Bento Coelho da Silveira na igreja matriz de S. João Baptista

Dissertação para obtenção do Grau de Mestre em Conservação e Restauro

Avaliação de estado de uma escultura de bronze: “Jean d’Aire” de Auguste Rodin

Dissertação para a obtenção do Grau de Mestre em Conservação e Restauro, Especialização em Metais

Analysis, testing and development of safe cleaning methods of rusted stone material

Three different treatments were applied on several specimens of dolomitic and calcitic marble, properly stained with rust to mimic real situations (the stone specimens were exposed to the natural environment for about six months in contact with rusted iron). Thirty six marble specimens, eighteen calcitic and eighteen dolomitic, were characterized before and after treatment and monitored throughout the cleaning tests. The specimens were characterized by SEM-EDS (Scanning Electron Microscopy coupled with Energy Dispersion System), XRD (XRay Diffraction), XRF (X-Ray Fluorescence), FTIR (Fourier Transform Infrared Spectroscopy) and color measurements. It was also made a microscopic and macroscopic analysis of the stone surface along with the tests of short and long term capillary absorption. A series of test trials were conducted in order to understand which concentrations and contact times best suits to this purpose, to confirm what had been written to date in the literature. We sought to develop new methods of treatment application, skipping the usual methods of applying chemical treatments on stone substrates, with the use of cellulose poultice, resorting to the agar, a gel already used in many other areas, being something new in this area, which possesses great applicability in the field of conservation of stone materials. After the application of the best methodology for cleaning, specimens were characterized again in order to understand which treatment was more effective and less harmful, both for the operator and the stone material. Very briefly conclusions were that for a very intense and deep penetration into the stone, a solution of 3.5% of SDT buffered with ammonium carbonate to pH around 7 applied with agar support would be indicated. For rust stains in its initial state, the use of Ammonium citrate at a concentration of 5% buffered with ammonium to pH 7 could be applied more than once until satisfactory results appear.

Análise elementar em tecidos biológicos

Os elementos traço são elementos que existem no organismo humano e que se apresentam em concentrações variadas. A variação da concentração destes elementos pode levar a intoxicações ou mesmo à formação de tecidos cancerígenos no organismo humano. Neste trabalho efectuaram-se dois estudos de elementos traço no organismo, sendo que numa das situações foram utilizados ratos Wistar e na outra situação utilizaram-se amostras de tecidos humanos recolhidos em biópsias. Foi utilizada a técnica de fluorescência de raios-X na análise de tecidos, nomeadamente, a espectroscopia de micro-fluorecência de raios-X ( -XRF) e a espectroscopia de energia dispersiva de raios-X com um sistema tri-axial (EDXRF). No estudo dos ratosWistar, pretendeu-se analisar a intoxicação por chumbo no organismo através da adição de acetato de chumbo na água ingerida. Conclui-se deste estudo que existe uma correlação positiva entre a acumulação de chumbo no organismo e a sua excreção através das unhas e do pêlo, sendo que o pêlo poderá vir a servir como método de diagnóstico de intoxicação por metais pesados. No estudo de tecidos cancerígenos pretendeu-se observar as possíveis alterações de elementos no organismo quando o tecido contém uma neoplasia. Analisaram-se amostras de tecidos de rim, pulmão e cólon, saudáveis e com neoplasia e concluiu-se que efectivamente existem alterações nas concentrações de elementos traço de amostras saudáveis para amostras com neoplasia variando estas concentrações de tecido para tecido.

