that the addition of polysaccharide in the hydrogel-forming solution enables the obtaining of homogeneous nanocomposite hydrogels. The incorporation of zeolite into hydrogels was confirmed by the presence of spectroscopic bands at 798 cm-1 and 600 cm-1 in the FTIR nanocomposite spectra. Other indicatives were the reduction in pore volume and the presence of micropores in the pore walls of zeolite hydrogels, and increase in the residual mass of nanostructured hydrogels at 800ºC, observed by scanning electron microscopy (SEM) and thermogravimetric analysis (TG), respectively. It was also observed that the presence of zeolite reduced the degree of swelling of these materials, due to the decrease in the elasticity of the polymeric chains. The results of desorption in saline medium show that the hydrogels studied in this work can reduce the presence of Al+3 ions, which in acidic soils are harmful to some crops. These results indicate that the hydrogel... (Complete abstract click electronic access below) / Doutor

Gegenstand der Arbeit sind Grundlagenuntersuchungen zu einem technischen Messsystem für Gerüche. Das System besteht aus Quarzmikrowaagen als Sensoren und einer Anreicherungseinheit zur Erhöhung der Sensitivität der Sensoren. Als neuartige chemisch sensitive Schichten der Quarzmikrowaage wurden 2 Typen von polymeren Komplexverbindungen untersucht und Erklärungen des Verhaltens vorgeschlagen. Feste Phasen aus der Gaschromatografie besitzen jedoch für den Sensor-Einsatz günstigere Eigenschaften. Die wichtigsten Betriebs-Parameter der Anreicherungseinheit werden unter praxisnahen Bedingungen mit einer rein empirischen Methode untersucht. Damit kann die Empfindlichkeit des Messsystems bei Reinstoffen die menschliche Nase übertreffen.

Replacing the lost Phosphates from different ecosystems is not a question it’s an onus. This none replaceable and renewable resource is one of the vital nutrients where without it, cells, crops and human beings cannot function and live. Though available in environment, its natural cycle is disturbed as its need especially in agriculture sector increases significantly. Phosphorus recovery from waste water sorbents is one of the innovative and promising concepts. The core goal of this paper is to evaluate the phosphorus desorbing capacity of two reactive materials (waste water sorbents) using chemical extracts. The experimental work emphasized on investigation four extracts, HNO3, NaHCO3, P-AL and H2O on phosphate desorption capacity of two inorganic reactive materials namely Polonite® and Sorbulite® which are widely known for their high P-sorption capacity. The kinetics and desorption were examined in batch experiments and consequently the plant availability were investigated using Flow Injection Analyzing (FIA) spectroscopy (wet chemistry) method. The maximum average orthophosphate desorption at 100 rpp for 48 hrs was interpreted to be 33.12 mg g−1and 3.11 mg g−1 from Sorbulite® and Polonite® respectively using 4M HNO3 extract. The orthophosphate desorption characteristic using the above extracts tended to decrease in the following order HNO3 ≤ P-AL ≤ NaHCO3 ≤ H2O. Polonite® shows a higher recovery potential, where almost 6 times higher ammonium lactate (AL)-extractable P was observed when compared with Sorbulite®. Batch experiment was proved to be a tool for investigating and evaluating Phosphorus desorption capacity of mineral-based filter materials.

I have investigated two different systems CO/Fe(100) and CO/Ru(0001), toobtain new information on the binding and desorption processes. The twodifferent systems have served as a model system, one for a static examination,CO on iron, and for the dynamic case, CO on ruthenium. To perform theseinvestigations, several types of techniques have been used such as, X-rayabsorption spectroscopy, X-ray emission spectroscopy, and femtosecond laserinduced desorption techniques such as two-pulse correlation. For the CO/Fe(100) system, we found that the on-top CO “<img src="http://www.diva-portal.org/cgi-bin/mimetex.cgi?%5Calpha" />1 phase” canbe described by the Blyholder-Nilsson-Pettersson model. The pre-dissociativephase of CO bound at hollow sites, “<img src="http://www.diva-portal.org/cgi-bin/mimetex.cgi?%5Calpha" />3 phase”, can be described in a Dewar-Chatt-Duncanson like picture. For the CO/Ru(0001) system, it was found that all our data could be fitted from an empirical friction heat bath model. Moreover, it turned out, thatthere is a strong frictional coupling to the substrate electrons and phonons.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23199号 / 工博第4843号 / 新制||工||1756(附属図書館) / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 邑瀬 邦明, 教授 宇田 哲也, 教授 作花 哲夫 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

