Submitted by ANA KARLA PEREIRA RODRIGUES (anakarla_@hotmail.com) on 2017-07-31T12:10:23Z No. of bitstreams: 1 arquivototal.pdf: 5468289 bytes, checksum: dc45efa53e8cc6251d00164b611309f9 (MD5) / Made available in DSpace on 2017-07-31T12:10:23Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 5468289 bytes, checksum: dc45efa53e8cc6251d00164b611309f9 (MD5) Previous issue date: 2016-05-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / In the last decade, the extraction magnetic solid phase (MSPE) has been intense study target in Analytical Chemistry, mainly because of its potential application in sample preparation. Recently, with the development motivation automatic analytical methods, this technique has been combined with flow systems. However, the synergistic integration of MSPE with these systems is still a challenge, especially when it involves the handling of viscous matrices. In this perspective, this thesis proposes the development of an effective automated method to perform the MSPE in aqueous and oily matrices. For be applied as magnetic adsorbent nanoparticles of Fe3O4 coated with alumina and functionalized with sodium dodecyl sulfate (SDS) and 1-(2-pyridylazo)-2-naphthol (PAN) were synthesized. The nanoparticles were characterized by diffraction analysis X-ray and scanning electron microscopy, where it was confirmed that the method used to obtain the particles was adequate. Secondly, the automatic system to run the MSPE was developed. To this end an extraction chamber was made of Teflon with a quartz window on the side, where all steps of MSPE was performed without the need for any auxiliary apparatus for immobilizing the adsorbent. For generating the magnetic field in the extraction chamber, a robotic device has been developed. After these steps, the applicability of the method was demonstrated in the extraction and preconcentration of Cd and Pb in drinking water samples and Cd in edible oils, using as detection atomic absorption spectrometry graphite furnace. Factors affecting MSPE, such as pH, the amount of adsorbent, the type and concentration of the eluent and the elution time were studied. In the best experimental conditions to the sample water, the detection limit was 0.004, and 0.043 ug L-1 for Cd and Pb, respectively. Even in this array, relative standard deviations less than 3.5% were achieved with a 15-fold enrichment factor for both analytes. In the case of determination of Cd in edible oils, detection limit (0.006 ug L-1) and standard deviation (< 3.3%) was obtained satisfactorily with a 9-fold enrichment factor. Interfering studies have been performed successfully for the two determinations, not revealing significant percentage interference in determinations. The developed automatic method is simple and robust since it does not require immobilization of the adsorbent, and was successfully applied in the determination of Cd and Pb in drinking water samples and Cd in edible oils. / Na última década, a extração em fase sólida magnética (MSPE) tem sido alvo de intenso estudo na Química Analítica, principalmente em virtude do seu potencial de aplicação no preparo de amostras. Recentemente, tendo como motivação o desenvolvimento de métodos analíticos automáticos, essa técnica vem sendo combinada aos sistemas em fluxo. Contudo, a integração sinérgica da MSPE com esses sistemas ainda é um desafio, principalmente quando envolve a manipulação de matrizes viscosas. Nessa perspectiva, a presente tese propõe o desenvolvimento de um eficiente método automático para realização da MSPE em matrizes aquosas e oleosas. Para serem aplicadas como adsorvente magnético foram sintetizadas nanopartículas de Fe3O4 revestidas com alumina e funcionalizadas com dodecil sulfato de sódio (SDS) e 1-(2-piridilazo)-2-naftol (PAN). As nanopartículas foram caracterizadas através da análise de difratometria de raios-X e da microscopia eletrônica de varredura, onde confirmou-se que o método empregado para obtenção das partículas foi adequado. Num segundo momento, o sistema automático para executar a MSPE foi desenvolvido. Para isso, uma câmara de extração foi confeccionada em Teflon, com uma janela de quartzo na lateral, onde todos os passos da MSPE foram realizados sem a necessidade de qualquer aparato auxiliar para imobilizar o adsorvente. Para geração do campo magnético, na câmara de extração, um dispositivo robótico foi desenvolvido. Depois de estabelecida essas etapas, a aplicabilidade do método foi demonstrada na extração e preconcentração de Cd e Pb em amostras de água de abastecimento e de Cd em óleos comestíveis, empregando como detecção a espectrometria de absorção atômica em forno de grafite. Fatores que afetam a MSPE, tais como o pH, a quantidade de adsorvente, o tipo e a concentração do eluente e o tempo de eluição foram estudados. Nas melhores condições experimentais, para a amostra água, o limite de detecção foi 0,004 e 0,043 μg L-1 para o Cd e o Pb, respectivamente. Ainda nessa matriz, desvios padrão relativos menores que 3,5 % foram alcançados com um fator de enriquecimento de 15 vezes para ambos os analitos. No caso da determinação de Cd em óleos comestíveis, limite de detecção (0,006 μg L-1) e desvio padrão relativo (< 3,3 %) satisfatório foi obtido com um fator de enriquecimento de 9 vezes. Os estudos de interferentes foram realizados com êxito para as duas determinações, não revelando interferência percentual significativa nas determinações. O método automático desenvolvido é simples e robusto, uma vez que não requer a imobilização do adsorvente, e foi aplicado com sucesso na determinação de Cd e Pb em amostras de água de abastecimento e de Cd em óleos comestíveis.