Otimização da técnica de micro Fluorescência de Raios- X para o estudo de ossos

Nos países desenvolvidos, as doenças reumáticas são o grupo de doenças mais fre-quentes da espécie humana, sendo por isso o primeiro motivo de consulta nos cuidados de saúde primários e a principal causa de incapacidade temporária para o trabalho e de reformas antecipadas por doença/invalidez (Canhão & Branco, 2013). O estudo destas doenças torna-se cada vez mais urgente visto que estas têm tendência crescente, tendo em conta os atuais esti-los de vida e o aumento da longevidade da população. Nesta dissertação foi estudada e otimi-zada a técnica de Micro Fluorescência de Raios-X (μ-XRF) de forma a permitir um estudo de elementos maioritários e elementos traço em ossos com doenças reumáticas, tendo em espe-cial atenção a razão Ca/P, já que, por estudos até agora efetuados, esta razão é considerada um biomarcador adequado para a avaliação da saúde dos ossos. Foram então verificados os erros aleatórios e sistemáticos existentes nesta técnica e concluiu-se quais os tipos de parâme-tros que devem ser tidos em conta para este estudo, tais como corrente, tensão do tubo, filtros, entre outros. As amostras foram ainda analisadas com a técnica de PIGE (Particle Induced Gamma-ray Emission) e comparados os resultados com os de μ-XRF de forma a avaliar a in-fluência da topologia da amostra. Pretende-se que este estudo seja o início do desenvolvimen-to de um método alternativo de diagnóstico precoce de doenças reumáticas, conduzindo a um tratamento mais eficaz e melhorando assim a qualidade de vida da população.

Efeito de background local e assinatura geoquímica de anomalias naturais em sedimentos de corrente e solos – aplicação à área envolvente do jazigo de urânio (Nisa, Portugal)

Na região de Nisa, concelho de Portalegre, situa-se um dos maiores e mais relevantes jazigos de urânio alguma vez descoberto em território nacional. Trata-se de um jazigo ainda inexplorado que encerra um potencial estimado em cerca de 32 milhões de toneladas de minério tal qual. Este jazigo ocorre à superfície e encontra-se em contexto metassedimentar embutido em xistos mosqueados, pertencentes ao Grupo das Beiras, nas proximidades do contacto com o granito do Maciço de Nisa. Este trabalho tem como objetivo estudar de forma qualitativa e quantitativa a dispersão geoquímica provocada por processos naturais de erosão e de transporte hidrogravítico na envolvente à anomalia geoquímica natural localmente induzida por este jazigo. Para o efeito estabeleceu-se uma metodologia com as seguintes etapas principais: (1) georreferenciação em SIG de elementos de cartografia; (2) planeamento e elaboração do plano de amostragem; (3) recolha e tratamento de amostras de solos e sedimentos; (4) ensaios não destrutivos de medição de radiação gama por SPP2 e determinações analíticas por XRF; (5) análise exploratória e tratamento estatístico de dados e análise espacial; (6) análise de resultados; (7) definição de teores geoquímicos de fundo local. As amostras de sedimentos foram retiradas de uma ribeira que intersecta a área da anomalia e alimenta uma barragem local de enrocamento; as amostras de solos foram retiradas de linhas de amostragem perpendiculares à ribeira. As determinações analíticas registaram os teores em diversos metais, como o urânio, crómio, molibdénio, nióbio, vanádio e zinco e do semimetal arsénio. Com exceção do zinco, os resultados evidenciam que as concentrações naturais nestes metais no local onde se localiza uma importante jazida de minérios de urânio são muito elevados, e quando comparados com os valores standard da norma Canadiana mostram poder existir risco para a saúde se não forem limitados os usos do local.

Caracterização de materiais plásticos usados na indústria têxtil e de vestuário por FTIR

Dissertação de mestrado em Técnicas de Caracterização e Análises Químicas

Una arqueometria del canvi tecnològic: producció i consum d'àmfores durant el canvi d'era en la zona nord de la costa catalana