The adsorption of oxygen on Rh(110) was investigated by thermal desorption spectroscopy (TDS), X-ray photoelectron spectroscopy (XPS) and scanning tunnelling microscopy (STM). The desorption of chemisorbed oxygen was observed at 700 K to 1200 K. Above 1400 K exists another desorption peak which is attributed to subsurface oxygen. The content of subsurface oxygen in Rh(110) influences the chemisorption states on the surface, so that the desorbing character of the surface oxygen species is changed. The subsurface-state needs high preparation temperature and has not any reaction with residual gas or added hydrogen in the chamber, which clarifies its spatial isolation. The XPS result showed that the binding energy of subsurface species is higher than the one of surface oxygen. This confirms the TDS observation. The subsurface-oxygen containing surface showed in STM oxygen induced hillock-like structures.

Developing a fundamental understanding of the interactions of chemical warfare agents (CWAs) with surfaces is essential for the rational design of new sorbents, sensors, and decontamination strategies. The interactions of chemical warfare agent simulants, molecules which retain many of the same chemical or physical properties of the agent without the toxic effects, with amorphous silica were conducted to investigate how small changes in chemical structure affect the overall chemistry. Experiments investigating the surface chemistry of two classes of CWAs, nerve and blister agents, were performed in ultrahigh vacuum to provide a well-characterized system in the absence of background gases. Transmission infrared spectroscopy and temperature-programmed desorption techniques were used to learn about the adsorption mechanism and to measure the activation energy for desorption for each of the simulant studied. In the organophosphate series, the simulants diisopropyl methylphosphonate (DIMP), dimethyl methylphosphonate (DMMP), trimethyl phosphate (TMP), dimethyl chlorophosphate (DMCP), and methyl dichlorophosphate (MDCP) were all observed to interact with the silica surface through the formation of a hydrogen bond between the phosphoryl oxygen of the simulant and an isolated hydroxyl group on the surface. In the limit of zero coverage, and after defect effects were excluded, the activation energies for desorption were measured to be 57.9 ± 1, 54.5 ± 0.3, 52.4 ± 0.6, 48.4 ± 1, and 43.0 ± 0.8 kJ/mol for DIMP. DMMP, TMP, DMCP, and MDCP respectively. The adsorption strength was linearly correlated to the magnitude of the frequency shift of the ν(SiO-H) mode upon simulant adsorption. The interaction strength was also linearly correlated to the calculated negative charge on the phosphoryl oxygen, which is affected by the combined inductive effects of the simulants' different substituents. From the structure-function relationship provided by the simulant studies, the CWA, Sarin is predicted to adsorb to isolated hydroxyl groups of the silica surface via the phosphoryl oxygen with a strength of 53 kJ/mol. The interactions of two common mustard simulants, 2-chloroethyl ethyl sulfide (2-CEES) and methyl salicylate (MeS), with amorphous silica were also studied. 2-CEES was observed to adsorb to form two different types of hydrogen bonds with isolated hydroxyl groups, one via the S moiety and another via the Cl moiety. The desorption energy depends strongly on the simulant coverage, suggesting that each 2-CEES adsorbate forms two hydrogen bonds. MeS interacts with the surface via a single hydrogen bond through either its hydroxyl or carbonyl functionality. While the simulant work has allowed us to make predictions agent-surface interactions, actual experiments with the live agents need to be conducted to fully understand this chemistry. To this end, a new surface science instrument specifically designed for agent-surface experiments has been developed, constructed, and tested. The instrument, located at Edgewood Chemical Biological Center, now makes it possible to make direct comparisons between simulants and agents that will aid in choosing which simulants best model live agent chemistry for a given system. These fundamental studies will also contribute to the development of new agent detection and decontamination strategies. / Ph. D.

