Le graphène est un matériau très intéressant grâce à ses excellentes propriétés optiques, électriques et mécaniques. Parmi les méthodes de synthèse du graphène monocouche, la croissance par le dépôt chimique en phase vapeur (CVD) sur un métal est des plus efficaces et économiques pour assurer une production industrielle. Cette méthode demande toutefois une étape de transfert du graphène à partir du substrat catalytique de la croissance (généralement du cuivre) vers le substrat désiré. Plusieurs méthodes permettent d’effectuer ce transfert et les plus répandues impliquent généralement l’usage d’un polymère, car il présente des avantages intéressants, comme la simplicité et le faible coût, mais également des désavantages liés à l’introduction de défauts ou de résidus organiques sur la surface du graphène transféré. Pour conserver la qualité et les propriétés du graphène après le processus de transfert, nous avons travaillé à développer une méthode qui vise à éliminer les désavantages du transfert avec un polymère tout en permettant un transfert simple et propre de graphène sans défaut. La méthode retenue utilise un film d’or comme support pour faciliter le transfert du graphène sur gaufre de silicium. Pour augmenter l’adhésion à la gaufre de silicium, il a été nécessaire d’introduire une étape de recuit des échantillons de graphène après le transfert avec le film d’or. Le film d’or est ensuite enlevé par la gravure chimique humide, en utilisant une solution aqueuse d’iode et d’iodure de potassium, ce qui permet de produire une monocouche de graphène sur de grandes dimensions. Après une optimisation du processus complet, nos résultats du graphène transféré sur substrat de silice présentent peu des défauts selon les mesures Raman et l’absence des résidus organiques sur la surface par la topographie AFM. / Graphene is an interesting material thanks to its excellent optical, electrical and mechanical properties. Among the methods for synthesizing high quality monolayer graphene, growth by chemical vapor deposition (CVD) on a metal is one of the most effective and economical for industrial production. However, this method requires a step to transfer graphene from the growth catalytic substrate (generally copper) to the desired substrate. Several methods allow this transfer to be carried out and the most widespread methods generally involve the use of a polymer. The main advantages are simplicity and low cost. However, there are also disadvantages related to the introduction of defects or organic residue on the surface of the transferred graphene. To maintain the quality and properties of graphene after the transfer process, we have developed a method aimed at eliminating the disadvantages of a transfer with polymer. The developed method uses a gold film as a support to facilitate the transfer of graphene onto a silicon wafer. It is a simple way to produce defect-free graphene. To increase the adhesion to the silicon wafer, it was necessary to introduce a step of annealing the graphene samples after the transfer with the gold film. The gold film was then removed by wet chemical etching with an aqueous solution of iodine and potassium iodide, which makes it possible to produce a monolayer of graphene over large dimensions. After optimizing the entire process, our results of graphene transferred on silicon substrate show few defects based on Raman measurements and the absence of organic residues on the surface by AFM topography.

No / RATIONALE: The carbon isotopic characterisation of ruminant lipids associated with ceramic vessels has been crucial for elucidating the origins and changing nature of pastoral economies. delta(13)C values of fatty acids extracted from potsherds are commonly compared with those from the dairy and carcass fats of modern domesticated animals to determine vessel use. However, the processing of wild ruminant products in pottery, such as deer, is rarely considered despite the presence of several different species on many prehistoric sites. To address this issue, the carbon isotope range of fatty acids from a number of red deer (Cervus elaphus) tissues, a species commonly encountered in the European archaeological record, was investigated. METHODS: Lipids were extracted from 10 modern red deer tissues obtained from the Slowinski National Park (Poland). Fatty acids were fractionated, methylated and analysed by gas chromatography/combustion/isotope ratio mass spectrometry (GCCIRMS). The delta(13)C values of n-octadecanoic acid and n-hexadecanoic acid, and the difference between these values (Delta(13)C), were compared with those from previously published ruminant fats. RESULTS: Nine of the ten deer carcass fats measured have Delta(13)C values of less than -3.3 per thousand, the threshold previously used for classifying dairy products. Despite considerable overlap, dairy fats from domesticated ruminants with Delta(13)C values less than -4.3 per thousand are still distinguishable. CONCLUSIONS: The finding has implications for evaluating pottery use and early pastoralism. The processing of deer tissues and our revised criteria should be considered, especially where there is other archaeological evidence for their consumption.

