[EN] An integrated methodology incorporating preliminary archaeometric studies, design and performance of conservative and preventive treatments, as well as the design of an expositive support for a Montefortino helmet conserved at the Museum of Requena (Valencia, Spain), is presented. It was a bronze helmet dated back at the 3rd century B.C., providing from a terrestrial archaeological context showing intense degradation caused by cyclic corrosion associated to cuprous chlorides known as "bronze disease". The object showed advanced intergranular corrosion with deep attack of nantokite and minerals of the atacamite family, giving rise to an important structural fragility. The singularity of the object either in regard to its historic and documental value as well as in regard to its problems of mechanical and physico-chemical deterioration, have been faced from an interdisciplinary perspective around three specific aspects: i) the archaeometric study, focused on the characterization of the mechanical and physico-chemical deterioration using radiographic and analytic techniques, mainly, Optical Microscopy (OM), Scanning Electron Microscopy (SEM/EDX), X-ray Fluorescence Spectrometry (XRF) and Volammetry of Microparticles (VMP); ii) structural study on the mechanical resistance of the helmet using digital modeling techniques; iii) application of chemical decloruration conservative treatments accompanied by the study of expositive systems, including the design of a specific support. The monitoring of the conservation state of the object was carried out by means of climatic control and analytical examination after seven years of Museum exposition, showing that the helmet still maintains an acceptable level of mechanical and physico-chemical stability. / [ES] Se desarrolla una metodología integrada que atiende a los estudios arqueométricos previos, el diseño y ejecución de tratamientos conservativos y preventivos, así como el diseño del soporte expositivo de un Casco Montefortino conservado en el Museo de Requena (Valencia). Se trata de un casco de bronce de en torno a la mitad del siglo III a.C., procedente de un contexto arqueológico terrestre y que presentaba un proceso de degradación avanzado a causa de la corrosión cíclica producida por los cloruros cuprosos conocida como "enfermedad del bronce", habiéndose detectado una corrosión intergranular avanzada con ataques profundos de nantokita y minerales del grupo de la atacamita dando lugar, como consecuencia, a una fragilidad estructural importante. Tanto la singularidad de la pieza en cuanto a su valor histórico y documental, como el interés derivado de sus problemas de deterioro mecánico y químico, se han abordado desde una perspectiva interdisciplinar en torno a tres ámbitos específicos: i) el estudio arqueométrico, centrado en la caracterización de los deterioros físico-químicos y estructurales mediante técnicas radiográficas y analíticas, incorporando Microscopía Óptica (MO), Microscopía Electrónica de Barrido (SEM/EDX), Espectrometría por Fluorescencia de rayos X y Voltamperometría de Micropartículas (VMP); ii) el estudio estructural mediante técnicas de modelización digital sobre la resistencia mecánica del casco; iii) la aplicación de tratamientos conservativos de decloruración química acompañados del estudio de sistemas expositivos incluyendo el diseño de un soporte específico. Se ha procedido igualmente a un seguimiento de la pieza en exposición mediante control climático y examen analítico tras siete años de exposición, evidenciando que el Casco continúa manteniendo unos niveles de estabilidad físico-químicos y estructurales aceptables / [CA] Es presenta una metodologia integrada atenent als estudis arqueomètrics previs, el disseny i realització de tractaments conservatius i preventius així com el disseny d'un suport expositiu d'un Casc Montefortí conservat al Museu de Requena (València). Es tracta d'un casc de bronze datat al voltant de la meitat del segle III a.C., provinent d'un context arqueològic terrestre i que mostrava un procés de degradació avançat a causa de la corrosió cíclica produïda pels clorurs cuprosos coneguda com "malaltia del bronze", havent-se detectat una corrosió inter-granular avançada amb atacs profunds de nantokita i minerals del grup de l'atacamita donant lloc, com a conseqüència, a una fragilitat estructural important. Tant la singularitat de la peça en quant al seu valor històric i documental, com l'interès derivat dels seus problemes de deteriorament mecànic i químic, se han abordat des d'una perspectiva inter-disciplinar al voltant de tres àmbits específics: i) l'estudi arqueomètric, centrat en la caracterització dels deterioraments físic-químics i estructurals mitjançant tècniques radiogràfiques i analítiques, tot i incorporant Microscòpia Òptica (MO), Microscòpia Electrònica de Escombrat (SEM/EDX), Espectrometria per Fluorescència de raigs X i Voltamperometria de Micropartícules (VMP); ii) l'estudi estructural mitjançant tècniques de modelització digital sobre la resistència mecànica del casc; iii) l'aplicació de tractaments conservatius de de-cloruració química acompanyats de l'estudi de sistemes expositius incloent el disseny d'un suport específic. S'ha procedit igualment a un seguiment de la peça en exposició mitjançant control climàtic i examen analític rere set anys de exposició, evidenciant que el Casc continua mantenint uns nivells d'estabilitat fisico-química i estructural acceptables. / Martínez Lazaro, ID. (2016). Estudios integrados de procesos analíticos y conservativos de bronce arqueológico. Aplicación a un casco montefortino y otros materiales afines [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/61456