L’objectiu de la recerca és definir un marc teòric i metodològic per a l’estudi del canvi tecnològic en Arqueologia. Aquest model posa èmfasi en caracteritzar els compromisos que configuren una tecnologia i avaluar-los en funció dels factors de situació —tècnics, econòmics, polítics, socials i ideològics. S’ha aplicat aquest model a un cas d’estudi concret: la producció d’àmfores romanes durant el canvi d’Era en la província Tarraconensis. L’estudi tecnològic dels envasos s’ha realitzat mitjançant diverses tècniques analítiques: Fluorescència de raigs X (FRX), Difracció de raigs X (DRX), Microscòpia òptica (MO) i Microscòpia electrònica de rastreig (MER). Les dades obtingudes permeten, a més, establir els grups de referència per a cada centre productor d’àmfores i, així, identificar la provinença dels individus recuperats en els centres consumidors. Donat que les àmfores en estudi són artefactes dissenyats específicament per a ser estibats en una nau i servir com a envàs de transport, l’estudi inclou la caracterització de les propietats mecàniques de resistència a la fractura i de tenacitat. En aquest sentit, i per primera vegada, s’ha aplicat l’Anàlisi d’Elements Finits (AEF) per a conèixer el comportament dels diferents dissenys d’àmfora en ésser sotmesos a diverses forces d’ús. L’AEF permet simular per ordinador les activitats en què les àmfores haurien participat durant el seu ús i avaluar-ne el seu comportament tècnic. Els resultats mostren una gran adequació entre les formulacions teòriques i el programa analític implementat per a aquest estudi. Respecte el cas d’estudi, els resultats mostren una gran variabilitat en les eleccions tecnològiques preses pels ceramistes de diferents tallers, però també al llarg del període de funcionament d’un mateix taller. L’aplicació del model ha permès proposar una explicació al canvi de disseny de les àmfores romanes.

Compositional data analysis in archaeometry

We shall call an n × p data matrix fully-compositional if the rows sum to a constant, and sub-compositional if the variables are a subset of a fully-compositional data set1. Such data occur widely in archaeometry, where it is common to determine the chemical composition of ceramic, glass, metal or other artefacts using techniques such as neutron activation analysis (NAA), inductively coupled plasma spectroscopy (ICPS), X-ray fluorescence analysis (XRF) etc. Interest often centres on whether there are distinct chemical groups within the data and whether, for example, these can be associated with different origins or manufacturing technologies

Ostoprosessin kehittäminen

Insinöörityön tavoitteena on selvittää Hakaniemen Metalli Oy ja sen tytäryhtiön High Metal Production ostotilakset ja tämän avulla tehdä analyysi tärkeimpien alihankkioiden taloustiedoista. Työssä perehdyttiin nykyiseen ostoluetteloon sekä kehitettiin sitä ABC-analyysin avulla. Tarkoituksena oli poistaa turhia alihankkijoita ja vähentää tilausten määrää nykyisestä. Ostotilauslistan laatimisen jälkeen koottiin taloustiedot tärkeimmistä alihankkijoista. Työn teoriaosassa käsitellään lisäksi logistiikan perusperiaatteita sekä logistiikan kilpailukyvyn kehittämistä. Työn tuloksena on pystytty vähentämään tilausten määrää sekä poistamaan tarpeettomia toimittajia yrityksen listoilta. Yritysten ostotilausten yhteenvedot sekä niiden yhteinen ostotilauslista on esitetty ainoastaan yrityksen käyttöön tarkoitetuissa liitteissä.

Survey on batch-to-batch variation in spray paints: a collaborative study

This study represents the most extensive analysis of batch-to-batch variations in spray paint samples to date. The survey was performed as a collaborative project of the ENFSI (European Network of Forensic Science Institutes) Paint and Glass Working Group (EPG) and involved 11 laboratories. Several studies have already shown that paint samples of similar color but from different manufacturers can usually be differentiated using an appropriate analytical sequence. The discrimination of paints from the same manufacturer and color (batch-to-batch variations) is of great interest and these data are seldom found in the literature. This survey concerns the analysis of batches from different color groups (white, papaya (special shade of orange), red and black) with a wide range of analytical techniques and leads to the following conclusions. Colored batch samples are more likely to be differentiated since their pigment composition is more complex (pigment mixtures, added pigments) and therefore subject to variations. These variations may occur during the paint production but may also occur when checking the paint shade in quality control processes. For these samples, techniques aimed at color/pigment(s) characterization (optical microscopy, microspectrophotometry (MSP), Raman spectroscopy) provide better discrimination than techniques aimed at the organic (binder) or inorganic composition (fourier transform infrared spectroscopy (FTIR) or elemental analysis (SEM - scanning electron microscopy and XRF - X-ray fluorescence)). White samples contain mainly titanium dioxide as a pigment and the main differentiation is based on the binder composition (Csingle bondH stretches) detected either by FTIR or Raman. The inorganic composition (elemental analysis) also provides some discrimination. Black samples contain mainly carbon black as a pigment and are problematic with most of the spectroscopic techniques. In this case, pyrolysis-GC/MS represents the best technique to detect differences. Globally, Py-GC/MS may show a high potential of discrimination on all samples but the results are highly dependent on the specific instrumental conditions used. Finally, the discrimination of samples when data was interpreted visually as compared to statistically using principal component analysis (PCA) yielded very similar results. PCA increases sensitivity and could perform better on specific samples, but one first has to ensure that all non-informative variation (baseline deviation) is eliminated by applying correct pre-treatments. Statistical treatments can be used on a large data set and, when combined with an expert's opinion, will provide more objective criteria for decision making.