No / Foodcrusts, the charred surface deposits on pottery vessel surfaces, provide a rich source of data regarding container function. This article reviews recent applications focusing on the detection of aquatic resources (marine and freshwater) in pottery vessels using a range of analytical approaches including bulk isotope measurements of carbon and nitrogen, lipid biomarker analysis, and compound-specific carbon isotope determinations. Such data can help to evaluate the presence of reservoir effects when undertaking radiocarbon dating of foodcrust samples. In particular, molecular and isotopic analysis can aid in the selection of suitable candidates for C-14 where it can be demonstrated that aquatic resources are unlikely to contribute to the residue. Prospects for compound-specific C-14 analysis of lipids in foodcrusts and ceramic-absorbed residues are also discussed.

Yes / Transport and storage vessels in Red Lustrous Wheelmade ware (RLWm ware) were traded across a large area of the eastern Mediterranean for approximately 300 years (c. 1500–1200 BCE) during the Late Bronze Age (c.1600–1000 BCE). The extreme consistency of the ceramic, in form, fabric, chemistry and mineralogy, points to a single production source for the ware, which, although no kiln sites have been identified, is generally accepted to have been on Cyprus. The aim of this study was to determine whether organic residues were present in this very fine, dense ware, and to characterise the contents of RLWm ware vessels from different sites, contexts and periods, and of different forms, to improve our understanding of the trade in this ceramic type. To that end, 101 RLWm ware sherds, together with three visible residues, were examined from sites in Turkey, Cyprus, Egypt and Syria. Residues were identified in more than half of the samples, indicating that organic material is absorbed into and preserved in this very fine fabric. Four commodities were identified: fat (probably plant oil), which in four residues was identified further as castor oil; beeswax; bitumen; and Pinaceae spp. resin. The commodities were found alone or, occasionally, one of the latter three was combined with the fat or oil. Fatty material was the only commodity present at all sites and its wide distribution may indicate that generally the vessels were used for a mixture or mixtures based on plant oils, in some cases containing castor oil. It was impossible to determine whether the beeswax, bitumen and resin formed part of this mixture or represented post-firing treatments of the ceramic to make it less porous. The identification of more than one type of residue indicates that RLWm ware vessels did not always contain the same commodity. No significant correlation could be detected between the vessel forms, and the dating of many of the sherds was not precise enough to reveal any variation through time. The type of residue present did vary depending on the geographical location of its final use. Beeswax was, with two exceptions, only present in samples from Turkey, while bitumen was found exclusively in samples from Cypriot sites. The occurrence of at least one example of every commodity in the samples from Cyprus is consistent with the theory that this ware was manufactured on Cyprus, and indicates that the vessels could also have been filled and exported from there. The variation in content of the vessels found in different geographical areas could highlight a special trading relationship between the Hittite heartland in Turkey and the Cypriot potters who produced the ware, and a possible trade in bitumen as a raw material between the north Syrian coastal area of Ugarit and Cyprus. / This research was funded by an AHRC PhD studentship (number 110786), awarded to V. Steele.

Red Lustrous Wheelmade Ware (RLWm ware) transport and storage vessels have been excavated from Late Bronze Age (LBA) sites across the eastern Mediterranean. These distinctive vessels were traded for the valuable commodity they contained so far unidentified. Seventy-three sherds (61 RLWm ware, 12 in local fabrics) and two visible residues were analysed for organic residues using standard lipid extraction techniques. Seven residues from a previous study were re-examined. Gas chromatography-mass spectrometry identified four materials - beeswax, bitumen, fat/oil and resin. Beeswax, found only in vessels from Hittite sites in Turkey, was probably used as a post-firing treatment. Fat/oil, present in some sherds from every site, represents the contents of the vessels and showed many of the characteristics of degraded plant oil. Two examples contained a plant sterol and three yielded ricinoleic acid, a biomarker for castor oil. Gas-chromatography compound-specific isotope ratio mass spectrometry of selected residues excluded dairy products, ruminant animal fats and fish oils as source materials for the fats/oils, while comparison with a small database of modern oils created during this study does not exclude plant oils. Selected samples analysed by high performance liquid chromatography-tandem mass spectrometry did not reveal wine residues. Data on the elemental composition of the fabric collected during another study was re-analysed and compared with data from a further published study, confirming the remarkable consistency of RLWm ware fabric. Volume calculations were also attempted to give an estimate of the capacity of the main vessel forms.