Nanoelectronics is a field undergoing rapid development, meaning knowledge of the materials and methods used in nano-scale systems is a driving force in the industry. Silicon is a well known material in nanoelectronics commonly used as a semiconductor and is therefore a good representative for nanomaterials in general. In this thesis work the effects of the helium and neon ions with the energies 100 keV and 200 keV respectively on surface contaminants and the bulk material of nanometer thick silicon membranes are being studied. Beyond interactions based on different incident ions, the effects are studied inboth the geometries of transmission and backscattering, giving information about the immediate effects on the surface, as well as bulk effects. Using Medium Energy Ion Scattering (MEIS), the positively charged particles on the surfaces and in the bulk of the materials, which are either sputtered or desorbed, can be detected. While the ions are different, the energies in this work are chosen to be such, that the electronic stopping power is the same, while the nuclear stopping of neon is vastly higher. From this work, it is concluded that both ions have the same qualitative effects on the membrane contaminants, consisting of hydrocarbons, which are desorbed electronically. Furthermore, neon has the effect of destructively sputtering the bulk material. A synergistic effect of electronic and nuclear deposition was also found, as quantitatively, more hydrocarbons per incident Ne+ ion were desorbed than per incident He+ ion. The change in effect based on different geometries can to a large extent be attributed to the energy loss of the ions in the material. The one change between geometries which can not be explained by energy loss in the material, is a 50% under representation of desorbed hydrogen ions in transmission geometryfor He+ incident ion. It is also concluded that the method used has the potential to be a viable, non-destructive and scalable cleaning and measuring method for contaminations on nano-scale materials, such as 2 dimensional materials. / Nanoelektronik är ett område under snabb utveckling, vilket gör kunskap kring de material som bygger upp elektroniken drivande i utvecklingen av teknologin. Kisel är ett välkänt material inom nanoteknologin då det är välanvänt som halvledare, vilket gör det till en bra representant för en mängd andra nanomaterial. I detta examensarbete undersöks de effekter som 100 keV helium- och 200 keV neonjoner har på ytföroreningar och bulkmaterial av kiselmembran i nanometertjocklek. Utöver olika jonslag undersöks även skillnaderna mellan membranets geometri i transmission och backåtspridning. Detta ger information, både om de direkta effekterna som jonerna har på materialets bestrålade yta, samt effekterna på den motsatta ytan. Genom användningen av ”Medium Energy Ion Scattering” (MEIS) kan de positivt laddade partiklarna på ytan och i bulkmaterialet, som genom elektronisk och nukleär växelverkan bryts läs, utforskas. Partiklarnas energier har valts så att den elektroniska bromsförmågan är densamma för de två partiklarna, medan den nukleära bromsförmågan skiljer sig kraftigt. Från detta arbete kan slutsatsen dras att båda joner har samma kvalitativa effekt på kiselmembranets föroreningar i form av kolväten. Dock har neon en betydlig nukleär, destruktiv effekt på bulkmaterialet. En synergistisk effekt har också kvantitativt observerats, där de elektroniska effekterna på kolväten är högre för neonjoner. De förändringar som påvisades i de olika geometrierna kan i stort förklaras av energiförlust av jonerna under passagen genom membranet. Den geometribaserade differens som inte följer förklaringen energiförlust är desorberat väte, vilket är 50 % mindre i transmissionsgeometri för heliumjoner. Den andra slutsatsen som kan dras från detta arbete är att den använda metoden har potentialen att utvecklas till en icke-destruktiv och skalbar metod för rengöring och mätning av föroreningar på nanomembran så som 2 dimensionella material.

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