Magma which intrudes into carbonate rich crust, interacts with the carbonate in several ways, for example by contact metamorphism and formation of marble or by metasomatism resulting in calc-silicate skarn. These processes release volatiles, such as CO2, from the carbonate and might thus cause climate change. One volcanic complex where the intrusions and their surrounding metamorphic aureole are well exposed and therefore convenient for investigation of magma-carbonate interaction is the Carlingford Igneous Centre in NE of Ireland. The complex is dominated by a gabbro lopolith and a microgranite ring dyke, which intruded into limestone and meta-siltstone at around 62-60 Ma. The purpose of this study is to investigate the extent of magma-carbonate interaction and assess the amount of CO2 which could have been released from the aureole at Carlingford. This is done by analysing major and trace elements as well as carbon and sulphur content in skarn and marble samples from a transect along the calc-silicate metamorphic aureole. The analytical methods used are SEM- EDX, XRF, LA-ICP-MS and carbon and sulphur analyses. The CO2 release is calculated by comparing the carbon and CO2 content in the skarn and marble samples with that in the unmetamorphosed limestone. The results show that the skarn has experienced a strong interaction with the magma, as it contains several high-grade minerals, such as wollastonite, vesuvianite and pyrope, and has lost almost all its carbon. The extent of interaction and amount of CO2 release is generally much lower in the marble, even though a few marble samples show a strong interaction and a high degree of degassing. On the other hand, the amount of marble in the aureole turns out to be significantly higher than the amount of skarn (70-90% compared to 10-30%). The total mass of CO2 release from the calc-silicate aureole is calculated to 0.64-9.06 Gt, where 1.30-2.67 Gt being the most realistic amount. This released CO2 has probably not caused any significant climate change on its own but may have had a small contribution to global warming together with other volcanoes that were active during the same period of time. / Magma som tränger in i karbonatrik jordskorpa, integrerar med karbonaten på flera olika sätt, t.ex. genom kontaktmetamorfos och bildande av marmor eller genom metasomatos, vilket resulterar i kalk-silikatisk skarn. Dessa processer släpper ut flyktiga ämnen, som exempelvis CO2, från karbonaten och kan därmed orsaka klimatförändring. Ett vulkaniskt komplex där intrusioner och deras omgivande metamorfa aureoler är välexponerade och därmed lämpliga för undersökning av magma-karbonat-interaktion är Carlingford Igneous Centre i nordöstra Irland. Komplexet domineras av en gabbro-lopolit och en mikrogranitisk ring-gång, som trängde in i kalksten och metasiltsten för ca 62-60 Ma. Syftet med studien är att undersöka graden av magma-karbonat-interaktion och bedöma mängden CO2 som kan ha släppts ut från aureolen i Carlingford. Detta utförs genom analysering av huvudelement och spårelement samt av kol- och svavelinnehåll i skarn- och marmorprover från en transekt genom den kalk-silikatiska metamorfa aureolen. De analytiska metoder som används är SEM-EDX, XRF, LA-ICP- MS samt kol- och svavelanalyser. Mängden CO2 beräknas genom att jämföra kol- och CO2-innehåll i skarn- och marmorprover med innehållet kol och CO2 i den ickemetamorfa kalkstenen. Resultaten visar att skarn har genomgått en stark interaktion med magman, då bergarten innehåller flera mineral av hög metamorf grad, som exempelvis wollastonit, vesuvianit och pyrop, samt har förlorat nästan allt sitt kol. Graden interaktion och mängden CO2-utsläpp är generellt mycket lägre i marmorn än i skarnen, även fast några marmorprover visar stark interaktion och en stor del avgasning. Å andra sidan är mängden marmor i aureolen signifikant högre än mängden skarn (70-90% jämfört med 10-30%). Den totala massan av CO2-utsläpp från den kalk-silikatiska delen av aureolen är beräknad till 0,64-9,06 Gt, där 1,30-2,67 Gt anses vara den mest realistiska mängden. Detta utsläpp av CO2 har troligtvis inte orsakat någon signifikant klimatpåverkan på egen hand, men kan ha haft en liten bidragande effekt till global uppvärmning tillsammans med andra vulkaner som var aktiva under samma geologiska tidsperiod.