Emission of greenhouse effect gases due to the agricultural use of the dejections of animals as fertilizers, as well as the mineralization of the carbon of those materials in the soil healthy aspects are still relatively a little studied in Brazil. This work was accomplished to evaluate: 1) the annual emission of nitrous oxide with the use, in the corn, of mineral and organic manuring (pig and cattle slurry and pig deep-bedding); 2) the mineralization of the carbon of pig slurry and of the corn straw, with and without incorporation to the soil. For that two experiments were driven in field conditions, in the period of October of 2007 to September of 2008, in the experimental area of the Departamento de Solos da Universidade Federal de Santa Maria (UFSM) in typic Hapludalf soil. In the first, it was evaluated the emission of N2O periodically for 342 days in the following treatments: T1: without dejections (control); T2: pig slurry in single application; T3: pig deep-bedding; T4: pig deep-bedding + urea; T5: cattle slurry; T6: pig slurry in parceled out application; T7: without slurry and with mineral fertilizer (NPK) recommended to the corn. Approximately 2/3 of the annual emission of N2O happened during the first 15 days after the application of the organic materials, and all of them provoked increase in the emission of N2O in relation to the control treatment, without use of fertilizers and also in relation to the treatment with the use of N-urea. With the parceled out application of the pig slurry the emission of N2O was inferior to the single application. At the end of approximately one year the factor of emission of N2O in the treatments with application of organic residues varied of 2.1% of applied N with the cattle slurry to 3.4% of applied N with the pig slurry. In the second experiment the effect of the addition of pig slurry was evaluated on the decomposition of corn straw, with and without incorporation to the soil. For such, the continuous C-CO2 emission was quantified for a period of 158 days in the following treatments: T1: soil without mobilization, T2: mobilized soil, T3: pig slurry in soil surface, T4: pig slurry incorporated, T5: corn straw in surface, T6: incorporate straw, T7: straw + pig slurry in surface and T8: straw + incorporate pig slurry. The incorporation of the corn straw to the soil favored the C mineralization of the straw while in the pig slurry his maintenance in the soil surface favored the C mineralization. The application of pig slurry increased the mineralization straw C in surface in 12% (320 kg ha-1 of added C) and of the incorporate straw in 1.3% (34 kg ha-1 of added C). / A emissão de gases de efeito estufa decorrente do uso agrícola dos dejetos de animais como fertilizantes, bem como a mineralização do carbono desses materiais no solo são aspectos ainda relativamente pouco estudados no Brasil. Este trabalho foi realizado para avaliar: 1) a emissão anual de óxido nitroso com o uso, no milho, de adubação mineral e orgânica (dejetos líquidos de suínos e de bovinos e cama sobreposta de suínos); 2) a mineralização do carbono dos dejetos líquidos de suínos e da palha de milho, com e sem incorporação ao solo. Para isso foram conduzidos dois experimentos em condições de campo, no período de outubro de 2007 a setembro de 2008, na área experimental do Departamento de Solos da Universidade Federal de Santa Maria (UFSM) em um Argissolo Vermelho distrófico arênico. No primeiro, avaliou-se periodicamente a emissão de N2O durante 342 dias nos seguintes tratamentos: T1: sem dejetos (testemunha); T2: dejetos líquidos de suínos em aplicação única; T3: cama sobreposta de suínos; T4: cama sobreposta + uréia; T5: dejetos líquidos de bovinos; T6: dejetos líquidos de suínos em aplicação parcelada; T7: sem dejetos e com adubação mineral (NPK) recomendada ao milho. Aproximadamente 2/3 da emissão anual de N2O ocorreu durante os primeiros 15 dias após a aplicação dos materiais orgânicos, sendo que todos eles provocaram aumento na emissão de N2O em relação ao tratamento testemunha, sem uso de fertilizantes e também em relação ao tratamento com o uso de N-uréia. Com a aplicação parcelada dos dejetos de suínos a emissão de N2O foi inferior à aplicação dos dejetos em dose única. Ao final de aproximadamente um ano o fator de emissão de N2O nos tratamentos com aplicação de resíduos orgânicos variou de 2,1 % do N aplicado com os dejetos líquidos de bovinos a 3,4 % do N aplicado com os dejetos líquidos de suínos. No segundo experimento foi avaliado o efeito da adição de dejetos sobre a decomposição de palha de milho, com e sem incorporação ao solo. Para tal, foi quantificada a emissão contínua de C-CO2 por um período de 158 dias nos seguintes tratamentos: T1: solo sem mobilização, T2: solo mobilizado, T3: dejetos líquidos de suínos em superfície, T4: dejetos incorporados, T5: palha de milho em superfície, T6: palha incorporada, T7: palha + dejetos em superfície e T8: palha + dejetos incorporados. A incorporação da palha de milho ao solo favoreceu a mineralização do C da palha enquanto nos dejetos de suínos a sua manutenção na superfície do solo favoreceu a mineralização do C. A aplicação de dejetos líquidos de suínos aumentou a mineralização do C da palha em superfície em 12% (320 kg ha-1 do C adicionado) e da palha incorporada em 1,3% (34 kg ha-1 do C adicionado).

