A cultura da cana-de-açúcar no Brasil é uma das atividades mais relevantes na agroindústria nacional devido ao alto potencial de produção e elevada importância econômica de seus subprodutos como e.g. açúcar e etanol. Embora o Si não seja considerado um elemento essencial, a adubação silicatada tem proporcionado aumentos apreciáveis na produtividade da cana-de-açúcar e na resistência a algumas pragas e doenças. Ainda não existem métodos bem estabelecidos para a determinação de Si em material vegetal visando à diagnose foliar. O objetivo deste trabalho foi desenvolver um método para determinação de Si em pastilhas de folhas de cana-de-açúcar por espectrometria de emissão óptica com plasma induzido por laser (LIBS). O arranjo experimental foi composto por um laser pulsado de Nd:YAG a 1064 nm (pulsos de 5 ns, 360 mJ, 10 Hz) e os sinais de emissão foram coletados por um telescópio acoplado por fibra óptica ao espectrômetro Echelle com detector ICCD. Amostras laboratoriais consistiram de pastilhas preparadas com folhas de cana-de-açúcar moídas criogenicamente por 40 min. Melhores resultados foram obtidos quando a linha de emissão Si I 212,412 nm foi selecionada e os parâmetros instrumentais foram ajustados em 25 pulsos acumulados, 50 J cm-2, diâmetro de focalização de 750 \'mü\'m, 2,0 \'mü\'s de atraso e 4,5 \'mü\'s de integração. Os resultados obtidos por LIBS na análise de pastilhas de 20 amostras laboratoriais foram comparados com os obtidos por espectrometria de emissão óptica com plasma acoplado indutivamente (ICP OES) após decomposição alcalina e por espectrometria de micro-fluorescência de raio-X por energia dispersiva (\'mü\'ED-XRF) após análise direta das pastilhas. Aplicando-se o teste t de Student pareado, não foram verificadas diferenças significativas ao nível de 95% de confiança nas determinações de Si por LIBS, ICP OES e \'mü\'ED-XRF. Os resultados obtidos nesta tese indicam a viabilidade de LIBS para determinação direta de Si em pastilhas de folhas de cana-de-açúcar e abrem uma expectativa para futuras explorações de LIBS em análises em campo / The high production of sugarcane and its subproducts (e.g. sugar and ethanol fuel) make this crop one of the most important for the Brazilian agro-industrial economy. Although Si is not considered an essential element, the Si-based fertilizers have provided considerable improvement in productivity of sugarcane and resistance to some pests and diseases. At moment, there are no well-established methods for the determination of Si in plant materials aiming at nutritional diagnosis. The aim of this work was to develop a method for Si determination in pellets of sugarcane leaves by laser-induced breakdown spectroscopy (LIBS). The experimental setup was designed by using a Q-switched Nd:YAG laser (5 ns, 360 mJ, 10 Hz, \'lâmbda\' = 1064 nm) and the emission signals were collected by lenses into an optical fiber coupled to an Echelle spectrometer equipped with an ICCD. Pellets prepared from cryogenically ground sugarcane leaves were used as laboratory samples. Best results were obtained when the Si I 212.412 nm emission line was selected and the instrumental parameters were adjusted at 25 laser shots, 50 J cm-2, 750 \'mü\'m laser spot size, 2.0 \'mü\'s delay time and 4.5 \'mü\'s integration time gate. The results obtained by LIBS in the analysis of pellets of 20 laboratory samples were compared with those from inductively coupled plasma optical emission spectrometry (ICP OES) after alkaline digestion and by microenergy dispersive X-ray fluorescence (\'mü\'ED-XRF) after direct analysis of pellets. By applying a paired t-test at 95 % confidence level, there was no significant difference in the Si determination by LIBS, ICP OES and \'mü\'ED-XRF. The findings of this thesis indicate the feasibility of LIBS for the direct determination of Si in pellets of sugarcane leaves and open expectations for future investigations of LIBS for field analysis

