No description available.

No description available.

No description available.

No description available.

No / This paper presents new chronological data applied to the problem of providing a date for the construction of a prehistoric building, with a case study from the Old Scatness Broch, Shetland. The innovative methodology employed utilises the combination of radiocarbon and optically stimulated luminescence (OSL) dates with the archaeological information, which includes the stratigraphic relationships of sampled deposits, context information, and evidence relating to the formation of the deposit. This paper discusses the scientific validity of the dates produced, and the advantages that the methodology employed at this site offers for archaeological interpretation. The combined dating evidence suggests that the broch at Old Scatness is earlier than the conventionally accepted dates for broch construction. More broadly it shows the value of integration of the specialists at the planning stages of the excavation. The application of a Bayesian statistical model to the sequences of dates allowed investigation of the robustness of the dates within the stratigraphic sequences, as well as increasing the resolution of the resulting chronology. In addition, the value of utilising multiple dating techniques on the same deposit was demonstrated, as this allowed different dated events to be directly compared as well as issues relating to the formation of the sampled deposit. This in turn impacted on the chronological significance of the resulting dating evidence, and therefore the confidence that could be placed in the results.

Rising sea levels present an ongoing threat to communities and resources around the Chesapeake Bay, east coast, USA, where tide gauges indicate that the relative rise of sea level is approximately twice the rate of average, eustatic sea-level rise. This has significantly compromised the health and viability of salt marsh habitat on the Eastern Shore during the 20th century, and the biologists who are charged with managing coastal resources in the coming decades need to understand the nature and causes of high rates of regional sea-level rise to develop suitable adaptation plans. Dated geologic deposits and geophysical models suggest that sea-level rise is relatively high on mid-Atlantic coastlines because the land surface is subsiding due to a collapsing glacial forebulge following the Last Glacial Maximum (LGM). To fully understand this process, past sea-level indicators such as dated shoreline deposits are needed to reconstruct regional sea-level behavior in the past, but rigorous age control on geologic deposits is largely restricted to the Holocene and to marine isotope stage (MIS) 5, so the rates and timescales over which these processes operate remain unknown. This research provides long-term paleoenvironmental records from ancient environments under east-central Chesapeake Bay to place the current sea-level threats into the context of a long geologic history of sea-level fluctuations. First, the Pleistocene geologic framework of the region is reconstructed through borehole drilling. Sediments from boreholes provided material for interpreting depositional environments, and for establishing age control for deposits, so that the entire stratigraphy was constrained both in space and time. The geologic framework and ages indicate that Chesapeake Bay alternated between a deeply incised fluvial system and a filled estuary repeatedly in response to major climate fluctuations since at least the early Pleistocene, ~2 Ma. The ages and sedimentology indicate that the field area was submerged intermittently in a shallow estuary until nearly the end of marine isotope stage 3. Because global sea-level proxies suggest that sea level was ~40-80 meters lower than present at that time, these ages suggest that the penultimate glacial forebulge must have remained significantly lowered for nearly 100 ky following the retreat of ice. The implication of this time lag is that mid-Atlantic coastlines are still in a relatively early state of forebulge collapse, and subsidence following retreat of ice from the Last Glacial Maximum will likely continue for the foreseeable future. Ongoing subsidence will continue to exacerbate projected eustatic sea-level rise due to changing global climate, and coastal adaptation plans must remain focused on encouraging the migration of vital habitat toward higher elevations in the landscape.

This thesis explores the surface assembly of mechanically interlocked molecular architectures at gold surfaces for potential applications in molecular switches, anion sensing and stimuli (redox and optical) responsive molecular films. <b>Chapter One</b> introduces the field of mechanically interlocked molecules focusing on rotaxane and catenane surface assemblies in the form of single molecule thick self-assembled monolayers. A review of the surface-attached characteristics of mechanically interlocked molecules is given before exploring specific anion template directed strategies for their construction. The potential to incorporate both redox-active and optically-active functional groups within these mechanically interlocked molecules is also discussed. <b>Chapter Two</b> provides the experimental details and procedures employed in this thesis to characterise the molecular systems under investigation. <b>Chapter Three</b> introduces several surface characterisation techniques such as; ellipsometry, contact angle, X-ray reflectivity and X-ray photoelectron spectroscopy, with a particular focus of applying these tools to probe the surface co-conformation of switchable and interlocked molecules at surfaces. Electroanalytical techniques such as cyclic voltammetry, chronoamperometry and electrical impedance spectroscopy are also introduced. <b>Chapter Four</b> details the surface assembly of a series of ferrocene containing anion templated catenane self-assembled monolayers on gold. Detailed electrochemical and angle resolved X- ray photoelectron spectroscopy characterisation elucidates the co-conformation upon surface attachment. <b>Chapter Five</b> details the anion templated surface assembly of a redox-active rotaxane self- assembled monolayer on gold. Subsequent electroanalysis and X-ray photoelectron spectroscopy characterisation confirms the structural integrity of the film and a possible co- conformation at the surface is discussed. <b>Chapter Six</b> describes efforts towards constructing optically responsive hybrid d-f lanthanide containing mechanically interlocked molecules. Initial work focuses on switching characteristics of a redox switchable antennae and its ability to modulate the luminescence of a series of lanthanide complexes in solution. Subsequent surface attachment of the lanthanide complexes in the form of emissive self-assembled monolayers is also investigated.

