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Mitt i Europas växande beroende av extern antimonproduktion har Europeiska kommissionen konsekvent betonat ett växande gap mellan utbud och efterfrågan sedan 2014. Som svar på denna utmaning riktade sig denna studie mot sekundära antimonkällor från underutnyttjade rester av guld, koppar och blymalm, som för närvarande utgör ett miljöproblem. Genom noggranna experiment, fastställde vi att optimal antimonurlakning uppnås vid 120 °C inom 2 timmar med en 250 g/L Na2S och 60 g/L NaOH-blandning. Detta tillvägagångssätt accentuerar selektiv extraktion, förbättrar antimonåtervinningen och minimerar kopparinterferens. En innovativ aspekt av denna studie var användandet utav mikrovågsassisterad urlakning, vilket visar fördelar i både utvinningseffektivitet och bevarande av mineralstrukturer jämfört med traditionella metoder. Våra resultat stöds av flera analytiska verktyg och ger en första förståelse, även om detaljerna kring mikrovågsassisterad urlakning och dess skalbarhet motiverar ytterligare utforskning. Denna studie introducerar en metod för urlakning av antimon från koppargruvavfall och föreslår ett motsvarande återvinningssystem som kan vara ekonomiskt lönsamt. Sådana ansträngningar kan ge ett blygsamt bidrag till att lindra den nuvarande situationen. / Amid Europe's growing reliance on external antimony production, the European Commission has consistently emphasized an expanding supply-demand gap since 2014. Responding to this challenge, our research targeted secondary antimony sources from underutilized residues of gold, copper, and lead ore processing, which currently pose environmental concerns. Through meticulous experimentation, we determined that optimal antimony leaching is achieved at 120°C within 2 hours, using a 250 g/L Na2S and 60 g/L NaOH mixture. This approach accentuates selective extraction, enhancing antimony recovery and minimizing copper interference. An innovative facet of this study was the adoption of microwave-assisted leaching, demonstrating advantages in both extraction efficiency and mineral structure conservation over traditional methods. Our results, backed by multiple analytical tools, provide an initial understanding, though areas like the specifics of microwave-assisted leaching and its scalability warrant further exploration. This study introduces a method for leaching antimony from copper mining waste and suggests a corresponding recycling system that may be economically viable. Such endeavors might offer a modest contribution to alleviating the present situation.

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Antimoine (Sb) et tellure (Te), sont des contaminants peu étudiés (isotopes stables) et leurs radionucléides artificiels peuvent être rejetés dans le milieu aquatique lors des accidents nucléaires. La connaissance de leurs comportements biogéochimiques respectifs est nécessaire à l'évaluation du risque radiologique post-accidentel.Ce travail présente des données originales sur le comportement biogéochimique de Sb et de Te dans les systèmes de transition continent-océan, tels que l'estuaire de la Gironde et la rivière du Rhône. Un suivi de 14 ans et des campagnes océanographiques dans le bassin versant de l’estuaire de la Gironde ont permis d’identifier des concentrations, des flux, et des réactivités (variabilités spatio-temporelles et distribution solide/liquide) plus élevés pour Sb que pour Te, mettant en évidence un comportement additif pour Sb et de soustraction pour Te le long des gradients de salinité et de turbidité estuariennes. Des expériences couplant l’adsorption d’isotopes marqués sur des matières en suspension (MES) et des extractions sélectives des phases porteuses, suggèrent que les formes apportées de Sb et de Te sont plus mobiles et potentiellement plus biodisponibles que leurs équivalents naturels. De plus, l’observation de la bioaccumulation non-négligeable de Sb et de Te naturels dans les huîtres sauvages à l’embouchure de l’estuaire permet d’envisager une absorption potentielle de leurs homologues radioactifs.Ainsi, le développement de scenarios de dispersion de radionucléides rejetés dans les zones de transition dépendra (i) de la position géographique de la source (Rhône) et/ou de la zone de turbidité maximale (ZTM; système fluvio-estuarien de Gironde), (ii) de la situation hydrologique pendant et post accident, ainsi que (iii) de la réactivité biogéochimique et des temps de demi-vies des radionucléides. Les premiers scénarios de dispersion de radionucléides dans l'estuaire de la Gironde suggèrent (i) un transport préférentiel de Sb dissous vers la zone côtière, et (ii) une forte rétention de Te radioactif dans la ZTM si la dernière est présente en aval du site d’accident, impliquant le risque de migration saisonnière de la radioactivité vers la ville de Bordeaux pendant l’étiage suivant. Ainsi, la dynamique intra estuarienne (marée, débit et migration de la ZTM) sera le facteur prédominant dans