No / Shallow oval bowls used on the Baltic coast in the Mesolithic have been suggested as oil lamps, burning animal fat. Here researchers confirm the use of four coastal examples as lamps burning blubber-the fat of marine animals, while an inland example burned fat from terrestrial mammals or freshwater aquatics-perhaps eels. The authors use a combination of lipid biomarker and bulk and single-compound carbon isotope analysis to indicate the origin of the residues in these vessels.

Red Lustrous Wheelmade Ware (RLWm ware) transport and storage vessels have been excavated from Late Bronze Age (LBA) sites across the eastern Mediterranean. These distinctive vessels were traded for the valuable commodity they contained so far unidentified. Seventy-three sherds (61 RLWm ware, 12 in local fabrics) and two visible residues were analysed for organic residues using standard lipid extraction techniques. Seven residues from a previous study were re-examined. Gas chromatography-mass spectrometry identified four materials ¿ beeswax, bitumen, fat/oil and resin. Beeswax, found only in vessels from Hittite sites in Turkey, was probably used as a post-firing treatment. Fat/oil, present in some sherds from every site, represents the contents of the vessels and showed many of the characteristics of degraded plant oil. Two examples contained a plant sterol and three yielded ricinoleic acid, a biomarker for castor oil. Gas-chromatography compound-specific isotope ratio mass spectrometry of selected residues excluded dairy products, ruminant animal fats and fish oils as source materials for the fats/oils, while comparison with a small database of modern oils created during this study does not exclude plant oils. Selected samples analysed by high performance liquid chromatography-tandem mass spectrometry did not reveal wine residues. Data on the elemental composition of the fabric collected during another study was re-analysed and compared with data from a further published study, confirming the remarkable consistency of RLWm ware fabric. Volume calculations were also attempted to give an estimate of the capacity of the main vessel forms. / Arts and Humanities Research Council / Extensive folders of data and appendices which accompany this thesis are not presently available online.

La Sardaigne, en raison de sa position géographique au cœur de la Méditerranée occidentale, constitue une zone clé pour la compréhension de la diffusion du Néolithique dans le domaine nord-tyrrhénien. La deuxième moitié du Ve millénaire cal BC marque l’essor et l’aboutissement du processus de diffusion de l’économie néolithique dans l’île, sous l’égide des groupes humains « San Ciriaco ». Des fouilles récentes dans la Sardaigne centre-occidentale, zone cruciale pour cette entité culturelle régionale, ont décelé des contextes inédits dont l’étude est fondamentale pour la connaissance de ces sociétés. Cette thèse se propose d’explorer le rôle des poteries dans les systèmes techniques et les comportements symboliques des groupes humains San Ciriaco en Sardaigne centre-occidentale, afin d’obtenir des indices économiques sur les stratégies de gestion des ressources et sur les modes de vie de ces populations. L’approche interdisciplinaire suivie combine l’analyse morphométrique des récipients, l’observation des traces d’usure et l’analyse chimique des résidus organiques (en CPG et CPG/SM) piégés dans la matrice céramique. Les résultats révèlent une structuration des assemblages céramiques en plusieurs gammes fonctionnelles, variablement représentées sur des sites à destination différente (habitat, sépultures, « dépôts » de vases). Des comportements techniques et symboliques liés à la gestion des récipients tout au long de leur cycle d’utilisation sont mis en lumière. Ces résultats offrent une première contribution à la plus large problématique de l’évolution de la fonction des poteries, tout au long du Néolithique, au sein du domaine méditerranéen occidental.zone cruciale pour cette entité culturelle régionale originale, ont décelé des contextes inédits dont l’étude s’avère être fondamentale pour la connaissance de ces sociétés. Cette thèse se propose d’explorer le rôle des poteries dans les systèmes techniques et les comportements symboliques des groupes humains San Ciriaco en Sardaigne centre-occidentale, afin d’obtenir des indices économiques sur les stratégies de gestion des