L'atmosphère terrestre est le siège d'un transport de matière, en particulier d'éléments d'origines diverses, dont une proportion importante résulte des activités humaines. Ce phénomène induit des conséquences parfois graves, pour la santé humaine et pour la fonctionnalité des écosystèmes. Les éléments ainsi transférés sont redéposés, de manière complexe, à la surface de la terre, avec une cartographie de distribution très inégale, des possibilités d'accumulation, ou au contraire de dilution, variables, conduisant à des altérations diversifiées de la composition des eaux et des sols et de la fonctionnalité des êtres vivants. La redéposition atmosphérique est étudiée depuis une cinquantaine d'année sur les troncs des arbres, qui constituent une matrice verticale commune, très enrichie par l'apport atmosphérique, et pouvant mener soit à une analyse de composition, soit à des études de bioindication. Il en a découlé des tests de routine largement utilisés. Cependant, pour définir avec précision les apports d'origine anthropique et mieux maîtriser, en vue de les réduire, les apports anormaux ou dangereux, une étude en profondeur de cette déposition corticale devait être entreprise. C'est l'objet de ce mémoire. Au regard de la complexité du problème abordé, nous nous sommes essentiellement limité à l'étude d'une seule espèce d'arbre : Fraxinus excelsior L., très commun dans notre zone d'étude et couvrant une vaste échelle d'altitude. Notre démarche analytique a consisté à combiner une analyse élémentaire très complète et sensible, l'ICP-MS avec une observation en microscopie à balayage couplée à la détermination de l'émission de rayons X spécifique des éléments présents. Cet ensemble de deux méthodes a permis de combiner identification - dosage précis - localisation - distinction entre états particulaire et dispersé. La déposition atmosphérique a été considérée sur une échelle de temps allant de 3 mois à 40 ans, en séparant les pousses successives des arbres. Nous avons séparé le dépôt superficiel sur les surfaces végétales d'une fraction solidement intégrée dans les tissus des tiges, spécialement le suber. Ces deux entités ne correspondent pas à la même chronologie. Nous avons montré que le dépôt de surface était, de fait, un écosystème construit sur un biotope alimenté conjointement par l'atmosphère et par l'arbre lui-même et qu'il comportait une phase vivante reviviscente et pour partie photosynthétique. Ce dépôt superficiel est déplacé en grande partie par la pluie. Le suber, couche apoplastique imperméable, a une bonne capacité de rétention des éléments à long terme et constitue, comparativement aux autres tissus des tiges, une matrice très intéressante pour percevoir l'apport atmosphérique sur plusieurs décennies. Pour déterminer valablement les apports atmosphériques d'origine anthropique qui s'accumulaient dans ces deux types de matrices, nous avons conçu un système de calcul (AAEF) permettant de les séparer des apports géogéniques et biologiques. Par ailleurs, constatant que l'apport atmosphérique comportait deux types de constituants, soit dispersés, soit particulaires, nous avons conçu et mis en oeuvre un protocole de fractionnement basé 1) sur l'incinération, 2) sur les traitements successifs à l'eau et à l'acide nitrique concentré (2N) qui nous a permis d'étudier isolément une phase particulaire dans laquelle la masse des matériaux géogéniques se trouve rassemblée avec l'essentiel du plomb et du manganèse, la phase HNO3 concentrant les éléments comme le cuivre et le zinc et une phase H2O contenant l'essentiel du potassium. Les profils de distribution entre les différentes fractions semblent constituer une information intéressante sur la spéciation de plusieurs types d'éléments. L'ensemble du corpus méthodologique ainsi édifié permet d'accéder à des études assez réalistes d'historique et de distribution géographique des polluants élémentaires à des échelles de distances variées.