le devenir de Te radioactif, depuis son rejet jusqu’à sa désintégration complète en iode radioactif. L’ensemble de ce travail met en évidence la nécessité d’une évaluation plus approfondie de la radiotoxicité potentielle de Sb et Te lors de leurs rejets en milieu aquatique. / Antimony (Sb) and tellurium (Te) are relatively uncommon contaminants (stable isotopes) and may form short-lived fission products (radionuclides) released into the environment during nuclear power plants accidents. Little is known about their respective biogeochemical behaviours, necessary for general contamination studies and post-accidental radiological risk assessment.This work provides original knowledge on Sb and Te biogeochemical behaviour in highly dynamic continent-ocean transition systems: the Gironde Estuary and the Rhône River. Concentrations, spatial/temporal variations, solid/liquid partitioning (Kd), and fluxes are studied from long-term records at the watershed scale. Four estuarine sampling campaigns during contrasting hydrological conditions show higher Sb solubility and Te particle affinity in the estuary than in the upstream fluvial reaches. Historical records (1984-2017) in wild oysters from the estuary mouth do not show clear trends of past or recent contamination, but measurable bioaccumulation suggests that potential uptake of radionuclides is likely to occur. Combined adsorption experiments using isotopically-labelled (spiked) Sb and Te, and subsequent selective extractions of carrier phases from suspended particulate matter (SPM) suggest that spiked Sb and Te are more mobile and potentially bioaccessible than their environmental (inherited) equivalents. Radiotracer adsorption experiments using environmentally representative concentrations of both Gironde and Rhône systems underpin that highly soluble elements may show contrasting reactivity between inherited and spiked forms.Radionuclide dispersion will greatly depend on (i) the geographical position of the source (Rhône) and/or the maximum turbidity zone (MTZ; Gironde fluvial-estuarine system), (ii) the succession of hydrological situations during and after the accident, and (iii) the biogeochemical reactivity and half-lives of the radionuclides. First scenarios on hypothetical dissolved radionuclide dispersion in the Gironde Estuary suggest (i) low sorption of Sb to the SPM, implying a transport of radionuclides in dissolved phase towards the coast, and (ii) high retention of Te within the MTZ, especially for accidental releases during flood conditions, linking the fate of radioactive Te to long estuarine SPM residence times (1-2 years). Potential upstream migration of Te radionuclides in the MTZ towards the city of Bordeaux during the following summer season and Te decay into radioactive iodine warrants further evaluation of the associated potential radiotoxicity.

Les phonons mous et le couplage électron-phonon sont considérés comme responsables d’un grand nombre de transition de phase. Pour en comprendre complétement les mécanismes, il est nécessaire d’étudier à la fois les modifications structurales, les changements de configuration électronique et les dynamiques de réseau cristallin. De toute évidence, cela représente une charge de travail expérimental et théorique considérable, voire même hors d’atteinte.Néanmoins, il est parfois possible d’introduire certaines simplifications et d’ainsi rendre une telle étude réalisable. C’est le cas pour les deux systèmes au cœur de ce travail de thèse, pour lesquels la transition de phase peut être diviser en deux instabilités : l’une est structurale, intrinsèque aux éléments constitutifs du système et l’autre, superposée, provient de la configuration électronique. L’interaction entre ces instabilités est illustrée à travers l’exemple de deux systèmes à priori hétérogènes, la famille des bronzes monophosphate de tungstène d’une part et l’antimoine d’autre part, qui révèleront finalement posséder des similarités inattendues. La combinaison des techniques de diffusion diffuse et de diffusion inélastique de rayons X permet des observations qualitatives et une meilleure compréhension de la situation pour les deux systèmes.Les bronzes monophosphate de tungstène font partie de la famille des oxydes quasi-2D, (PO2)4(WO3)2m, qui ont la particularité d’être sujet à des instabilités de type onde de densité de charges (ODC). Ces bronzes sont constitués d’une structure de perovskite vide composée par des couches octaédriques (WO3)2m. L’épaisseur de chacune de ces couches est définie par la valeur de m, qui mène ainsi à différents types de phase d’ODC. Le cas du terme m=2 a aussi été étudié car le fait que les chaînes zig-zag y soient isolées conduit à une instabilité quasi-1D. La présence d’une phase d’ODC a été découverte à TC=270K avec q=0.25b*. Cette phase est engendrée par le mouvement à corps rigide, plus exactement, par les basculements corrélés des octaèdres. Pour les autres termes (m=6,7 et 8), l’instabilité structurale a