Tato diplomová práce je zaměřena na analýzu lehkých prvků (tj. uhlík, sýra a fosfor) v železných slitinách pomocí metody laserem indukovaného plazmatu (LIBS). Hlavním cílem je vyvinout a implementovat nový modul, který bude umožňovat analýzu v hluboké ultrafialové oblasti (VUV), což je nezbytné jak pro stanovení chemického složení lehkých prvků v ocelích tak pro mnoho dalších aplikací metody LIBS. V první části je vytvořen přehled moderních přístupů optické emisní spektroskopie (OES) a rovněž jsou shrnuty tradiční techniky používané v metalurgii pro analýzu ocelí. Teorie absorpce ultrafialového záření vzduchem a optickými skly byla důkladně studována a shrnuta k získání potřebného teoretického základu k vývoji modulu. Před návrhem finální verze modulu byl navržen experimentální modul s cílem otestovat navržený koncept analýzy ve VUV oblasti metodou LIBS. Na základě testování byla navrhnuta finální verze založená na unikátním klínovém mechanismu. Funkční vzorek byl vyroben ve spolupráci s extérním výrobcem a vlastnosti modulu byly následně demonstrovány naměřením pěti certifikovaných ocelových standardů. Experiment určil limity detekce pro uhlík jako 0.028 hm.%. Nicméně, síra ani fosfor nebyly detekovány v žádném ze vzorků. Tato práce vytvořila modul nezbytný pro budoucí zkoumání metody LIBS v oblasti VUV v Laboratoři laserové spektroskopie v Brně.

Laser-induced breakdown spectroscopy (LIBS) is a fast analytical method, but can also be complicated. This spectroscopic method is used to provide a qualitative and quantitative analysis of a sample. The analysis is carried out by capturing the emission radiation of the generated plasma. The accuracy and stability of the measurement is affected by several parameters, such as stability of the laser, physical and chemical properties of the sample, its homogeneity and others, that can not always be eliminated. For this reason other methods are being added to the LIBS experiment that could improve the quality of this analysis. This diploma thesis is focused on a research of the literature on the standardization of laser-induced plasma signal and the possibility of using an acoustic signal for this purpose. For this reason , it is necessary to perform basic experiments and to verify if the acoustic signal correlates with the emission signal. If these signals correlate together, it would be possible to use the acoustic signal for standardization og the LIBS data, which would improve the accuracy of the analysis. In the theoretical part at the beginning other spectroscopic methods are summarised. Then the work is focused on the description of the LIBS method, possible ways of the analysis, standardization of emission signals and its review in the literature. The experimental part is aimed at the study of the acoustic signal that was performed in the framework of this study. At the beginning, there are introduced results of the basic measurements on steel and brass samples. These results were important for an optimization of the experiment. The following section shows the results obtained from the measurements of the acoustic signal on the samples with the same chemical composition but different hardness. At the end the correlation between the acoustic and emission signals is discussed.

This diploma thesis deals with evaluation of toxicity and bioaccumulation of photon-upconversion nanoparticles (UCNPs) in model plant maize (Zea mays). Lanthanide-doped UCNPs with different composition and size were tested in three different concentrations in this work. The exposure took place for 168 hours. Toxicity was assessed based on four macroscopic toxicological endpoints (mortality, the length of belowground part of the plants, the length of aboveground part of the plants and whole plants length). Spatial distribution of elements yttrium, ytterbium, erbium and gadolinium in model plants was determined using laser induced breakdown spectroscopy with spatial resolution of 100 m and 26 m. Distribution of UCNPs in plants was further studied with photon-upconversion microscanning with spatial resolution of 40 m. Stability of UCNPs during and after the plant exposure was also discussed in this thesis.

