[pt] O crescimento populacional vem acarretando um incremento no consumo de combustíveis fósseis e na queima de biomassa e, como conseqüência, um aumento na fonte de partículas de carbono negro (ou black carbon - BC) em ambientes costeiros e estuarinos. Este material orgânico refratário vem sendo estudado nos últimos 30 anos e é considerado um importante reservatório geoquímico. Todavia, sua função no ciclo do carbono ainda não é totalmente caracterizada. O BC desempenha um papel de causador de problemas ambientais (como aquecimento global) e também de atenuador dos riscos representados pelos contaminantes orgânicos devido ao seu efetivo poder sorvente. Este trabalho apresenta de forma inédita a distribuição de BC em sedimentos e sua relação com compostos HPAs de uma região estuarina do Estado do Rio de Janeiro - Baía de Guanabara (ambiente conhecidamente afetado por poluição crônica de diversos compostos). Para realização da pesquisa, foi realizado primeiramente uma validação e escolha metodológica entre 2 protocolos de determinação de BC encontrados na literatura: oxidação química com dicromato/ácido sulfúrico e oxidação térmica a 375 oC, em que este último apresentou maiores vantagens e foi selecionado para determinar BC nas amostras de sedimento. Os teores de BC foram determinados por um analisador elementar Carlo Erba EA1110. Os teores de BC nos sedimentos superficiais (0-2 cm) de 25 estações da região interna da baía foram de 0,19 %p.s. . +- 0,07 %p.s. ., variando entre 0,03 %p.s. . e 0,31 %p.s. . A distribuição na baía de Guanabara sugere a presença de um gradiente decrescente de partículas pirogênicas da região de fundo da baía em direção à zona costeira. Determinações de carbono orgânico total (TOC), razões molares C/N e distribuições BC:TOC (5,35 % +- 2,45 %, n = 25) foram dados adicionais avaliados. Testemunhos de sedimento de 90 cm de comprimento de 3 manguezais da região norte foram estudados: Suruí, Nova Orleans e Piedade, que exibiram teores de BC de 0,11 %p.s. . +- 0,08 %p.s. . e BC:TOC de 1,99 % +- 1,59 % (n = 62). A relação entre o material BC e HPAs (determinados em estudo anterior) nas camadas sedimentares pôde ser analisada através de correlações e da análise de componentes principais e revelaram uma tendência de sorção destes compostos contaminantes com BC nos bosques de Nova Orleans e Suruí. Em Piedade, as razões de compostos HPAs alquilados (1,7-dimetilfenantreno e 2,6- dimetilfenantreno) apontaram para um domínio de produtos de combustão de madeira, que não pode ser isolado pela metodologia aplicada. Adicionalmente, a sorção de HPAs no material BC foi confirmada pela realização de um experimento de fortificação de pireno (concentrações monitoradas por análise de fluorescência - espectrofluorímetro de luminescência Perkin Elmer LS55B). Os resultados discutidos aumentaram o conhecimento sobre as diferentes frações da matéria orgânica nos sedimentos da Baía de Guanabara e apontam para a importância da fração carbono negro (ainda pobremente pesquisada no Brasil) no carbono orgânico total e na regulação da liberação de contaminantes hidrofóbicos para o ambiente e biota. / [en] Black carbon (BC) is a term used to represent the continuum of charred materials produced during incomplete combustion of fossil fuel and biomass. Since the emission rates of BC are increasing in the last decades due to energy requirements from modern human population, there is great interest in the distribution of BC in the environment (atmosphere, water and sediment) because their role in the biogeochemical cycle of carbon is not fully understood and, also, because the high adsorption capacity of BC particles may decrease the bioavailability of organic contaminants (PAH, for example). In the present work it was determined the distribution, for the first time ever, of BC in superficial sediments from Guanabara Bay and it was evaluated the relation between BC (quantified in the present work) and known concentration of polycyclic aromatic hydrocarbons (PAHs) in sediment cores from 3 mangrove regions in the bay (Suruí, Nova Orleans and Piedade). Two analytical protocols for BC quantification were compared (chemical oxidation with dichromate/sulphuric acid and thermal oxidation at 375 ºC), and the second one was chosen for routine analysis. After treatment, the BC content was measured by a dry-oxidation method in a Carlo Erba EA110 elemental analyser. Total organic carbon (TOC) was also measured using the same instrument. In the superficial sediments (0-2 cm) from Guanabara Bay, the mean BC carbon content (n = 25) was 0.19 +- 0.07 % (dry-weight mass), ranging from 0.03 % to 0.31 %. The percentage of BC to TOC was 5,35 +- 2,45 (n = 25). The sediments in the northern sector of the bay had higher contents of BC, what is related to the input of pyrolitc materials from river and urban runoff and local restricted water circulation. In the mangrove sediments, the BC content was 0.11 +- 0.08 % (dry- weight mass) and the BC:TOC fraction was 1.99 +- 1.59 % (n = 62). Linear regression and principal components analysis revealed that the distribution of PAH is closed related to the BC contents in the sediment from Suruí and Nova Orleans, but not for Piedade sediments, probably due to uncertainties in the origin of PAHs in these sediments. An experiment with fortification of sediment with pyrene confirmed the importance of adsorption of PAH to the BC particles. In conclusion, the data obtained in the present work permitted a better understanding of the different fractions of organic matter in the sediments from Guanabara Bay and showed the importance of BC in the fate and possible effects of PAH in this coastal contaminated system.