The focus of this study was analytical investigations of Egyptian paintings, mainly Coptic icons and Islamic wooden ceilings, dating from 1300-1900 using multi-instrumental techniques. Twenty three Coptic icons and three wooden ceilings dated from different periods and painted by different painters in case of icons were examined. The materials used including pigments, media, varnishes, ground layers and gold layers. The surface stratigraphy of paint samples, their layered structured and the composition of materials used in each layer were analysed. Variations in painting techniques, pigments palettes, paint media and varnishes applied in Egyptian paintings according to painters, time and type of paintings were revealed. A total of twenty-eight organic and inorganic pigments were identified in this study, of which nine have never been previously included as a part of the Egyptian pigment palettes, namely; smalt, lapis lazuli, indigo, pararealgar, Prussian blue, chrome yellow, barium yellow, barium white and hydromagnesite. The identification of hydromagnesite, which has never been to date considered as a pigment either in Egypt or elsewhere and the identification of smalt from the mid-14th century, whose reported earliest large scale use was in the 16th century. Two types of resins were identified as a constituent of the oil/resin varnish applied on Coptic icons of which Venice turpentine has been identified for the first time as an ingredient of Egyptian varnishes. The identification of mosaic gold in an 18th C. icon, a novel usage of dammar resin and the multilayered structure of the white ground layers were revealed.

No description available.

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.

The thermal formation of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), and naphthalenes (PCNs) is a major problem in waste incineration. Ideally, rather than relying on air cleaning systems and treatment techniques, their formation should be minimized or, if possible eliminated. The work presented in this thesis was conducted to obtain a deeper understanding of the thermal formation of PCDDs, PCDFs, PCBs, and PCNs during incineration using a 5 kW laboratory scale incinerator and two artificial wastes that were designed to reflect regional differences in waste composition. The first part of the thesis focuses on the validation of a recently-developed flue-gas sampling probe with enhanced cooling capabilities. Artifact formation of PCDDs and PCDFs can occur during the sampling of hot flue gases if the cooling is insufficient. The new probe was successfully used to collect samples at 700 °C without biasing the measured POP levels. The thermal formation of PCDDs, PCDFs, PCBs, and PCNs in the post-combustion zone of the incinerator was then studied by collecting flue gas samples at 400 °C, 300 °C, and 200 °C during the incineration of the two artificial wastes. Highly chlorinated POPs were formed in larger quantities when burning the waste with the higher content of metals and chlorine, which suggests that high metal levels in the waste favor the chlorination of less chlorinated POPs or otherwise facilitate the formation of highly chlorinated polyaromatics, possibly via the condensation of highly chlorinated phenols. The concentrations of these pollutants and the abundance of highly chlorinated homologues increased as the flue gas cooled. Fly ash particles play an important role in thermal POP formation by providing essential elements (carbon, chlorine, etc.) and catalytic sites. The chemical and mineralogical properties of fly ash samples were studied by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), Scanning Electron Microscopy/Energy Dispersive X-ray (SEM/EDX), and X-ray photoelectron spectroscopy (XPS) to determine their impact on thermal POP formation. Orthogonal Partial Least Squares (OPLS) modeling was used to identify correlations between the observed POP distributions and the physicochemical data. This investigation provided new insights into the impact of fly ash chemistry on thermal POP formation. In addition, the POP isomer distribution patterns generated during waste combustion were examined. These patterns are used to “fingerprint” mechanisms of POP formation. It was found that wastes containing large quantities of metals and chlorine favored the formation of highly chlorinated homologues including the very toxic 2,3,7,8-congeners. The data suggest that reducing fly ash emissions might increase the SO2 content of the flue gas and thereby suppress the Deacon process and the formation of harmful highly chlorinated aromatic species.

Iron-tannate dyes have been used for thousands of years and on many continents to colour materials that are now part of our cultural heritage shades of black, grey, or brown. Cellulosic and proteinaceous yarns and woven textiles have been dyed with iron-tannate dyes to form objects or components of objects for domestic and ceremonial use. Unfortunately, the longevity and useful lifetime of iron-tannate dyed objects is threatened by the dye itself which accelerates the degradation of organic materials through metal-catalysed oxidation and acid-catalysed hydrolysis. The accelerated degradation causes weakening, discolouration, and embrittlement of the organic materials at a faster rate than undyed equivalents and if left unimpeded, weakens the objects to the point that they are no longer able to be exhibited without damage. In some cases the degradation is so great that the dyed areas of the objects have crumbled to dust. At present there is no suitable chemical stabilisation method available with which to inhibit this degradation. An aqueous treatment is available for successfully stabilising paper containing iron gall ink; iron gall ink is chemically similar to iron-tannate dye. However, the aqueous nature of this treatment makes it unsuitable for weakened fibres, water soluble components, and water sensitive materials which may be part of a composite material containing iron-tannate dye. Non-aqueous treatments are therefore urgently needed in order to preserve our iron-tannate dyed cultural heritage for future generations.In this project a range of non-aqueous antioxidants and a non-aqueous deacidifier (described in Chapter 8) were tested alongside existing aqueous treatment in order to establish their ability to slow down the degradation of a range of model iron-tannate dyed textiles (Chapters 9 and 10). Model textiles were developed as part of the project (Chapters 3-5) to be substitutes for historic materials in these stabilisation studies. Validation of the model textiles for this purpose (Chapter 6) involved the comparison of the model textiles with selected historic iron-tannate dyed objects within the British Museum’s collection (Chapter 6). The historic objects and the properties of the model textiles before and after accelerated ageing (Chapters 5 and 6) and before and after treatment application (Chapters 9 and 10) have been characterised using a variety of analytical techniques (Chapter 2). In order to determine which accelerated ageing conditions were the most suitable for this project various combinations of elevated temperature and either cycling or stable relative humidity were tested for their ability to produce noticeable changes in the properties of the dyed model textiles within four weeks of ageing (Chapter 7). This project is an AHRC/EPSRC funded Science and Heritage Programme PhD in which the British Museum has been a collaborative institution. Among other wider dissemination methods, research from this project has been presented to the public on numerous occasions at gallery tours and Science Day events at the British Museum.