une origine différente et est liée à l’agencement en couches de WO3, plus particulièrement aux déplacements corrélés des chaînes W-O-W-O. Ces derniers sont la cause d’une forte diffusion diffuse sur des plans spécifiques, résultant de la présence de phonons ’relativement’ mous localisés dans la même région. Ensuite, l’emboitement de la surface de Fermi quasi-2D est à l’origine de l’ancrage du vecteur de modulation sur une valeur spécifique de transfert de moment, définit par l’interaction de deux instabilités, structurale et électronique. De façon remarquable, l’amplitude des déplacements des atomes de tungstène dans le terme m=8 est beaucoup plus élevée que dans le m=6.L’antimoine à température ambiante possède une structure rhomboédrique, dérivant d’une légère distorsion de la structure cubique primitive (CP) par transition de Peierls. Sous pression, la distorsion se réduit sans toutefois disparaître complétement, puisque l’antimoine se transforme dans un premier temps en une série de structures complexes, pour finalement adopter celle possédant la plus grande symétrie, la structure cubique centrée (CC). De la même façon que pour les bronzes, les caractéristiques de la diffusion diffuse ainsi que, dans une certaine mesure, les particularités de la dynamique du réseau rhomboédrique, s’expliquent à travers de l’instabilité du réseau cubique primitif. Cette dernière est liée aux déplacements corrélés dans les chaînes avec direction pseudo-cubique <100>. En outre, les détails de la transition de phase peuvent être explicités par l’association de l’analyse des vecteurs critiques de la transformation CC-CP avec les résultats expérimentaux obtenus sur la dépendance en pression de l’énergie des phonons. / A large number of phase transitions can be interpreted as being driven by phonon softening and/or electron-phonon coupling. Thus, a full mechanistic description requires the understanding of structural transformation, changes in electronic structure and lattice dynamics. All together this represents an enormous, for many cases unrealisable, experimental and theoretical effort.However, with the introduction of appropriate assumptions the problem may be simplified. Here we concentrate on two systems, where the interpretation of the phase transition may be split into an intrinsic instability of the building blocks combined with a superimposed electronic instability. We illustrate the interplay between the framework and electron-phonon-related instabilities using the seemingly heterogeneous examples of phosphate tungsten bronzes and elementary antimony. Based on the combined results from diffuse and inelastic X-ray scattering, we propose for the two systems a picture that explains the experimental observations. The similarities found between these two systems are deemed to be rather surprising.Monophosphate tungsten bronzes are a family of quasi-2D-oxides, (PO2)4(WO3)2m, that exhibits charge density wave (CDW) instability. They contain empty perovskite WO3 slabs with varying thickness between different members, characterised by the $m$ value. This thickness defines the sequence of charge density wave phases that appear on cooling. The degenerate case of $m$=2, presenting a quasi-1D instability, was explored since the WO3-octahedra zig-zag chain is isolated. A CDW phase (TC=270K and q=0.25b*) is found to be linked to a rigid-body motion, precisely, to a correlation in the tilting of the octahedra. For the others studied members, as m=6,7 and 8, we found another kind of structural instability. In this case the origin comes from the WO$_3$ slabs framework, realised as correlated displacements of tungsten atoms along the octahedral 4-fold axis direction (W-O-W-O direction). This leads to a strong x-ray diffuse scattering localised in specific planes, linked to relatively soft phonons modes. Specific Fermi surface nesting, close to the 2D case, gives rise to a freezing of the modulations at the specific momentum transfer, defined by the interplay of two instabilities, the structural and electronic one. Remarkably, the displacements of W for m=8 are much superior than in m=6.Elemental antimony at ambient condition has an A7 rhombohedral structure, obtained by small distortion from primitive cubic (PC) lattice through a Peierls transition. Under pressure, the distortion is reduced, but remains finite, as antimony transforms through a series of highly complex structures, before adopting as last the highest-symmetry body-centred cubic (BCC) phase. The main diffuse scattering features and to some extent the peculiarities in the lattice dynamics of the A7 phase – as above - can be explained by the instability of the primitive cubic network with respect to correlated displacements along the chains with <100> pseudo-cubic directions. Analysis of critical vectors for the BCC-PC transformation together with experimentally obtained phonon-energies pressure dependence provides further insights into the details of the phase transformation.