Materiais de Referência (MR) de substâncias químicas têm ampla aplicação, sobretudo na área analítica, servindo de referência para validação de métodos, calibração de instrumentos e controle de qualidade, estabelecendo a comparabilidade de resultados analíticos em escala global e permitindo a transferência da exatidão entre métodos, laboratórios e padrões. Norteado por essas necessidades, o trabalho apresenta uma proposta para certificação de MR baseada nas orientações preconizadas por diretrizes e normas internacionais, principalmente as que seguem o ISO Guia 34, para estabelecer as propriedades certificadas através de técnicas analíticas de Espectrometria de Massas de Alta Resolução, Ressonância Magnética Nuclear, de ¹H e de ¹³C, e de Análise Elementar CHN. A certificação contemplou as caracterizações qualitativa e quantitativa, ensaio de estabilidade e o cálculo da estimativa da incerteza da medição. Como resultado, foi produzido e certificado um lote piloto de MR de β-N-metilamino-alanina (BMAA), uma toxina obtida in-house através de síntese química e purificação, cujos valores de propriedades certificadas foram rastreáveis ao SI e acompanhadas da estimativa da incerteza da medição. / Reference Materials (RM) of chemicals have wide application, particularly in the analyses, providing a reference for validation of methods, instrument calibration and quality control, establishing the comparability of analytical results on a global scale and enabling the transfer of accuracy between methods, laboratories and standards. Guided by these requirements, the paper presents a proposal for certification of MR based on the guidelines recommended by international guidelines and standards, especially those which follow the ISO Guide 34, to establish the certified properties through analytical techniques of mass spectrometry High resolution Nuclear Magnetic Resonance, ¹H and ¹³C, and CHN elemental analysis. The certification included qualitative and quantitative characterization, stability test and the calculation of the estimate of measurement uncertainty. As a result, was produced and certified a pilot batch of RM β-N-methylamino-alanine (BMAA), a toxin obtained in-house via chemical synthesis and purification, whose property values are certified and traceable to the SI accompanied by an estimative of the uncertainty of measurement.