O chumbo é um metal muito tóxico e que tem ampla distribuição pela sua grande utilidade. Mesmo a exposição a baixos níveis (que não causam sintomas de intoxicação aguda) de chumbo é associada a desordens cognitivas e neurológicas. O osso é considerado o melhor marcador de exposição a chumbo. No tecido ósseo, vários elementos estão presentes, e alguns deles poderiam ter sua concentração modificada pela exposição a chumbo. Testou-se a hipótese de que haja variações nos elementos Zn e Mg nas tíbias de animais expostos a chumbo (por técnica de química analítica convencional). Testou-se também se variações em microelementos poderiam ser detectadas por técnicas semiquantitativas nas tíbias de controles e animais expostos a chumbo. O objetivo deste projeto foi caracterizar em animais expostos ao chumbo desde a gestação e controles as concentrações deste elemento no osso (tíbia) de animais de 28 e 60 dias. Além do chumbo, investigamos também a concentração de 2 outros microelementos no osso: zinco e magnésio. As medidas quantitativas de chumbo foram feitas no sangue total coletado ao final dos períodos. As medidas quantitativas de chumbo, cálcio, zinco e magnésio foram realizadas a partir de soluções ácidas obtidas pela dissolução total do osso, sendo estas utilizadas para quantificar por Espectrometria de Absorção Atômica no modo chama ou com Forno e Grafite. Mandíbulas foram análisadas em Microscopia Eletrônica de Varredura e utilizando os acessórios Eletron Dispersive Spectroscopy para os elementos mais abundantes e Wavelenght dispersive Spectroscopy para investigar por análise semiquantitativa os mais abundantes elementos inorgânicos no osso destes animais, como forma de verificar se há variações nestes microelementos nos animais expostos a chumbo em comparação com controles. Como o chumbo se concentra na superfície do esmalte, também analisou-se o esmalte de primeiros molares inferiores, a fim de verificar se era visto o sinal do elemento chumbo nestes dentes. Foram usados ratos Wistar machos de 28 e 60 dias divididos em 2 grupos: C 28D (n=5) e Pb 28D (n=5) e, C 60D (n=12) e Pb 60D (n=17). Em todas as medidas de chumbo dos grupos controle as concentrações obtidas foram próximas ao limite de detecção, e houve sempre diferença estatisticamente significante (P<0.0001) quando os controles foram comparados aos grupos expostos a chumbo. As concentrações de chumbo obtidas no sangue de animais do grupo Pb 28D foi de 8,0 ug/dl (± 1.1) e no grupo Pb 60D foi de 7,2 ug/dl (± 0.89). Houve diferença estatisticamente significante entre as massas das tíbias (aferidas em balança e também a partir da quantidade de cálcio dissolvida em solução) do grupo C 60D (0,86 g ± 0,13) e Pb 60D (0,61 g ±0,11)(p=0.0004). As concentrações de chumbo detectadas nos ossos do grupo Pb 28D foi 8,02 (± 1,12) e no grupo Pb 60D foi de 43,3ug/g (± 13,26). Concentração de zinco no osso do grupo C 60D foi 0,22 mg/g e no grupo Pb 60D foi 0,22 mg/g (p>0.05). A concentração de magnésio no osso do grupo C 60D foi de 4,89 mg/g ± 0,74 e no grupo Pb 60D foi de 4,98mg/g ±0,79 (p>0.05). Os microelementos mais abundantes detectados nas tíbias contralaterais por Microscopia Eletrônica de varredura por EDS/WDS foram cálcio, fósforo, carbono, oxigênio, magnésio, sódio e potássio, não tendo sido detectadas variações nestes elementos entre os grupos controle e expostos a chumbo de 60 dias. O chumbo foi detectado apenas na região cervical dos dentes molares por MEV-EDS, e, nesta posição, apenas na forma de óxido de chumbo (deposição extrínseca) que pode ser útil para fins forenses ou de determinação de contaminação desconhecida. As conclusões deste estudo são: Houve diferença estatisticamente significante entre as massas de osso do grupo Pb 60D e C 60D. Mesmo não havendo diferença entre as concentrações de chumbo no sangue total de animais de 28 e 60 dias, houve quantidade de chumbo 5 vezes maior nos animais Pb 60D. Não houve diferenças nas concentrações de zinco e magnésio entre controles e animais expostos a chumbo. Os microelementos mais abundantes detectados nas tibias contralaterais por Microscopia Eletrônica de varredura por EDS/WDS foram cálcio, fósforo, carbono, oxigênio, magnésio, sódio