Apis mellifera Linnaeus (1758) è un insetto eusociale conosciuto in tutto il mondo sia per la produzione di miele sia per il suo ruolo di impollinatore, uno dei servizi ecosistemici fondamentali per la biodiversità del pianeta. Durante la sua attività di foraggiamento, l’ape è esposta agli inquinanti ambientali tra cui il particolato atmosferico aerodisperso (PM). Il particolato atmosferico può depositarsi sul corpo dell’insetto e infine contaminare anche i prodotti apistici come polline e miele. Il PM può avere diverse dimensioni (es. PM10, PM2.5, PM0.1), composizione chimica, morfologia e fonti di emissione (naturale o antropica). Nel presente elaborato di tesi, tecniche di microscopia elettronica a scansione (SEM-EDX) sono state utilizzate per caratterizzare la contaminazione da PM di origine antropica del corpo dell’ape e dei suoi prodotti (Capitolo 2 e Capitolo 3) e analisi molecolari per studiare gli eventuali effetti sub-letali sul microbiota intestinale di api esposte ai PM per via orale (Capitolo 4). / Apis mellifera Linnaeus (1758) order Hymenoptera family Apidae, is a eusocial insect widely known for its role in pollination, a fundamental ecosystem service for plant biodiversity and ultimately for the planet. During flight and foraging activity, the honey bee can collect airborne particulate matter (PM) on their own body, especially on the forewings, and can also contaminate bee products as pollen and honey. Particulate matter can originate from natural or anthropic sources, and is characterised by size (e.g., PM10, PM2.5, PM0.1), chemical composition, and morphology. In this thesis, honey bee, pollen and honey were used as bioindicator of PM – from coarse to ultrafine – in industrial areas of the Po Valley, Italy (Chapter 2 and Chapter 3). The (sub-lethal) effects of Titanium dioxide – a widespread airborne PM1 pollutant – on the honey bee through oral exposure was then investigated (Chapter 4). The technique used to analyse the PM contaminating bees and bee products is the scanning electron microscopy (SEM) coupled with X-ray spectrometer (EDX). EDX spectra allowed us to obtain chemical information from specimens, while backscattered-electron (BSE) imaging and elemental mapping provided both compositional and topographic information of PM.

The focus of this study was analytical investigations of Egyptian paintings, mainly Coptic icons and Islamic wooden ceilings, dating from 1300-1900 using multiinstrumental techniques. Twenty three Coptic icons and three wooden ceilings dated from different periods and painted by different painters in case of icons were examined. The materials used including pigments, media, varnishes, ground layers and gold layers. The surface stratigraphy of paint samples, their layered structured and the composition of materials used in each layer were analysed. Variations in painting techniques, pigments palettes, paint media and varnishes applied in Egyptian paintings according to painters, time and type of paintings were revealed. A total of twenty-eight organic and inorganic pigments were identified in this study, of which nine have never been previously included as a part of the Egyptian pigment palettes, namely; smalt, lapis lazuli, indigo, pararealgar, Prussian blue, chrome yellow, barium yellow, barium white and hydromagnesite. The identification of hydromagnesite, which has never been to date considered as a pigment either in Egypt or elsewhere and the identification of smalt from the mid-14th century, whose reported earliest large scale use was in the 16th century. Two types of resins were identified as a constituent of the oil/resin varnish applied on Coptic icons of which Venice turpentine has been identified for the first time as an ingredient of Egyptian varnishes. The identification of mosaic gold in an 18th C. icon, a novel usage of dammar resin and the multilayered structure of the white ground layers were revealed. / Egyptian Ministry of Higher Educations