Antimoine et tungstène, deux "petits métaux" qui, à différentes périodes, eurent une importance stratégique liée à l'industrialisation et l'armement. L'antimoine, connu depuis l'Antiquité, fut exploité en France à partir du XVIe siècle mais c'est aux XIXe et XXe siècles qu'il fit l'objet d'une exploitation significative. Les applications industrielles du tungstène, plus récentes, datent de la fin du XIXe siècle. Aux XIXe et XXe siècles, plusieurs périodes présentent une convergence entre la taille des gisements, les méthodes d'exploitation et de traitement employées, la structure des entreprises et la consommation de ces métaux. Cette conjonction s'avère favorable à la prospérité, dans la période préindustrielle puis au XXe siècle, au développement des mines métropolitaines. La dispersion des compagnies et la multitude de petits gisements fut, au contraire, préjudiciable à la prospérité de cette activité. Dans les années 1960, l'implication de l'Etat dans la recherche minière, à travers le BRGM, puis les mesures de soutien à la prospection privée, aboutirent à la découverte de nouveaux gisements de métaux non-ferreux. En revanche, l'implication de l'Etat dans l'exploitation minière, à travers COFRAMINES, fut moins favorable. La gestion administrative et peu réactive s'avéra inadaptée à la versatilité du marché de ces métaux. Aujourd'hui, en France, la mine se heurte à de telles contraintes, sociales, administratives et environnementales, que la relance d'une exploitation de l'antimoine et du tungstène parait peu probable, dans les conditions économiques actuelles. / Antimony and tungsten, two "small alloy metals" that both, at different periods of time, had a strategic importance, linked to industrialisation and armament. Antimony which was known in Antiquity, has been mined in France since the 16th century, but it was truly during the 19th and 20th centuries. Industrial applications of tungsten are recent, dating back to the last decade of the 19th century. During the 19th and 20th centuries, several periods present a convergence between the size of deposits, the methods used to exploit and process, the companies' structure, and the consumption of these two metals. This conjunction was favourable to the antimony mines' prosperity during the pre-industrial period then, in the 20th century, to the development of several mines. The dispersion of companies, on a multitude of small deposits, is prejudicial to the development of antimony and wolfram-rich districts like those of the Massif Central. The French State's implication, through the BRGM's actions starting in the 1960s, then by the establishment of aids towards private prospecting, was beneficial for the discovery of non-ferrous metals deposits. However, the State's decision to change from exploration to mining, through COFRAMINES, was less favourable. The administration management, sometimes burdened and slow to react, showed itself to be inadequate in a context as versatile as the antimony and tungsten market. Today the mining industry, in its whole, faces such social, administrative and environmental constraints, that the antimony and tungsten mining industry's revival, in today's economic and political situation, remains improbable.