Dispersion of natural arsenic in the Malcantone watershed, Southern Switzerland: field evidence for repeated sorption-desorption and oxidation-reduction processes

In recent years, elevated arsenic concentrations have been found in waters and soils of many, countries, often resulting in a health threat for the local population. Switzerland is not an exception and this paper deals with the release and subsequent fate of arsenic in a 200-km(2) mountainous watershed, characterized by crystalline silicate rocks (gneisses, schists, amphibolites) that contain abundant As-bearing sulfide ore deposits, some of which have been mined for iron and gold in the past. Using analytical methods common for mineralogical, ground water and soil studies (XRD, XRF, XAS-XANES and -EXAFS, electron microprobe, extraction, ICP, AAS with hydride generator, ion chromatography), seven different field situations and related dispersion processes of natural arsenic have been studied: (1) release by rock weathering, (2) transport and deposition by water and ice; (3) release of As to the ground and surface water due to increasing pH; (4) accumulation in humic soil horizons; (5) remobilization by reduction in water-saturated soils and stagnant ground waters; (6) remobilization by using P-rich fertilizers or dung and (7) oxidation, precipitation and dilution in surface waters. Comparison of the results with experimental adsorption studies and speciation diagrams from the literature allows us to reconstruct and identify the typical behavior of arsenic in a natural environment under temperate climatic conditions. The main parameters identified are: (a) once liberated from the primary minerals, sorption processes on Fe-oxy-hydroxides dominate over Al-phases, such as Al-hydroxides or clay minerals and limit the As concentrations in the spring and well waters between 20 and 300 mug/l. (b) Precipitation as secondary minerals is limited to the weathering domain, where the As concentrations are still high and not yet too diluted by rain and soils waters. (c) Although neutral and alkaline pH conditions clearly increase the mobility of As, the main factor to mobilize As is a low redox potential (Eh close or below 0 mV), which favors the dissolution of the Fe-oxy-hydroxides on which the As is sorbed. (d) X-ray absorption spectroscopy (XAS) of As in water-logged humic forest soils indicates that the reduction to As III only occurs at the solid-water interface and that the solid contains As as As V (e) A and Bh horizons of humic cambisols can effectively capture As when As-rich waters flow through them. Complex spatial and temporal variation of the various parameters in a watershed results in repeated mobilization and immobilization of As, which continuously transports As from the upper to the lower part of a watershed and ultimately to the ocean. (C) 2004 Elsevier B.V. All rights reserved.

Geochemistry and 40Ar/39Ar geochronology of pseudotachylyte associated with UHP whiteschists from the Dora Maira massif, Italy