ressources et sur les modes de vie de ces populations. L’approche interdisciplinaire suivie combine l’analyse morphométrique des récipients, l’observation des traces d’usure et l’analyse chimique des résidus organiques (en chromatographie en phase gazeuse et chromatographie en phase gazeuse couplée à la spectrométrie de masse), piégés dans la matrice céramique. Les résultats obtenus révèlent une structuration des assemblages céramiques en plusieurs gammes fonctionnelles distinctes et variablement représentées sur des sites à destination fonctionnelle différente (habitat, sépultures, « dépôts » de vases). Des comportements techniques et symboliques liés à la gestion des récipients tout au long de leur cycle d’utilisation sont également mis en lumière. Ces résultats offrent une première contribution à la plus large problématique de l’évolution de la fonction des poteries, tout au long du Néolithique, au sein du domaine méditerranéen occidental. / The isle of Sardinia (Italy) is a key zone in understanding the spread and the diffusion of the Neolithic in North Tyrrhenian region, due to its position in the middle of western Mediterranean Sea. Here, the rise and culmination of Neolithic economy is carried by San Ciriaco populations in the second half of V millennium cal BC. Recent archaeological excavations in central-western Sardinia revealed new contexts the study of which is fundamental in increasing our knowledge of these Neolithic societies.The aim of this work is to investigate the role of pottery in technical systems and symbolical behaviours of San Ciriaco societies in central-western Sardinia, in order to find evidence of strategies of use and explore their way(s) of life. The interdisciplinary approach in this study combines morphometrical analysis of vessels, use-wear observation and GC / GC-MS chemical analysis of organic residues absorbed in pottery.This research revealed a structuration of pottery assemblages into several functional categories which are differently represented in sites with a different function (settlements, burials, vessels “deposits”). The results contribute to highlight technical and symbolical behaviors linked to the use of pottery during its life cycle phases. These data offer a contribution to the issue of the evolution of pottery function during the Neolithic period in Western Mediterranean. / La Sardegna, in virtù della sua posizione centrale nel Mediterraneo occidentale, rappresenta una zona cruciale per la comprensione del processo di propagazione del Neolitico e della sua evoluzione nell’area nord-tirrenica. Il pieno sviluppo dell’economia neolitica nell’isola è segnato dalla formazione e diffusione di un’entità culturale regionale originale, denominata “cultura di San Ciriaco”, durante la seconda metà del V millennio cal BC (Neolitico Medio B). Alcuni recenti scavi nella Sardegna centro-occidentale, scenario fondamentale nello sviluppo di tale entità culturale, hanno portato alla luce dei contesti inediti, il cui studio si rivela essenziale per la conoscenza di queste società neolitiche.L’obiettivo di questa ricerca è specificamente quello di indagare il ruolo dei recipienti ceramici nei sistemi tecnici e nei comportamenti simbolici dei gruppi umani San Ciriaco della Sardegna centro-occidentale, nell’intento di acquisire degli indizi sulle strategie di gestione delle risorse naturali e sulle modalità di sussistenza delle popolazioni durante il Neolitico medio B.L’approccio interdisciplinare seguito associa l’analisi morfometrica dei recipienti all’osservazione delle tracce d’uso e all’analisi chimica dei residui organici assorbiti nella matrice ceramica, mediante la tecnica della gascromatografia (GC) e della gascromatografia/spettrometria di massa (GC/MS).I risultati ottenuti rivelano una strutturazione delle collezioni ceramiche in molteplici gamme funzionali distinte e variabilmente rappresentate in siti con destinazione funzionale differente (abitato, sepolture, “depositi” di recipienti). L’analisi di tali contesti ha permesso di evidenziare alcuni specifici comportamenti tecnici e simbolici legati alla gestione dei recipienti durante tutto il loro ciclo d’utilizzo.L’interpretazione storica dei dati acquisiti con questa ricerca offre un contributo alla più vasta questione dell’evoluzione della funzione dei recipienti ceramici, nel corso del Neolitico, nell’area del Mediterraneo occidentale.