Die oxidative Transformation der Thiol-Gruppe des Cysteins in verschiedene andere funktionelle Gruppen wird als sehr wichtige posttranslationale Modifikation (PTM) angesehen. Cysteinsulfensäure (SA) ist eine Zwischenstufe der Thiol-Oxidation: Sie kann entweder mit freien Thiolen reagieren, um Disulfide zu bilden oder durch reaktive Sauerstoffspezies (reactiveoxygenspecies, ROS) weiter oxidiert werden. Jede Störung des zellulären Redox-Haushalts wird mit altersbedingten Erkrankungen , daher stellt die Überwachung des SA-Spiegels einen vielversprechenden Wegdar, den Status dieses Redox-Haushalts festzustellen. Da bereits kleinste Änderungen der Proteinmengen und PTMs tiefe Einblicke in den Zustand des biologischen Systems liefern können, ist eine quantitative Bestimmung von großer Bedeutung.Technologische Fortschritte im Bereich der Trennungsmethoden und Massenspektrometrie (MS) erlaubten die Entwicklung umfassender Möglichkeiten in der Protein-Analytik. In dieser Arbeit wurde eine neue, hochsensitive und selektive Methode zur Detektion von SA entwickelt. Dafür wurde ein Alkin-β-Ketoester (KE) an einen Lanthanid-haltigen (Ln) Chelatkomplex. Zum Nachweis des Funktionsprinzips wurden, mittels H2O2, Sulfensäuren in verschiedenen Peptidsequenzen erzeugt, um die in biologischen Systemen durch ROS hervorgerufenen Oxidationen nachzustellen. Diese Sulfensäuren wurden anschließend durch den Ln-DOTA-KE-Komplex gebunden. Die Bildung dieser SA-Ln-DOTA-KE-Einheit wurde mittels (Elektronenspray-Ionisation/ ESI-MS) und (induktiv gekoppeltem Plasma/ICP-MS) nachverfolgt. Die entwickelte Methode wurde weiterhin auf die Bestimmung von SA-Bildung in humanem Serum angewandt, humanes Serumalbumin wurde angereichert via Affinitätschromatographie. ICP-MS diente der Bestimmung der SA-Ln-DOTA-KE-Einheit, durch Kombination mit einer Isotopenverdünnungsanalyse (IDA) wurde eine absolute Quantifizierung durchgeführt. Die Ergebnisse zeigen oxidative Schäden bis zu 40 % des vorhandenen Albumins. / Oxidative transformation of cysteine thiol group into different functional groups is considered a significant posttranslational modification (PTM) of great importance. Cysteine sulfenic acid (SA) is the transient state for thiol group oxidation; it can react with free thiols to form disulfide bonds or can be further oxidized with reactive oxygen species (ROS) to form sulfinic and sulfonic acids. As any disturbance in the cellular reduction-oxidation (redox) balance is correlated to age-related diseases, the detection of SA transient state formed a sensor for such redox-mediated events. Whereas only any small change in the quantity of proteins, as well as the formed PTMs, can provide deeper insights into the status of the biological system, quantitative analysis should be carried out to reveal the status of the system. On the other hand, the technological advances, in particular the separation techniques and mass spectrometry (MS), allowed the development of several approaches for the comprehensive assessment of proteome analysis. Herein, we provide a new strategy for the highly sensitive and specific detection of SA using alkyne β-ketoester (KE) previously linked to a lanthanide (Ln)-containing chelator (Ln-DOTA. SA was generated by hydrogen peroxide (H2O2) in different peptide sequences by ROS and was detected by the prepared compound Ln-DOTA-KE. Molecular mass spectrometry (electrospray/ ESI-MS) and (Inductively coupled plasma mass spectrometry /ICP-MS) have been used to monitor the formation of SA linked to Ln-DOTA-KE. The developed strategy has been further applied to the determination of SA-induced formation in human serum by using affinity chromatography for purification of albumin followed by ICP-MS to monitor the formed SA linked to Ln-DOTA-KE in combination with isotope dilution analysis (IDA) for the absolute quantification. Quantitative results showed levels of oxidative damage regarding SA formation in human serum up to 40% of the albumin present.

In this thesis complexes of acylchalcogoureas with cadmium (II), lead (II) and nickel (II) have been synthesised and investigated as single source precursors for the formation of metal chalcogenide thin films viaaerosol assisted chemical vapour deposition (AACVD). Routes to binary thin films have been explored using homoleptic complexes of the general structure bis(N,N-diethyl-N'-naphthoylchalcogoureato)metal(II). Analysis of the thin films produced showed the successful deposition of the binary materials from the synthesised complexes when characterised by powder XRD, ICP-OES, SEM and EDX. Routes to ternary thin films with the general structure MExE'1-x, where M represents a metal (Cd, Ni and Pb); and E chalcogen (S or Se) have been investigated using heteroleptic metal complexes of cadmium, nickel or lead including different chalcogen containing N,N-diethyl-N'-naphthoylchalcogoureato ligands and diethyldithiocarbamate. The precursors were fully characterised and novel compounds had their crystal structures determined. The heteroleptic complexes were thermolysed by AACVD forming the MExE'1-x thin films. In the cases of lead, nickel and cadmium the thin films produced showed that the composition of the film tended heavily towards the metal selenide. Ternary films of type MS1-xSex was prepared by mixing their binary precursors of type bis(N,N-diethyl-N'-naphthoylselenoureato)metal(II) and bis(N,N-diethyl-N'-naphthoylthioureato)metal(II) [metal = Cd, Ni and Pb]. In the case of lead and cadmium chalcogenide films variation of the ratio of sulphur and selenium containing precursors allowed for the full transition in composition between metal sulphide and metal selenide. In the case of CdS1-xSexthe band gap of the films was determined from UV-visible spectroscopy to vary from 2.4 eV (CdS) to 1.7 eV(CdSe). In the case of NiS1-xSex the movement from sulphide to selenide was less simple with multiple phases of nickel chalcogenides produced.