e potássio, não tendo sido detectadas variações semi-quantitativas nestes elementos. O chumbo não foi detectado nem nos grupos controle ou expostos por MEV, e nos molares só foi detectada no grupo exposto como uma deposição extrínseca. / Lead is a highly toxic metal that is ubiquitous do to its great usefulness. Exposure to even low levels of lead (which do not cause symptoms of acute poisoning) is associated with cognitive and neurological disorders. Bone is considered the best marker of exposure to lead. Several chemical elements are found in bone, and some of them may have a different concentration or distribution due to exposure to lead. We tested the hypothesis that there are variations in the elements zinc and magnesium in the tibia of animals exposed to lead (being those elements determined by a conventional analytic chemistry technique). It was also tested whether variations in microelements could be detected by semiquantitative microanalysis in tibias of controls and animals exposed to lead. The objective of this project was to determine the concentration of lead in bone (tibia) of animals exposed to lead from pregnancy to day 28 and day 60. Besides lead, zinc and magnesium were also determined. Lead was also determined in whole blood collected at the end of the 2 time points. Quantitative measurements of lead, calcium, zinc and magnesium have been made in solutions obtained by dissolution of the bone by Atomic Absorption Spectrometry using flame or Graphite Furnace. Tibias were analyzed by scanning electron microscopy using the accessories Electron Dispersive Spectroscopy and Wavelength dispersive Spectroscopy for semiquantitative analysis of inorganic elements in the bone and molars of these animals. Lower molars were also analyzed by these means. Male Wistar rats aged 28 and 60 days were used in these study. In both these ages there were animals in the control (C 28D, n = 5 and C 60D, n=12) and lead exposed group (Pb 28D, n = 5 and Pb 60D, n = 17). Lead concentrations found in control groups were close to the detection limit, and there was always statistically significant differences (P <0.0001) when control groups were compared with those exposed to lead. Blood lead of groups Pb 28D and Pb 60D was 8.0 ug/dl (± 1.1) and 7.2 ug/dl (± 0.89), respectively. There was a statistically significant difference between the masses of the tibia (measured in balance and also from the amount of calcium dissolved in solution): C 60D showing 0.86 g (± 0.13 g) and 0.61 g (± 0, 11) of the Pb 60D group (p = 0.0004). Lead concentrations increased five times when the Pb 28D group was compared with the Pb 60D (8.02 and 43.3 ug/g)(p<0.0001). Zinc concentrations were not different in the C 60D (0.22 mg/g) and in the Pb 60D group (0.22 mg/g)(p>0.05). Magnesium concentrations were 4.89 mg/g in the C 60D and 4.98 mg/g in the Pb 60D (p>0.05). The most abundant trace elements detected in the contralateral tibiae by SEM-EDS/WDS were calcium, phosphorus, carbon, oxygen, magnesium, sodium and potassium and no variations in these elements were detected between the control and lead exposed groups. Lead was detected only in the cervical region of molar teeth of the lead exposed groups by SEM-EDS. This finding revealed lead in the lead oxide (extrinsic deposition) which may be useful for forensic purposes or for determining unknown contaminations. Conclusions: There was a statistically significant difference between the bone masses of the Pb 60D and C 60D groups. While there is no difference between lead concentrations in whole blood of animals 28 and 60 days, the amount of lead was 5 times higher in animals Pb 60D. There were no differences in the concentrations of zinc and magnesium between controls and lead exposed animals. The most abundant trace elements detected in the contralateral tibiae by SEM-EDS/WDS were calcium, phosphorus, carbon, oxygen, magnesium, sodium and potassium, and no semi-quantitative variations in these elements were detected in relation to exposure to lead. Lead was not detected either in control or exposed groups by SEM, and in molars it was only detected in the exposed group as an extrinsic deposition.