The presented diploma thesis deals with the elemental composition of hard tissues – human and murine jaws studied by laser-induced plasma spectroscopy (LIBS). Samples of human teeth contained a disease called ankylosis and the difference in elemental composition of healthy and diseased tissue was observed to localize ankylosis in the tooth. When evaluating the map of the spatial distribution of phosphorus and calcium, a decrease in the concentration of these elements in the ankylosis infected area was observed. Furthermore, murine jaws containing lead were analyzed. When assessing the spatial distribution of lead in tissue, it was found that lead was incorporated in murine teeth in the enamel at the tip of the incisor and molars. In conclusion, LIBS method achieved good results considering the detection of the elemental distribution of hard tissues. It enables to differentiate parts of the tooth in terms of elemental composition and tissue hardness and also to detect changes in the matrix caused by a disease or bioaccumulation of heavy metals.

The diploma thesis deals with the use of Laser-Induced Breakdown Spectroscopy (LIBS) for depth profiling and 3D mapping of the zinc-coated steel used in the automotive industry. Before creating depth maps and depth profiles, optimization of the experiment was performed. It was shown that the LIBS technique is suited for making depth profiles and depth maps. The theoretical part deals with the description of the LIBS instrumentation, characteristics of plasma, and assembling of scientific papers which reflect the up to date knowledge about depth profiling and mapping with the use of the LIBS technique. The experimental part describes the optimization of the experiment. Gate delay, the depth and the diameter of craters using the profilometer, the position of the focal plane relative to the sample surface, and selection of spectral lines with the smallest residual signal and small scattering of data were optimized. Depth profiles of zinc, iron, chromium and manganese with the depth map of zinc and iron were made, and also the depth resolution for both elements was calculated.

Ziel der vorliegenden Arbeit ist die Untersuchung der Methode der Laserinduzierten Plasmaspektroskopie (LIPS) zur Bestimmung des Aufmischungsgrades ([Eta]) in durch Laserstrahl-Präzisionsauftragschweißen (LAP) hergestellten Beschichtungen. Grund- und Zusatzwerkstoff müssen sich hierbei in ihrer Elementzusammensetzung voneinander unterscheiden. Als Substratmaterial diente unlegierter Baustahl, als Zusatzwerkstoff wurde Stellit 21 eingesetzt. [Eta] stellt eine wichtige Qualitätskenngröße dar und kann nach vorheriger Kalibrierung des LIPS-Messsystems sowohl offline als auch online detektiert werden. Der Aufmischungsgrad korreliert mit dem detektierten Emissionslinienverhältnis. Im untersuchten Fall besteht in guter Näherung ein linearer Zusammenhang zwischen beiden Größen. Die Vorteile von LIPS gegenüber anderen Verfahren liegen insbesondere in der berührungslosen Analyse und der entfallenden Probenpräparation. Prinzipiell lässt sich das Vorgehen auf andere Werkstoffsysteme übertragen. Das verwendete LISP-Messsystem kann in den Fertigungsprozess integriert werden und steht als Technologiemodul für eine qualifizierte Überwachung des Aufmischungsgrades beim LAP-Prozess zur Verfügung.

Táto práca sa zaoberá prenosom analytických modelov medzi rôznymi systémami spektroskopie laserom indukovanej plazmy (LIBS) a porovnaním LIBS výsledkov získaných na rôznych systémoch. Instrumentácia LIBS aj spracovanie LIBS spektier sú vysoko flexibilné. Bohužiaľ, kvôli týmto flexibilitám sú výsledky získané na jednom LIBS systéme zriedka priamo porovnateľné s výsledkami získanými na inom systéme. Toto je ďalej komplikované rôznymi, často neznámymi, účinkami algoritmov spracovania LIBS spektier. V dôsledku toho sú modely analýzy spravidla špecifické pre systém (a parametre). Prenos analytických modelov medzi rôznými systémami by viedol k významnému zlepšeniu analytických schopností metódy LIBS a k miernemu zníženiu nákladov v priemyselných aplikáciách LIBS. Práca skúma vplyv rôznych stratégií merania metódou LIBS. Naďalej, práca skúma transformáciu získaných LIBS spektier prostredníctvom spracovávania údajov. Práca sa napokon zaoberá prenosom analytických modelov medzi rôznymi LIBS systémami.