L‘arsenic et l‘antimoine bien que n‘étant pas recensés parmi les polluants majeurs de l‘environnement sont souvent retrouvés associés à d‘autres contaminants. En France, et plus particulièrement dans la région Auvergne, de nombreux sites miniers où s‘effectuait l‘extraction de l‘antimoine sont désormais à l‘abandon. Pouvant présenter des risques pour les populations avoisinantes, leur réhabilitation est donc une mission d‘intérêt public. L‘idée de ce travail de doctorat est de tester l‘effet d‘un catalyseur : le ver de terre sur l‘efficacité des processus de phytoremédiation. En tant qu‘« ingénieurs du sol », ils sont à la base des processus de pédogénèse et peuvent donc assurer la restructuration du sol. De plus, de nombreuses études ont montré leurs effets positifs sur la production de biomasse végétale. Cependant, les mécanismes moléculaires responsables de cette acroissement de production demeurent méconnus. Un système expérimental novateur, jamais utilisé en Ecologie des Sols et couplant la plante modèle Arabidopsis thaliana (L.) Heynh et Aporrectodea caliginosa (Savigny), un ver de terre endogé commun des régions tempérées, a été mis en place afin de 1) identifier les principales voies métaboliques modifiées en réponse aux vers de terre et pouvant expliquer leurs effets positifs sur la croissance et le développement des végétaux, 2) étudier la nutrition minérale en fer et en phosphate, notamment au niveau des variations d‘expression des transporteurs de ces deux éléments, 3) tester ce système pour la phytoextraction de sédiments, issus d‘un ancien site minier, contaminés à l‘arsenic et à l‘antimoine. Les résultats montrent que l‘amélioration des processus de minéralisation est déterminante dans l‘accroissement de la biomasse d‘Arabidopsis thaliana qui se traduit aussi par une élévation des teneurs en azote dans les parties aériennes. Cependant, la présence de phytohormones, produites par des bactéries activées par leur transit dans le ver de terre semble également impliquée dans le renforcement de l‘absorption d‘azote. A l‘échelle moléculaire, les vers entraînent une surexpression du gène HBT, impliqué dans la division cellulaire et semblent diminuer le stress oxydant puisque la quantité de transcrits SOD Cu/Zn diminue. Les résultats montrent de plus que les vers de terre augmentent de façon significative l‘absorption et l‘accumulation de fer, de phosphate et d‘autres minéraux essentiels à la croissance du végétal. Moléculairement, l‘augmentation de l‘absorption des nutriments se traduit par une augmentation de la transcription de certains gènes codant des transporteurs tels que PHT1.3, qui est un transporteur de haute affinité pour le phosphate. Une augmentation de la transcription et également de l‘activité de la protéine FRO2, qui est à l‘origine de la chélation et de la réduction du fer a été observée. Dans les feuilles, les vers de terre induisent de manière systémique la surexpression d‘un transporteur de phosphate localisé dans les chloroplastes, PHT2.1 et la surexpression de transporteurs du fer appartenant à la famille des NRAMPs, notamment NRAMP1,2 et 6. Dans le contexte d‘une problématique de phytoremédiation, l‘effet des vers de terre sur la capacité de phytoextraction d‘Arabidopsis a été testé et, il ressort clairement de cette étude que les vers de terre permettent une meilleure absorption d‘antimoine et d‘arsenic. Cependant, ces deux métalloïdes tendent à rester dans les racines et ne sont que faiblement transferrés vers les parties aériennes. Cette formidable augmentation des concentrations en polluants dans les racines entraîne un retard de croissance considérable et affecte, dans une moindre mesure cependant, l‘activité photosynthétique et les échanges gazeux d‘Arabidopsis. Ainsi, ce travail de thèse a donc tout d‘abord démontré la sensibilité aux vers de terre de la plante modèle Arabidopsis thaliana. Ce système expérimental novateur offre de nouvelles possibilités de recherches dans le domaine des études des interactions entre les vers de terre et les plantes, notamment en raison de la grande diversité de mutants d‘Arabidopsis. De plus, ce travail a également permis de démontrer le rôle crucial de catalyseur que peuvent jouer les vers de terre en vue d‘optimisation des processus de phytoextraction. / Arsenic and antimony do not belong to the major pollutants of the environment but are offen foun associated with other contaminants. In France, more specifically