Devido à inexistência de um laboratório de padronização primária na América Latina, para calibração e dosimetria de fontes de radiação beta, neste trabalho uma câmara de extrapolação Böhm foi caracterizada e estabelecida como um sistema padrão primário no Laboratório de Calibração de Instrumentos (LCI) do IPEN. Como objetivo principal deste trabalho, a câmara de extrapolação Böhm foi caracterizada com relação à sua resposta em feixes padrões secundários de radiação beta de fontes de 90Sr+90Y, com duas janelas de entrada diferentes: Mylar aluminizado e Hostaphan grafitado, e com dois métodos de determinação de taxa de dose absorvida, para verificação do seu desempenho com cada material. Embora se trate do instrumento mais adequado para a calibração de detectores e fontes de radiação beta, a câmara de extrapolação deve ser utilizada apenas em laboratórios de calibração e não em programas de controle de qualidade, pois ela tem 7 kg e é de alto custo. Assim, é importante ter sistemas considerados padrões de trabalho e métodos alternativos para substituir a câmara de extrapolação em medições realizadas em campo, como em hospitais ou clínicas. Por este motivo, foram caracterizadas três câmaras de ionização de placas paralelas, com o objetivo de se verificar a possibilidade de seu uso como sistemas padrões de trabalho em programas de controle de qualidade, e também foram estudados materiais dosimétricos diferentes, em campos de radiação beta de 90Sr+90Y, utilizando-se os fenômenos da termoluminescência (TL) e da luminescência opticamente estimulada (LOE), como métodos alternativos na calibração de fontes de radiação beta. Inclui-se aqui o desenvolvimento de um sistema postal dosimétrico para a calibração de aplicadores clínicos de 90Sr+90Y. Os resultados obtidos com a câmara de extrapolação Böhm permitiram o seu estabelecimento como sistema padrão primário na calibração de fontes de 90Sr+90Y, pois a câmara com as duas janelas de entrada diferentes permitiram a determinação de taxas de dose absorvida no ar e no tecido, à profundidade nula e a 0,07 mm. A caracterização das três câmaras de ionização de placas paralelas mostraram que elas podem ser usadas em programas de controle de qualidade de fontes de radiação beta, pois suas respostas se apresentaram adequadas para esta finalidade. Os materiais dosimétricos testados com relação às suas respostas TL e LOE também se mostraram adequados para uso em campos de radiação beta, pois suas respostas foram satisfatórias. O sistema dosimétrico, utilizando dosímetros TL, foi testado em hospitais e, posteriormente, foi enviado na forma postal a um laboratório, contendo detectores TL e LOE, e o resultado da calibração dos aplicadores clínicos foi adequado. / Due to the lack of a primary standard laboratory at the Latin America, for the calibration and dosimetry of beta radiation sources, it was decided to establish the Böhm extrapolation chamber at the Calibration Laboratory (LCI) at IPEN as a primary standard. As a main objective of this work, the Böhm extrapolation chamber was characterized in relation to its response in beta radiation secondary standard beams of 90Sr+90Y sources, using two different entrance windows: aluminized Mylar and graphited Hostaphan, and using two methods of determination of absorbed dose rates, to verify its performance in each material. Although it is the most adequate instrument for the calibration of beta radiation detectors and sources, the extrapolation chamber should only be used at calibration laboratories, and not in quality control programs, because it weights 7 kg, and it is expensive. Thus, it is important to have systems considered work standards and alternative methods to replace the extrapolation chamber in measurements performed outside laboratories, such as in hospitals and clinics. For this reason, three parallel plate ionization chambers were characterized, with the objective to verify the possibility of their use as work standard systems, and different dosimetric materials were also studied, in beta radiation fields, using the thermoluminescence (TL) and optically stimulated luminescence (OSL) phenomena, as alternative methods for the calibration of beta radiation sources. The development of a dosimetric postal system for the calibration of 90Sr+90Y clinical applicators was included in this objective. The results obtained using the Böhm extrapolation chamber allowed its establishment as a primary standard system at the calibration of 90Sr+90Y sources, because it was possible to determine the absorbed dose rates in air and in the tissue, at null depth and 0.07 mm using the chamber with the two different entrance windows. The characterization of the three parallel plate ionization chambers showed that they can be used in quality control programs of beta radiation sources, because their responses were adequate to this purpose. The dosimetric materials were tested in relation to their TL and OSL response, and their use showed also to be adequate in beta radiation fields. The dosimetric postal system, using TL dosimeters, was tested in hospitals, and afterwards, it was sent to a laboratory, by conventional mail, with TL and OSL detectors, and the results of the calibration of the clinical applicators was adequate.