Materiais de Referência (MR) de substâncias químicas têm ampla aplicação, sobretudo na área analítica, servindo de referência para validação de métodos, calibração de instrumentos e controle de qualidade, estabelecendo a comparabilidade de resultados analíticos em escala global e permitindo a transferência da exatidão entre métodos, laboratórios e padrões. Norteado por essas necessidades, o trabalho apresenta uma proposta para certificação de MR baseada nas orientações preconizadas por diretrizes e normas internacionais, principalmente as que seguem o ISO Guia 34, para estabelecer as propriedades certificadas através de técnicas analíticas de Espectrometria de Massas de Alta Resolução, Ressonância Magnética Nuclear, de ¹H e de ¹³C, e de Análise Elementar CHN. A certificação contemplou as caracterizações qualitativa e quantitativa, ensaio de estabilidade e o cálculo da estimativa da incerteza da medição. Como resultado, foi produzido e certificado um lote piloto de MR de β-N-metilamino-alanina (BMAA), uma toxina obtida in-house através de síntese química e purificação, cujos valores de propriedades certificadas foram rastreáveis ao SI e acompanhadas da estimativa da incerteza da medição. / Reference Materials (RM) of chemicals have wide application, particularly in the analyses, providing a reference for validation of methods, instrument calibration and quality control, establishing the comparability of analytical results on a global scale and enabling the transfer of accuracy between methods, laboratories and standards. Guided by these requirements, the paper presents a proposal for certification of MR based on the guidelines recommended by international guidelines and standards, especially those which follow the ISO Guide 34, to establish the certified properties through analytical techniques of mass spectrometry High resolution Nuclear Magnetic Resonance, ¹H and ¹³C, and CHN elemental analysis. The certification included qualitative and quantitative characterization, stability test and the calculation of the estimate of measurement uncertainty. As a result, was produced and certified a pilot batch of RM β-N-methylamino-alanine (BMAA), a toxin obtained in-house via chemical synthesis and purification, whose property values are certified and traceable to the SI accompanied by an estimative of the uncertainty of measurement.

Biogeochemical changes across oceanic interfaces, and method development to study such changes, are described in this work. The interfaces studied include the Subtropical Front in the Pacific Ocean and the boundary at the base of the euphotic zone. Both interfaces are characterized by accumulations of phytoplankton, although the forcing functions that result in increased biomass are distinctly different. The Subtropical Front, located at approximately 30°N in the Pacific Ocean, was detected during a cruise in the summer of 2002 by its diagnostic 34.8 salinity outcrop, in spite of the absence of its associated temperature signature. The front displayed elevated concentrations of large diatoms; Rhizosolenia and Hemiaulus, with concentrations penetrating deeper in the water column south of the front. Rhizosolenia species were dominant on the warmer, high salinity side of the front, while Hemiaulus prevailed on the cooler, low salinity side. While high cell counts were enumerated by net tows, the elevated biomass was not visible in satellite color imagery. Size fractionated chlorophyll data revealed > 10 um cells were found below 200 m, indicating export of large cells out of the euphotic zone. This confirms observations by other investigators that fronts represent important regions of episodic export, although such export may go undetected if the biomass is not visible in ocean color images. Another region of interest was the narrow layer at the base of the euphotic zone. During stratified conditions, the layer was characterized by a fluorescence maximum, a primary nitrite maximum, and a nutricline. While fluorescence maxima have proven easy to detect using commercial fluorometers, nutrient distributions have proven more difficult. The Spectrophotometric Elemental Analysis System (SEAS) permitted detection of low concentrations of nitrite, nitrate, and phosphate with nanomolar sensitivity and 1 Hz or better sampling frequency. Using multiple wavelength spectroscopy, the range of nitrate concentrations from 2 nM to 20 uM have been detected. Profiles of nitrite obtained across the North Pacific Subtropical Gyre revealed the close correlation between nitrite and chlorophyll fluorescence maxima, suggesting that the nitrite maximum is formed by phytoplankton when insufficient light is available to permit reduction of nitrite to ammonia.