in Auvergne region, a large number of old mining site where antimony was extracted are currently abandoned. As they present several risks for the neighbourhood populations, their habilitaion appears to be essential. The main idea if this PhD work is to test a catalysor: the earthworms in order to increase phytoremédiation efficacity. As ―soils ingeniors‖, they are involved in pedogenesis process and can lead to soil reorganization. Moreover, several studies have presented their positive effects on plant biomass. Nevertheless, the molecular mechanisms responsible of this production enhancement remain still unknown. An innovative experimental system, never used in Soil Ecology, using the model plant Arabidopsis thaliana (L.) Heynh and the endogeic temperate earthworms Aporrectodea caliginosa (Savigny) has been set up. This research work has three goals. First, identify the main metabolic pathway affected by earthworm presence and able to explain their positive effects on plant growth and development. Then, this research work focused on phosphorus and iron nutrition particularly by studing the molecular variation of several transporters of these elements. Lastly this system has been tested for phytoextraction of wastes from an old mining site polluted by arsenic and antimony. In the first part of this study, the mineralization process improvement appears to be a determining factor in Arabidopsis growth enhancement due to nitrogen increase in the shoots. Nevertheless, phytohormones producted by bacteria activated during their transit into earthworm gut seem to be involved in nitrate assimilation. At the molecular scale, earthworms enhance an overaccumulation of HBT transcripts involved in cell division and they seem to decrease the oxidative stress as SOD transcripts are underexpressed. The second part of this study focused on mineral nutrition. Results show that earthworms enhance significantly the uptake and accumulation of phosphorus, iron and other growth essential minerals. At the molecular scale, the nutrient uptake increase result in an increase of several transporters such as Pht1.3, which is a high affinity phosphate transporter and also an overexpression and an increase in enzymatic activity of the ferric chelate reductase protein FRO2. In the leaves, this experiment also show the overaccumulation of a phosphate chloroplastic transporter Pht2.1 and over expression of iron transporter belonging to the NRAMPS family, especially NRAMP1,2 and 6. Then, this system has been transposed to the phytoremédiation and earthworm effects have been tested on the phytoextraction properties of Arabidopsis. Earthworms allow a better uptake of arsenic and antimony. Nevertheless the pollutants tend to remain in the root system and are not translocated in the aerial part. This incredible increase in pollutant tissue concentration leads to a growth and development delay and affect the Arabidopsis photosynthetic activity. To conclude, this PhD work has first shown earthworm sensitivity of Arabidopsis. This innovative system offers new investigation possibilities in the interaction between earthworms and plant area, especially due to the large range of Arabidopsis mutants. Moreover, this work has also demonstrated the key role as catalysor that can play earthworms in order to optimize phytoremédiation process.

O objetivo deste trabalho é o estudo das Mudanças Estruturais Fotoinduzidas em filmes do sistema vítreo [Sb(PO3)3]n &#8722;Sb2O3 bem como a produção e caracterização do sistema vítreo em questão. Vidros de x[Sb(PO3)3]n&#8722;(100&#8722;x)Sb2O3 (5 &#8804; x &#8804; 40) foram produzidos pela fusão dos precursores Sb2O3 e [Sb(PO3)3]n a 900°C em cadinhos de carbono vítreo e em seguida vertidos e resfriados rapidamente em moldes de aço inox. Dessa forma foi possível obter vidros homogêneos e estáveis com dimensões de 1,0 x 1,0 x 0,5 cm3. A caracterização do sistema vítreo e parâmetros como região de formação vítrea e temperaturas características foram obtidos por meio de técnicas como DSC, Difração de Raios&#8722;X, FTIR, e MAS&#8722;NMR. A região de formação vítrea neste sistema ocorre para composições entre 10 &#8804; x &#8804 25 sendo que para x = 5, x = 30, e x = 35 forma&#8722;se um vidro com pequena fração de microcristalinidade que apresenta coloração amarelada sendo visualmente transparente, já para x = 40 forma&#8722;se um vidro com maior fração de microcristalinidade e totalmente opaco. Este