Um estudo sistemático a respeito da utilização de padrão interno em determinações multielementares por espectrometria de absorção atômica (ETAAS) foi desenvolvido. O objetivo principal do presente trabalho foi verificar a possibilidade de melhorar a precisão e a exatidão dos resultados analíticos, que são obtidos na análise de fluidos biológicos. O pré-tratamento dessas amostras foi simplificado e reduzido a uma única etapa de diluição com surfactante (Triton X-100) e ácido (HNO3). Conseqüentemente, a complexidade da solução diluída de amostra, a ser introduzida no tubo de grafite, apresenta uma elevada quantidade de concomitantes que podem provocar interferências químicas. A seleção preliminar dos elementos a serem testados como padrão interno considerou a semelhança de parâmetros físico-químicos relacionados com o processo de atomização. Desta forma, Ag, Bi, In e Tl foram testados como padrão interno para a determinação simultânea de Cd/Pb em sangue e urina, enquanto Bi, Ge, In, Sb, Sn e Te foram os elementos selecionados para a determinação de Mn/Ni/Se em soro sangüíneo. A melhoria da qualidade dos resultados analíticos obtidos na determinação simultânea de Cd e Pb em sangue foi observada quando Ag foi utilizada como padrão interno, na presença de NH4H2PO4 como modificador químico. Verificou-se uma melhoria na exatidão dos resultados obtidos para Cd e Pb, após a correção com padrão interno. Por outro lado, os resultados obtidos na análise de urina não foram corrigidos por nenhum dos elementos testados. Os melhores resultados para a determinação simultânea de Mn, Ni e Se foram obtidos com a utilização de Bi, Sn e Te como padrão interno. Entretanto, verificou-se que a correção de todos os resultados não seria viável com o uso de um único padrão interno. O melhor desempenho nos testes realizados na presença de soro sangüíneo foi obtido com Bi, que melhorou discretamente a precisão dos resultados obtidos para Se. Desta forma, a padronização interna visando a determinação simultânea de Mn, Ni e Se não foi eficiente. A padronização interna em ETAAS, com a finalidade de melhorar a precisão e a exatidão dos resultados analíticos, é uma estratégia tão complexa, quanto os efeitos interferentes que se pretende corrigir: são necessários mais estudos para compreender melhor como a utilização de uma condição de compromisso afeta os processos de atomização, bem como mais informações a respeito das interferências físicas e químicas causadas por amostras complexas, analisadas por ETAAS após uma simples etapa de diluição. Deve-se considerar com especial atenção o modificador químico e as temperaturas das etapas de pirólise e de atomização empregadas, que são parâmetros críticos para o desempenho de um elemento como padrão interno. / A systematic study involving the use of internal standard for multielement determinations by electrothermal atomic absorption spectrometry was developed. The main objective of this work was evaluate the possibility of improving precision and accuracy of the analytical results for biological fluids. The sample pre-treatment was reduced to a single dilution step with surfactant (Triton X-100) and acid (HNO3), increasing the amount of concomitant introduced into the atomizer. The preliminary selection of the elements to be tested as internal standard considered the resemblance of physico-chemical parameters related with the atomization process. Thus, Ag, Bi, In and Tl were tested as internal standard for the simultaneous determination of Cd/Pb in blood and urine, and Bi, Ge, In, Sb, Sn and Te were the selected elements for the determination of Mn/Ni/Se in blood serum. The correction of the results obtained for the simultaneous determination of Cd and Pb in blood was achieved when Ag was used as internal standard, in presence of NH4H2PO4 as chemical modifier. An improvement for the accuracy of the results was observed for both analytes after their correction with the internal standard. On the other hand, the results obtained for the urine analysis were not corrected by using the tested elements. The best results for the simultaneous determination of Mn, Ni and Se were observed when Bi, Sn and Te were used as internal standard. However, the correction for the results for all analytes was not possible by using only one internal standard. The best performance in presence of the serum was obtained for Bi, which improves slightly the precision for the Se results. Thus, the internal standardization for the simultaneous determination of Mn, Ni and Se was not efficient. The internal standardization in ETAAS, aiming the improvement of precision and accuracy of the analytical results, is a strategy as complex as the interference effects to be corrected: more studies are required in order to better understand how the adoption of a compromised condition disturbs the atomization processes, as well as to get more information about the physical and chemical interference caused by complex samples, analyzed by ETAAS after a single dilution step. The chemical modifier and the selected temperatures for the pyrolysis and atomization steps are critical parameters for the performace of an internal standard and they should be carefully considered.