<p>The results of the multivariate analyses suggest that most of the variation in the composition of the samples was of an intra-sample nature, illustrating large scale patchiness in foraminiferal distribution. There were, however, definite differences between communities around Robben Island and in St Helena Bay, and least variation was found between the control and pipeline sites, and between the stations of each site. When the trace metal concentrations and the percentage nitrogen increased, the richness, diversity and abundance of foraminifera tended to decrease. Sediment grain size positively affected abundance but negatively affected diversity and richness. In both areas mean grain size did not, however, appear to play a very large role in influencing diversity. Cadmium, copper, chromium, the percentage nitrogen and the mean grain size were identified as the most important variables influencing the community structure by the BIOENV BEST routine in PRIMER. The trace metals and percentage nitrogen only had negative effects on the diversity and abundance as well as on the abundance of the dominant genera, whereas the mean grain size had variable effects.</p>

Magistro darbe tiriama dirvinio ir karčiojo kiečių biologinės cherakteristikos nevienodos amoniakinės taršos vietose. Darbo tema: Dirvinio ir karčiojo (pelyno) kiečių biologinės charakteristikos nevienodos amoniakinės taršos vietose Darbo objektas - dirvinis kietis ir pelynas - paplitę Lietuvoje augalai, pasižymintys gausiomis vaistingomis medžiagomis - eteriniais aliejais ir flavonoidais. Darbo tikslas - nustatyti skirtingų (AB "Achema" atžvilgiu) vietų karčiojo kiečio, pelyno (Artemisia absinthum L.) ir dirvinio kiečio (Artemisia campestris L.) fiziologines-biochemines savybes. Darbo metodai - Kjeldalio metodas azoto nustatymui, atominės absorbcijos spektroskopija sunkiųjų metalų nustatymui. Salsburo ir sojos agaras mikroorganizmų auginimui. Darbo rezultatai - ištirtos tokios dviejų rūšių kiečių fiziologinės-biocheminės savybės: dirvožemio azoto ir sunkiųjų metalų koncentracija, kiečių įvairių organų masė, kiečių įvairių organų azoto koncentracija, kiečių antžeminių organų flavonoidų koncentracija, kiečių epifitinių mikroorganizmų skaičius, įvertinta kaip oro amoniakinė tarša ir dirvožemio tarša sunkiaisiais metalais reikšmingai įtakoja ištirtus kiečių fiziologinius rodiklius. Atlikti tyrimai parodė, kad dirvožemio ir abiejų rūšių augalų azoto koncentracija išsidėsto tokia tvarka: dirvožemio < stiebų < lapų < žiedų < skrotelių. Tirtos vietos pagal dirvožemio ar organų azoto koncentraciją nesiskyrė. Didžiausios dirvožemio sunkiųjų metalų koncentracijos nustatytos abiejų... [toliau žr. visą tekstą] / Topic of the master degree diploma: Various biological parameters of Artemisia absinthum L. and Artemisia campestris L. growing in the areas effected by different level pollution by ammonia. Artemisia absinthum L. and Artemisia campestris L. are common wild growing species in Lithuania. Despite these species are rich in flavonoids and essential oils till now in our country biology and biochemistry of these species have not received bigger attention. Present work aimed at evaluation of Artemisia absinthum L. and Artemisia campestris L. physiological-biochemical parameters depending on sampling site distance from the nitrogen fertilizer factory. Methods. Following physiological-biochemical parameters of these species were analysed: soil nitrogen and heavy metal concentrations, dry mass and nitrogen concentration of various organs of selected plant species, abundance of epiphytic microflora. Results. During vegetation period sampling was performed three times: in July, 2; July, 24, and September, 24. Obtained parameters were evaluated in respect of aerial ammonia pollution and heavy metal pollution of the soil. Present study showed that nitrogen concentration of the soil and various organs of both Artemisia species fell into following ascending order: soil < stems < leaves < inflorescences and fruits < rosettes. Between selected sites no differences were observed according to the soil and plant nitrogen concentration. The highest concentrations of heavy metals were observed... [to full text]