O Grupo Guaritas (Eocambriano da Bacia do Camaquã, RS) é formado por rochas siliciclásticas, predominantemente arenosas e conglomeráticas, interpretadas como de origem aluvial e eólica. Esta unidade estratigráfica pode apresentar mais de 1500 m de espessura de sedimentos e abrange as formações Guarda Velha, Pedra das Torrinhas, Varzinha, Pedra Pintada e Serra do Apertado. O Grupo Guaritas relaciona-se a importantes eventos geológicos do sul do Brasil, pois registra o encerramento da sedimentação em bacia extensional do tipo rifte (Bacia do Camaquã) durante o Cambriano, a qual se desenvolveu em área que seria posteriormente recoberta por ampla bacia intracratônica (a Bacia do Paraná), a partir do Ordoviciano. Para contribuir com novas informações sobre a proveniência das unidades eopaleozóicas brasileiras, as rochas arenosas do Grupo Guaritas foram submetidas à análise de minerais pesados, petrografia de lâminas delgadas e luminescência opticamente estimulada (LOE). As análises de minerais pesados foram realizadas na fração areia muito fina de 44 amostras coletadas em afloramentos. Essas análises abrangeram a identificação e quantificação da assembléia de minerais pesados transparentes não-micáceos, além da determinação dos índices ZTR (zircão+turmalina+rutilo), ATi (apatita/(apatita+turmalina)), ZTi (zircão/(turmalina+zircão)) e ZRi (zircão/(rutilo+zircão). As seções delgadas foram utilizadas para descrever os componentes deposicionais e diagenéticos e para classificar os arenitos estudados. Quatro amostras selecionadas foram submetidas ainda à análise da sensibilidade LOE de grãos individuais de quartzo. A sensibilidade LOE foi calculada utilizando a integral da curva LOE assim como de seus componentes, chamados informalmente de rápido, médio e lento. A sensibilidade LOE foi usada para avaliação de grau de retrabalhamento sedimentar. As amostras estudadas foram classificadas como arcóseos, subarcóseos e sublitoarenitos. Os minerais pesados identificados e suas porcentagens médias foram: zircão (36%), turmalina (13%), rutilo (3%), apatita (23%), granada (16%), anatásio (7%), titanita (1%), sillimanita (1%), monazita (<1%), epidoto (<1%), hornblenda (<1%), estaurolita (<1%) e cianita (<1%). Esses minerais pesados foram descritos em todas as unidades estudadas do Grupo Guaritas. Os valores médios do índice ZTR variam de 20 (Fm. Serra do Apertado) a 40 (Fm. Pedra Pintada) enquanto que o índice ZTi apresenta valores médios entre 62 (Fm. Guarda Velha) e 73 (Fm. Pedra Pintada). Os valores médios dos índices ZRi e ATi variam de 81 (Fm. Guarda Velha) a 90 (Fm. Varzinha) e de 79 (Fm. Guarda Velha) a 83 (Fm. Serra do Apertado), respectivamente. As médias da sensibilidade LOE total do quartzo apresentaram valores médios maiores para as unidades inferiores (Fm. Guarda Velha = 3295 contagens e Fm. Varzinha = 3655 contagens) em relação às superiores (Fm. Pedra Pintada = 2271contagens e Fm. Serra do Apertado = 2457 contagens). As médias dos componentes LOE rápido (15-19%), médio (37-38%) e lento (43-46%) não apresentam diferenças marcantes entre as unidades. A assembléia de minerais pesados dominada por zircão, apatita e turmalina sugere que os sedimentos arenosos do Grupo Guaritas são derivados principalmente de rochas ígneas ácidas (granitos neoproterozóicos). A pequena variação do índice ZRi aponta manutenção da configuração litológica da área-fonte durante a deposição das unidades estudadas. A abundância de feldspatos, fragmentos líticos e, principalmente, de apatita indica deposição em ambiente árido e/ou soterramento rápido. Isto é coerente com a sensibilidade LOE do quartzo, que é relativamente reduzida, indicando baixo grau de retrabalhamento sedimentar para as areias do Grupo Guaritas. A sensibilidade LOE mais elevada das areias da Formação Guarda Velha representaria maior contribuição de sedimentos distais mais retrabalhados.A sensibilidade LOE do quartzo permite avaliar o grau de retrabalhamento de sedimentos antigos (Cambriano), já que até então este método tinha sido aplicado somente à sedimentos quaternários. / The