(EN) The presented dissertation thesis summarizes the results contained in five original research papers that were published in prestigious international scientific journals in the field of analytical chemistry and atomic spectrometry. It is devoted to the method of generation of volatile compounds using a tetrahydroborate reaction and detection in a quartz multiatomizer by atomic absorption spectrometry. The thesis can be divided into two thematic parts - speciation analysis of arsenic based on hydride generation technique with collection and separation in a cryogenic trap and generation of volatile species of transition metals. In the first thematic part pre-reduction of pentavalent inorganic and methylated arsenicals has been studied. A simple setup for on-line pre-reduction employing thioglycolic acid as a fast pre-reductant has been developed, connected with a current hydride generator and applied/verified to oxidation state specific arsenic speciation analysis of human urine samples. In the same method the possibility of drying the gaseous phase from water vapor has been investigated to avoid incidental blocking the cryogenic trap by frozen water and to decrease fluctuations of signal baseline. Pronounced losses of methylated species have been discovered on Nafion tube dryer currently used in...

This diploma thesis is focused on the study of electrochemical generation volatile species of gold and silver. Two non-membrane electrolytic cells were constructed for electrochemical generation volatile species. These cells differ in the volume of electrode chamber. An atomic absorption spectrometry with quartz tube atomizer was used in most experiments. The equipment was performed in flow continuous mode. Experiments confirmed, that it is possible to use an atomic absorption spectrometry with quartz tube atomizer for generate volatile species of gold and silver by using two non-membrane electrolytic cells. The main part of this thesis was to find optimal conditions for the electrochemical generation of volatile species of gold and silver. These optimized parameters were: the cathode material, the type of electrolyte, the flow rate of the carrier gas, the generation current and the electrolyte flow rate. The calibration curves for both analytes were measured for both non-membrane electrolytic cells and the basic characteristics of the measurement were observed. Detection limit for electrochemical generation of gold was 1,61mg dm 3 and repeatability 3,93 %, detection limit for electrochemical generation of silver was 0,20 mg dm 3 and repeatability 7,33 %. Thanks to the experiments with a...

This thesis deals with the study of UV-photochemical generation of volatile compounds (UV-PVG) in connection with atomic absorption spectrometry (AAS). Selenium (Se(IV)) was selected as a model analyte and many experiments were carried out to expand the current sum of knowledge of the topic. The study was commenced by assembling the UV-PVG apparatus in the continuous flow mode. The detection method used was AAS with externally heated quartz furnace atomizer. The focus of the first step of the study was on the construction of the volatile compounds generator (UV-photoreactor) with emphasis on the material used; tubes made of teflon or quartz of different diameters were tested. The construction of the apparatus was followed by optimization of the reaction conditions (the type and concentration of the photochemical agent and other agents, which increase the analytical signal; the carrier gas and the auxiliary hydrogen gas flow rate; the sample flow rate). Eventually, the analytical figures of merit of the selenium determination using the proposed method were found. The results showed that teflon reaction tubes are a good competitor to those made of quartz. The accuracy of the method has been successfully verified by analysis of certified reference material and its applicability has been further tested...