sistema vítreo possui interessantes propriedades como larga janela de transmitância (&#8764; 0,4 a 8 &#181;m), alto índice de refração (n &#8764; 2,0), baixa temperatura de fusão (Tf&#8764;900 &#176;C) e baixa temperatura de transição vítrea, (Tg&#8764;300 &#176;C). Filmes de x[Sb(PO3)3]n&#8722;(100&#8722;x)Sb2O3 foram produzidos por evaporação térmica dos vidros através de canhão de elétrons (EB&#8722;PVD) em um sistema não comercial de evaporação desenvolvido em nosso laboratório, onde conseguimos produzir de maneira eficiente e com boa qualidade óptica filmes de até 10 &#181;m de espessura. Estes filmes apresentam um atípico fenômeno de fotocontração em torno de 8 % da espessura do filme, acompanhado de fotoclareamento após irradiação com laser UV em 350,7 nm. Além da caracterização a nível macroscópico do fenômeno de fotocontração (comportamento em função da potência e tempo de irradiação com laser UV) nossa atenção ficou voltada para o estudo desse efeito a nível estrutural, através de técnicas como Difração de Raios&#8722;X, XANES, FTIR, RPE, RBS e Holografia Óptica. Além da ampla caracterização mostramos a possibilidade de aplicação do material para holografia ou armazenamento óptico, redes de difração, e matrizes de microlentes. O efeito de fotocontração nos filmes foi notado devido ao fotoclareamento observado visualmente após a exposição ao UV e foi confirmado por medidas de perfilometria da região exposta ao UV. O efeito de fotoclareamento (simultâneo a fotocontração da superficie) ocorre gerando deslocamento de &#8764; 30 nm do bandgap (3,58 eV, 347 nm) para maiores energias (4,01 eV, 310nm). Também observamos um pequeno deslocamento do bandgap para irradiações com &#955;.=482 e 460 nm. A fotocontração evolui não linearmente com o tempo e potência de irradiação. Depende também do tempo de exposição e da potência do laser, tendendo a saturação após 4 horas de exposição a 5 W&#8260;cm2 (100 mW) ou 2 horas de exposição a 15 W&#8260;cm2 (300 mw). O efeito de fotocontração tem forte dependência com a concentração de polifosfato de antimônio na composição dos filmes do sistema vítreo x[Sb(PO3)3]n&#8722;(100&#8722;x)Sb2O3. Filmes de 1,0 &#181; de espessura irradiados com 100 mW (5,0 W&#8260;cm2) por 4 horas (região de saturação) apresentam fotocontração (&#8722;&#916;V&#8260;V) de até 8,0 % da espessura do filme (para x = 25) quando irradiados com laser UV (&#955;.=350 nm) Para x = 10 a contração é menor que 2,0 %, e para concentrações de polifosfato acima de 25 % efeito é diminuído drasticamente. A atmosfera na qual o filme é irradiado tem grande influência no efeito de fotocontração. Filmes de 20 % [Sb(PO3)3]n&#8722;80 % Sb2O3 (espessura: 1,0 &#181;m)irradiado com laser UV por 4 horas a 100 mW (5,0 W&#8260;cm2) apresentaram fotocontração (&#8722;&#916;V&#8260;V) de &#8764; 8 % (&#8764; 50 % maior) em atmosfera de O2, 5 % no ar, e menor que 2 % para o vácuo, N2 e He. Apesar de se partir da evaporação dos vidros para produção dos filmes, a principal diferença de estrutura entre vidro e filme é que estes últimos apresentam estrutura com grande número de vazios intersticiais ao redor de unidades estruturais, o que não ocorre para os vidros. Nossos resultados mostraram efetivamente que o efeito de fotocontração em filmes irradiados com UV está relacionado com mudanças de estrutura de grupos fosfatos e efeitos fototérmicos cooperativos. Na parte de aplicações gravamos redes holográficas de relevo nos filmes estudados. Utilizando uma montagem tipo espelho de Lloyd para holografia foi possível gravar redes com período de 600 nm até 20 &#181;m e medimos a eficiência de difração em tempo real utilizando um feixe de prova de laser He&#8722;Ne. As redes gravadas em filmes de filmes de 20% [Sb(PO3)3]n&#8722;80 % Sb2O3 com período de 20 &#181;m de espessura apresentam eficiência de difração de 3 a 10,5 % para aproximadamente 1 hora de gravação e potencia variando de 50 a 600 mW (2,5 a 30 W&#8260;cm2), respectivamente. / The aim of this work is the study of the Photoinduced Structural Changes (PSC) in films of the [Sb(PO3)3]n &#8722;Sb2O3 glassy system, as well as the production and characterization of the glassy system. The glass samples x[Sb(PO3)3]n&#8722;(100&#8722;x)Sb2O3 (5 &#8804; x &#8804; 40) were produced by the melt&#8722;quenehing technique of suitable quantities of the precursors Sb2O3 and [Sb(PO3)3]n, fused at 900&#176;C in glassy carbon crucibles and verted into stainless steel