Guaritas Group (Eocambrian of the Camaquã Basin, southern Brazil) is mainly composed of fine to coarse-gravelly sandstones, interpreted as a record of fluvial and aeolian depositional systems. This stratigraphic unity may present more than 1500m thick of sediments, comprising the Guarda Velha, Pedra das Torrinhas, Varzinha, Pedra Pintada and Serra do Apertado formations. The Guaritas Group relates to important geological events occurred in southern Brazil during the Eopaleozoic. Its deposition marks the final episode of sedimentary filling of an extensional rift basin (Camaquã Basin) during the Cambrian, in an area after covered by a huge intracratonic basin (Paraná Basin) during the Ordovician. To contribute with new information about the provenance of Eopalaezoic Brazilian sediments, the sandy rocks of the Guaritas Group were analyzed through heavy minerals, thin section petrography and luminescence methods. Heavy minerals analyses were carried out in the very fine sand fraction of 44 rock samples collected from outcrops. These analyses included the identification and quantification of the transparent non-micaceous heavy minerals as well as the determination of the ZTR (zircon+tourmaline+rutile), ATi (apatite/(apatite+tourmaline)), ZTi (zircon/(tourmaline+zircon)) and ZRi (zircon/(rutile+zircon) indices. Thin section petrography was used to describe depositional and diagenetic components and classify the studied sandstones. Further, four samples were selected for measurements of optically stimulated luminescence (OSL) sensitivity in quartz single-grains. The OSL sensitivity was calculated using the total OSL curve as well as specific components, informally named fast, medium and slow. The OSL sensitivity of quartz has been used as a proxy for sedimentary reworking. The studied sandstones were classified as arkoses, subarkoses and sublitharenites. The identified heavy minerals and their mean percentages were: zircon (36%), tourmaline (13%), rutile (3%), apatite (23%), garnet (16%), anatase (7%), titanite (1%), sillimanite (1%), monazite (<1%), epidote (<1%), hornblende (<1%), staurolite (<1%) and kyanite (<1%). These heavy minerals were described in all studied units of the Guaritas Group. The mean values of the ZTR indice varied from 20 (Serra do Apertado Fm.) to 40 (Pedra Pintada Fm.) while the ZTi indice presented mean values between 62 (Guarda Velha Fm.) and 73 (Pedra Pintada Fm.). The mean values of the ZRi and ATi indices ranged from 81 (Guarda Velha Fm.) to 90 (Varzinha Fm.) and from 79 (Guarda Velha Fm.) to 83 (Serra do Apertado Fm.), respectively. The total OSL sensitivity of quartz demonstrated higher mean values for the bottom units (Guarda Velha Fm. = 3295 counts; Varzinha Fm. = 3655 counts) than for the upper units (Pedra Pintada Fm. = 2271 counts, and Serra do Apertado Fm. = 2457 counts). The means of the fast OSL component (15-19%), medium (37-38%) and slow (43-46%) did not differ markedly among the units. The heavy minerals assemblage dominated by zircon, tourmaline and apatite suggests that the sandy sediments of the Guaritas Group are mainly derived from acid igneous rocks (neoproterozoic granites).The low range of variation of the ZRi indice points out the maintenance of similar primary source rocks during the deposition of the Guaritas sediments. The abundance of unstable grains such as feldspars, lithic fragments and apatite indicates deposition under arid climate and/or high rate of sediment accumulation. The OSL sensitivity of quartz grains is relatively low, suggesting sands with low degree of reworking. This is compatible with the high content of unstable sand grains (apatite, feldspar and lithic fragments) and elevated rate of sediment accumulation. The greater proportion of grains with higher OSL sensitivity in the Guarda Velha Formation represents an increased contribution of sediments from distal more reworked sources.The OSL sensitivity of quartz allows evaluate the degree of reworking of older sediments (Cambrian), since this method had been applied only to Quaternary sediments.