Aufgrund der höheren elektrischen Leitfähigkeit und des größeren Widerstandes gegen Elektromigration im Vergleich zum Aluminium wird seit einigen Jahren Kupfer als Leitbahnmaterial in der Mikroelektronik eingesetzt. Da Kupfer jedoch eine hohe Beweglichkeit in den für die Halbleitertechnologie relevanten Werkstoffen aufweist, sind zur Verhinderung einer Diffusion effektive Barrieren notwendig. Dabei muss die u. a. geforderte hohe thermische Stabilität der Barrierematerialien auch im Zuge der fortschreitenden Miniaturisierung der mikroelektronischen Bauelemente und damit der Reduzierung der Barriereschichtdicken sichergestellt sein. Im Rahmen der Arbeit wurden mittels Magnetron-Sputtern neben Ta- und TaN-Einfachschichten sowie Ta-TaN-Mehrfachschichten auch Ta-Si-N-Einfachschichten jeweils mit und ohne Cu-Metallisierung sowohl auf blanke als auch auf thermisch oxidierte Si-Scheiben abgeschieden. Die Dicken der Barriereeinzelschichten und die der Cu-Schichten betrugen 10 nm bzw. 50 nm. Die Beurteilung der Barrierestabilität sowie die Charakterisierung der Ausfallmechanismen erfolgten nach Wärmebehandlungen durch den kombinierten Einsatz von Röntgenstreumethoden, spektroskopischen sowie mikroskopischen Analyseverfahren. In Abhängigkeit von ihrer Zusammensetzung und damit von der Mikrostruktur im Ausgangszustand finden für die zwischen Kupfer und SiO2 abgeschiedenen Diffusionsbarrieren unterschiedliche Prozesse während thermischer Belastungen statt. Bei den mehrstufigen Ta-TaN-Barrieren setzt bereits bei T = 300 °C eine Umverteilung von Stickstoff ein, die bei T = 500 °C in der Bildung von Ta2N-Kristalliten resultiert. Im Fall der Ta-Si-N-Barrieren führt die vorhandene Cu-Metallisierung zu einer an der Cu/Barriere-Grenzfläche beginnenden Kristallisation. Dabei hängen sowohl deren Einsatzzeitpunkt während einer bei konstanter Temperatur durchgeführten Wärmebehandlung als auch das entstehende Kristallisationsprodukt von der Barrierezusammensetzung ab. Im Zuge der Kristallisation erfolgt die vollständige Zerstörung der ursprünglichen Schichtintegrität, so dass Kupfer in unmittelbaren Kontakt zum SiO2-Substrat gelangt. Der sensitive Nachweis einer Cu-Diffusion durch die Barriere erfolgte einerseits durch die Charakterisierung von Cu/Barriere/SiO2/Si-Systemen mit Hilfe spurenanalytischer Methoden und andererseits durch die Untersuchung von Proben mit geändertem Aufbau. Durch Abscheidung der Barrieren zwischen Kupfer und Silizium ist mittels Röntgenbeugung die nach Diffusion von Cu-Atomen ins Substrat einsetzende Bildung von Cu3Si detektierbar. Mit den kritischen Temperaturen für die Bildung dieses Kupfersilizids erfolgte die vergleichende Bewertung der thermischen Stabilitäten der Barrieren. Werden die dünnen Ta-basierten Schichten zusätzlich bezüglich ihres spezifischen elektrischen Widerstandes beurteilt, so stellt sich eine Ta56Si19N25-Diffusionsbarriere als am geeignetsten für den Einsatz in Cu-Metallisierungssystemen heraus. Die mikrostrukturellen Untersuchungen gestatten Aussagen zu den Versagensmechanismen der einzelnen Barrieren. Für die Ta-TaN-Mehrfachschichten wird durch die einsetzende Stickstoffumverteilung und die sich anschließende Ta2N-Bildung bereits frühzeitig die stabile Mikrostruktur der TaN-Schicht zerstört. Während für Ta-Si-N-Schichten mit einem N-Gehalt von bis zu 25 at.% eine Cu-Diffusion ins Substrat erst nach vorzeitiger Barrierekristallisation beobachtet wird, erfolgt sie im Fall der stickstoffreichen Ta-Si-N-Barrieren in einem Zustand, für den mittels Röntgenbeugung eine Kristallisation noch nicht nachweisbar ist. Die Untersuchung der Abhängigkeit der sich während des Cu-Schichtwachstums bzw. einer nachträglichen Wärmebehandlung ausbildenden Cu-Texturkomponenten von der chemischen Zusammensetzung der Unterlage erfolgte mittels röntgenographischer Texturanalyse. Zur Diskussion der beobachteten Vorzugsorientierungen wurde das Modell des zweidimensionalen Kornwachstums in dünnen Schichten herangezogen.