Diese Arbeit handelt von der Anwendbarkeit laserinduzierter Plasmaspektroskopie (englisch: laser-induced breakdown spectroscopy, LIBS) mit Detektion im vakuumultravioletten Spektralbereich (VUV), im Folgenden VUV-LIBS genannt, im Bereich der Planetenforschung. Für LIBS wird ein gepulster Laser auf die zu untersuchende Probe fokussiert. Dabei wird Probenmaterial abgetragen, verdampft und teilweise ionisiert. Die im Plasma enthaltenen Atome und Ionen werden elektronisch angeregt und strahlen in der Folge Licht charakteristischer Wellenlängen ab, welches spektroskopisch analysiert werden kann. Diese Analyse erlaubt einen Rückschluss auf die im Plasma und somit in der Probe enthaltenen chemischen Elemente. Mit LIBS können alle Elemente detektiert werden. Allerdings sind insbesondere die Nichtmetalle schwerer zu detektieren, deren intensivste Emissionslinien im VUV-Bereich liegen, d.h. bei Wellenlängen kürzer als 200 nm, der oft nicht untersucht wird. In diesem Spektralbereich wird ein Großteil der Strahlung von der irdischen Atmosphäre absorbiert. Auf atmosphärelosen Himmelskörpern wie dem Mond ist dies nicht der Fall, sodass für die Elemente C, Cl, H, N, O, P und S eine verbesserte Detektierbarkeit erwartet wird als mit konventionellem LIBS im typischerweise untersuchten Spektralbereich über 200 nm. Die hier präsentierten Ergebnisse deuten darauf hin, dass VUV-LIBS in der Tat eine verbesserte Detektierbarkeit für S und Cl im Kontext einer Mondmission bewirken kann. Für eine umfassende Beurteilung der Methode in dieser Anwendung und zur Verbesserung der Nachweisgrenzen sind jedoch weitere Untersuchungen mit einem verbesserten Messaufbau notwendig. Da wichtige gesteinsbildende Elemente wie Ca, Na und Mg im VUV-Bereich keine oder nur schwache Emission zeigen, liegt das größte Potenzial von VUV-LIBS möglicherweise in der Kombination mit LIBS in anderen Spektralbereichen oder mit anderen analytischen Methoden. / This thesis investigates the application of laser-induced breakdown spectroscopy (LIBS) with detection in the vacuum ultraviolet (VUV) spectral range for in-situ space exploration. For LIBS, a pulsed laser is tightly focused onto the sample, thereby ablating material and exciting a luminous plasma. The atoms and ions contained in the plasma radiate light of characteristic wavelengths, which can be analysed with spectrometers. The spectral analysis allows to identify the chemical elements in the plasma, which are assumed to be representative for the elements contained in the sample. With LIBS, all elements can be detected. However, especially the non-metal elements are challenging to detect because their strongest lines are located in the VUV spectral range, i.e. below 200 nm, which is often not investigated. Detection in this range brings its own challenges, since large parts of the radiation spectrum are absorbed by the atmosphere surrounding the sample. On celestial bodies without an atmosphere, such as the Moon, the ambient conditions are well suited for VUV-LIBS analyses. In such a scenario, a better detectability for the otherwise challenging elements C, Cl, H, N, O, P and S is expected compared to LIBS in the usually employed detection range above 200 nm. The results shown in this thesis indicate that VUV-LIBS is promising for the improved detection of light elements such as S and Cl in a lunar context. However, more extensive studies with an optimized set-up are necessary to properly assess the true capabilities of the method and to further reduce the detection limits. Although emission from the most abundant chemical elements in geological samples, Al, Si and O, could be reliably detected in all samples containing them, VUV-LIBS might in the end be best used in combination with LIBS in the UV-VIS range or with other analytical techniques, because the major rock forming elements Ca, Na and Mg hardly show emission lines in the VUV spectral range.

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