In situ UV-Iaser ablation Ar-40/(39) Ar geochronological and geochemical data, together with rock and mineral compositional data, have been determined from pseudotachylyte and surrounding mylonitic gneiss associated with the UHP whiteschists of the Dora Maira Massif, Italy. Several generations of fresh pseudotachylyte occur as irregular veins up to a few cur thick both parallel and at high angles to the foliation. Whole rock XRF data collected from representative lithologies of mylonitic gneiss are uniformly consistent with a mildly alkalic granitic protolith. Minimal compositional variation is observed between the pseudotachylyte and its surrounding mylonitic gneiss. The pseudotachylyte contains newly crystallized grains of biotite and K-feldspar in a matrix of glass with partially fused grains of quartz, zircon, apatite, and titanite. Electron microprobe analyses of the glass show significant compositional variation that is probably strongly influenced by micrometer-scale changes in mineralogy. UV-Iaser ablation ICP-MS traverses across the mylonitic gneiss-pseudotachylyte contact are consistent with cataclastic communition of REE carriers such as epidote, monazite, allanite, zircon, and apatite before melting as an efficient mechanism of REE homogenization in the pseudotachylyte. The 40Ar/39Ar data from one band of pseudotachylyte indicate formation at 20.1 +/- 0.5 Ma, when the mylonitic gneisses were already in a near surface position. The variable effects of top-to-the-west shear deformation within outcrops of the coesite-bearing unit are reflected in localized zones of protomylonite, cataclasite, ultracataclasite, and pseudotachylyte. Preservation of several generations of pseudotachylyte suggests that seismic events may have played a significant role in triggering late unroofing of the UHP rocks. It is speculated that deeper crustal seismic events potentially played a role in the unroofing of the UHP rocks at earlier stages in their exhumation history. (c) 2005 Elsevier B.V. All rights reserved.

Electrical Conductivity and Chemical Composition of Soil Solution: Comparison of Solution Samplers in Tropical Soils

ABSTRACT Soil solution samplers may have the same working principle, but they differ in relation to chemical and physical characteristics, cost and handling, and these aspects exert influence on the chemical composition of the soil solution obtained. This study was carried out to evaluate, over time, the chemical composition of solutions extracted by Suolo Acqua, with the hydrophilic membrane (HM) as a standard, using soils with contrasting characteristics, and to determine the relationship between electrical conductivity (EC) and concentration of ions and pH of soil solution samples. This study was carried out under laboratory conditions, using three soils samples with different clay and organic matter (OM) contents. Soil solution contents of F−, Cl−, NO−3, Br−, SO42−, Na+, NH4+, K+, Mg2+, Ca2+, were analyzed, as well as inorganic, organic, and total C contents, pH, and EC, in four successive sampling times. Soil solution chemical composition extracted by the Suolo Acqua sampler is similar to that collected by the HM, but the Suolo Acqua extracted more Na+ and soluble organic C than the HM solution. Solution EC, cation and anion concentrations, and soluble C levels are higher in the soil with greater clay and OM contents (Latossolo and Cambissolo in this case). Soil solution composition varied over time, with considerable changes in pH, EC, and nutrient concentrations, especially associated with soil OM. Thus, single and isolated sampling of the soil solution must be avoided, otherwise composition of the soil solution may not be correctly evaluated. Soil solution EC was regulated by pH, as well as the sum of cation and anion concentrations, and the C contents determined in the soil liquid phase.

Concrete Pavement Mixture Design and Analysis (MDA): Application of a Portable X-Ray Fluorescence Technique to Assess Concrete Mix Proportions , TPF-5(205), 2012

Any transportation infrastructure system is inherently concerned with durability and performance issues. The proportioning and uniformity control of concrete mixtures are critical factors that directly affect the longevity and performance of the portland cement concrete pavement systems. At present, the only means available to monitor mix proportions of any given batch are to track batch tickets created at the batch plant. However, this does not take into account potential errors in loading materials into storage silos, calibration errors, and addition of water after dispatch. Therefore, there is a need for a rapid, cost-effective, and reliable field test that estimates the proportions of as-delivered concrete mixtures. In addition, performance based specifications will be more easily implemented if there is a way to readily demonstrate whether any given batch is similar to the proportions already accepted based on laboratory performance testing. The goal of the present research project is to investigate the potential use of a portable x-ray fluorescence (XRF) technique to assess the proportions of concrete mixtures as they are delivered. Tests were conducted on the raw materials, paste and mortar samples using a portable XRF device. There is a reasonable correlation between the actual and calculated mix proportions of the paste samples, but data on mortar samples was less reliable.