Im ersten Teil wurde Probenvorbereitungs-Methoden und instrumentelle Methoden zur Organofluor-Bestimmung verglichen, um Vor- und Nachteile bei der Summenparameter-Analytik von per- und polyfluorierten Alkylverbindungen (PFAS) zu identifizieren. Daher wurden Oberflächenwasserproben aus der Spree in Berlin und Industrieabwasserproben mit zwei PFAS-Summenparametern analysiert – dem extrahierbaren (EOF) und dem adsorbierbaren organisch gebundenen Fluor (AOF). Beide PFAS-Summenparameter wurden mit zwei fluorsensitiven Detektionssystemen analysiert – Hochauflösender Kontinuumstrahler-Graphitofen Molekülabsorptionsspektrometrie (HR-CS-GFMAS) und combustion Ionenchromatographie (CIC). HR-CS-GFMAS erwies sich im Vergleich zu CIC als der empfindlichere und schnellere Ansatz mit höherer Präzision. Im zweiten Teil wurde eine neue Methode zur PFAS-Summenparameteranalyse und EOF-Bestimmung in Bodenproben auf Basis von HR-CS-GFMAS entwickelt und optimiert. EOF-Massenanteile wurden bei mehrfacher Extraktion und Nutzung der Festphasenextraktion (SPE) zur Entfernung anorganischen Fluors untersucht. Bei einem Vergleich der optimierten Methode mit und ohne SPE zeigte sich eine drastische Diskriminierung von Organofluor-Verbindungen mittels SPE. Im dritten Teil wurden Organofluor-Massenbilanzen in aquatischen Systemen anhand von Oberflächenwasser- und Schwebstoffproben (SPM) untersucht. SPM-Proben wurden mit vier komplementären Analysemethoden analysiert – target und non-target, direct total oxidizable precursor assay (dTOPA) und EOF. Daher wurden drei Organofluor-Massenbilanzansätze für die räumlich und zeitaufgelöste SPM-Probenanalyse verwendet: (I) Identifizierung von oxidierbaren PFAS-Vorläufer, (II) Identifizierung des Anteils der identifizierten und nicht identifiziertes EOF und (III) PFAS-target, PFAS dTOPA, non-target-Screening und EOF-Analyse, um das nicht identifizierte EOF aus Ansatz (II) weiter zu entschlüsseln. / In the first part, a comparison of sample preparation and instrumental methods for organofluorine determination was used to identify advantages and disadvantages in sum parameter analysis of per- and polyfluoroalkyl substances (PFASs). Therefore, surface water samples from the Spree River in Berlin, Germany and industrial effluent samples were analyzed using two PFAS sum parameters – the extractable (EOF) and adsorbable organically bound fluorine (AOF). Both PFAS sum parameters were analyzed using two fluorine sensitive detection systems – high-resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) and combustion ion chromatography (CIC). HR-CS-GFMAS turned out to be the more sensitive and faster approach accompanied with higher precision compared to CIC. In the second part, a new method for PFAS sum parameter analysis and EOF determination in soil samples based on HR-CS-GFMAS was developed and optimized. EOF mass fractions were investigated upon multiple extraction and utilization of solid phase extraction (SPE) for inorganic fluorine removal. In a comparison of the optimized method with and without SPE, a highly biased discrimination of organofluorines using SPE was shown. In the third part, organofluorine mass balances were investigated in aquatic systems using surface water and suspended particulate matter (SPM) samples. SPM samples were analyzed using 4 complementary analytical methods – target and non-target HRMS, direct total oxidizable precursor assay (dTOPA) and EOF. Therefore, 3 organofluorine mass balance approaches were used for SPM sample analysis in spatial and time resolved manner: (I) Identification of oxidizable PFAS precursors, (II) Identification of the proportion of identified and unidentified EOF and (III) PFAS target, PFAS dTOPA, non-target screening and EOF analysis to further unravel the unidentified EOF from approach (II).