A luminescência opticamente estimulada (OSL) é a luminescência emitida por um material, isolante ou semicondutor, durante exposição à luz e que foi previamente exposto à radiação ionizante. Portanto, depende da quantidade de cargas armadilhadas na estrutura do material, o que por sua vez depende da dose de radiação absorvida pela amostra. Dessa forma, a busca por novos materiais para serem utilizados como detectores de radiação envolve a criação de defeitos que atuem como armadilhas e/ou centros luminescentes. Recentemente, as interações entre os plásmons de nanopartículas metálicas e centros luminescentes têm sido utilizadas para aumentar a intensidade luminescente emitida por diversos materiais. Nesse trabalho, foi investigada a possibilidade de aplicação das propriedades plasmônicas de nanoestruturas de prata e ouro, no aumento da emissão OSL. Para isso, foram testados como dosímetros OSL, compósitos de cloreto de sódio contendo nano e micropartículas de prata; compósitos de óxido de zinco contendo nanopartículas de ouro e prata; e amostras de cloreto de sódio depositado sobre filmes de nanopartículas de prata e ouro. As amostras foram caracterizadas por diversas técnicas como espectroscopia UV-Vis, espalhamento dinâmico de luz, espectroscopia na região do infravermelho, espectroscopia de fotoluminescência, microscopia eletrônica de transmissão, microscopia de força atômica, entre outras. Foi possível verificar que a intensificação dos campos elétricos locais em torno de nanopartículas metálicas em condições de ressonância plasmônica aumenta a taxa de desarmadilhamento de elétrons durante a estimulação OSL. O acoplamento plasmônico causou aumento das taxas de decaimento radiativo e redução das taxas de decaimento não radiativo, produzindo aumento da intensidade OSL. Além disso, as interações entre as armadilhas/centros luminescentes e os plásmons variam de acordo com a distância entre as partes, e a maior intensidade OSL foi obtida para amostras em que houve um espaçamento de aproximadamente 15 nm entre o NaCl o filme de nanopartículas de prata. Portanto, é possível utilizar as propriedades plasmônicas de nanoestruturas metálicas para aumentar a intensidade da luminescência opticamente estimulada, dando origem a novos e mais sensíveis detectores e dosímetros das radiações ionizantes. / Optically stimulated luminescence (OSL) is a well-known light emission process involving light stimulation of an insulator/semi-conductor material previously exposed to ionizing radiation. The intensity of the emitted light is proportional to the ionizing radiation dose previously absorbed by the material. Developing appropriate OSL materials for radiation detection and dosimetry is based on the doping and co-doping of a host material to create defects that can act as traps and/or luminescent centers. In this context, plasmon interaction with luminescent centers from OSL materials could be a new, different, and unexplored method to achieve enhanced OSL intensity and consequently improve their sensitivity as radiation detectors. In this study, we investigated whether it is possible to use the plasmonic properties of noble metal nanoparticles to obtain plasmon-enhanced OSL. To this end, we produced samples of NaCl containing nano and microparticles; composites of ZnO containing silver and gold nanoparticles; as well as samples of NaCl deposited over films of gold and silver nanoparticles. Each sample has been tested as a radiation detector by means of optically stimulated luminescence, in addition to having their materials properties analyzed by UV-Vis absorption spectroscopy, dynamic light scattering, transmission electron microscopy (TEM), atomic force microscopy, and Fourier Transform Infrared spectroscopy (FTIR). We discovered that the electric field intensification around nanoparticles under plasmon resonance conditions enhances the excitation rate of trapped electrons. The plasmon coupling during the emission process increases the radiative and diminishes the non-radiative decay rates, leading to enhanced OSL intensities. Furthermore, the interaction between traps/luminescent centers and plasmons is highly dependent on the distance between them, and the maximum OSL intensity was observed for samples with 15 nm spacing between the NaCl and the silver nanoparticle films. Therefore, it is possible to use the plasmon properties of metal nanostructures to increase OSL, giving rise to new and more sensitive ionizing radiation detectors and dosimeters.