<p>The results of the multivariate analyses suggest that most of the variation in the composition of the samples was of an intra-sample nature, illustrating large scale patchiness in foraminiferal distribution. There were, however, definite differences between communities around Robben Island and in St Helena Bay, and least variation was found between the control and pipeline sites, and between the stations of each site. When the trace metal concentrations and the percentage nitrogen increased, the richness, diversity and abundance of foraminifera tended to decrease. Sediment grain size positively affected abundance but negatively affected diversity and richness. In both areas mean grain size did not, however, appear to play a very large role in influencing diversity. Cadmium, copper, chromium, the percentage nitrogen and the mean grain size were identified as the most important variables influencing the community structure by the BIOENV BEST routine in PRIMER. The trace metals and percentage nitrogen only had negative effects on the diversity and abundance as well as on the abundance of the dominant genera, whereas the mean grain size had variable effects.</p>

Die außerordentlichen Steigerungen der Funktionalität und Produktivität in der Halbleiterindustrie sind zum wesentlichen Teil auf eine Verkleinerung der Strukturdetails auf einer logarithmischen Skala über die letzten Jahrzehnte zurückzuführen. Sowohl zur Kontrolle des Fertigungsergebnisses als auch zur Klärung von Fehlerursachen ist die Nutzung transmissionselektronenmikroskopischer Methoden unabdingbar. Für die Zielpräparation von Halbleiterstrukturen sind Techniken unter Nutzung der Focused Ion Beam Geräte etabliert, die je nach der konkreten Aufgabenstellung variiert werden. Die Abbildung von Strukturdetails mit Abmessungen von wenigen Nanometern erfordert die Anwendung unterschiedlicher Kontrastmechanismen. Die Ergänzung der Abbildung durch die analytischen Techniken der energiedispersiven Röntgenmikroanalyse und der Elektronenenergieverlustanalyse ist ein wertvolles Werkzeug bei der Klärung von Fehlerursachen oder bei prozesstechnischen Fragestellungen. Die Nutzung der Rastertransmissionselektronenmikroskopie erlaubt die unmittelbare Kombination von Abbildung und Elementanalyse. Die lokale Verteilung von Dotierstoffen als wesentliche Grundlage für die Funktion von Bauelementen in der Halbleiterindustrie ist nur über ihre Auswirkung auf die Phase der transmittierten Elektronenwelle nachweisbar. Mittels Elektronenholographie kann dieser Einfluss gemessen werden und das Prozessergebnis von Implantationen dargestellt werden. Für die Charakterisierung von Details, die kleiner als die Probendicken sind, die im TEM genutzt werden, ist die Anwendung der Elektronentomographie ein geeignetes Werkzeug. Dazu sind spezielle Präparations- und Abbildungsstrategien erforderlich. / The strong improvements in functionality and productivity in the semiconductor industry are mostly a result of the decrease of structural details on a logarithmic scale during the last decades. The monitoring of the production process, as well as failure analyses, utilize methods of transmission electron microscopy. For targeted preparations of semiconductor structures, techniques based on focused ion beams are established, with adaptions to the current task. The imaging of structural details with dimensions of a few nanometers requires the application of different contrast techniques, depending on the detailed request. Different opportunities of elemental analysis, such as energy dispersive X-ray analysis or electron energy loss analysis, deliver additional information about the chemical composition and binding states on a nanoscale. The use of scanning transmission electron microscopy enables a direct combination of imaging and elemental analysis. The local distribution of dopants, as one of the major basics for the function of semiconductor devices, can be observed via the phase shift of the transmitted electron wave only. This influence requires the application of electron holography, a technique which enables the visualization of the process result of implantations or diffusion processes. The characterization of details which are smaller than the thickness of a TEM-sample is enabled through the use of electron tomography. This technique requires special strategies for preparation and imaging and delivers a 3D-dataset, describing the structure.