moulds. Homogeneous and stable glass plates of 1.0 x 1.0 x 0.5 cm3 were obtained. The characterization of the glass system and the obtaining of parameters such as the glass forming region and characteristic temperatures were possible through DSC, X&#8722;ray Diffraction, FTIR and MAS&#8722;NMR techniques. The studied glass system possess remarkable properties such as broad transmittance window (from 0.4 to 8.0 &#181;m), high index of refraction (n &#8764; 2.0), low melting temperature (Tf&#8764;900 &#176;C) and low glass transition temperature (Tg&#8764;300 &#176;C). The films were produced by electron beam physical vapor deposition (EB&#8722;PVD) of the glasses, in a non&#8722;commercial evaporation system developed in our laboratory, where is possible to produce high quality films with thickness of up to 10 &#181;m. The films samples presented an atypical photocontraction behavior that consists of a decrease of up to 10 % in the thickness, accompanied of photobleaching after UV irradiation using a 350.7 nm laser line. Besides the macroscopic characterization of the photocontraction effect (behavior as function of the UV laser power density and irradiation time), our attention was focused on the study of the effect at structural level using techniques such as X&#8722;ray diffraction, XANES, FTIR, EPR, RBS and Optical Holography. In addition to the wide characterization we shown in this work the possibilities of application of this material for optical storage and holography, diffraction gratings, micro-lens array.

Diariamente milhares de profissionais da área de segurança utilizam armas de fogo, quer em ações de combate a criminalidade; quer em treinamentos obrigatórios que a atividade exige. Apesar disso a quantidade de informação sobre os riscos à saúde desses profissionais devido da exposição aos resíduos de disparos, especialmente quando são usadas armas de grosso calibre, ainda é escassa. Este trabalho pretendeu trazer uma contribuição às discussões sobre o tema com uma proposta de normalização para ser observada no planejamento dos procedimentos de treinamento e atividades desses profissionais. Para tanto foram estudados dois grupos de profissionais: o primeiro, profissionais militares da Polícia Militar do Estado de São Paulo durante intensas jornadas de treinamento com esforço físico e grande numero de disparos com armas de fogo de grosso calibre O segundo grupo envolvendo peritos criminais do núcleo de balística do Instituto de Criminalística da Secretaria de Segurança do Estado de São Paulo. Foram utilizadas amostras de materiais biológicos (sangue, urina e saliva) e amostras do ar dos ambientes fechados onde estas rotinas de trabalho ocorrem. No caso dos profissionais militares, os níveis dos metais monitorados no ar variaram de acordo com o tipo de arma e munição utilizada, sendo ultrapassado o limite de tolerância estabelecido na NR-15 (100 &mu;g/m3) após o uso de espingarda (216 &mu;g/m3). A média e desvio padrão dos níveis de chumbo no sangue antes (3,3 &mu;g/dL ± 0,7) e depois (18,2 &mu;g/dL ± 5,1) do curso indicam que ouve um aumento importante num curto período de tempo, também houve aumento nos níveis de chumbo e antimônio na urina. No segundo caso de exposição ocupacional aos resíduos de disparo no núcleo dos peritos balísticos se verificou uma baixa quantidade de resíduos no ambiente de trabalho, se comparado com o Limite de Tolerância preconizado na norma NR-15, e uma baixa quantidade de chumbo no sangue (3,9 &mu;g/dL ± 0,8) se comparado com o Índice Biológico Maximo Permitido IBMP (60 &mu;g/dL) estabelecido na NR-7, sem embargo quando comparado o grupo de balísticos com o grupo controle (1,8 &mu;g/dL ± 0,7) estabeleceu se uma diferença. O estudo dos cenários de exposição permitiu gerar uma proposta para trabalho seguro nestes ambientes e recomendações para o desenho e uso de estantes fechados de disparo. Os câmbios que se introduzam nos costumes e comportamentos dos profissionais levaram uma diminuição do risco associado ao uso de armas de fogo nestes estantes. As conclusões do presente trabalho contribuem para a adequação das medidas de proteção dos trabalhadores de segurança, e na adequação da legislação relativa aos limites de tolerância e índices bilógicos empregados no controle de saúde ocupacional. / Daily thousands of military officers from security forces use fire arms, sometimes in actions against crime or in mandatory training seasons. Despite of this, there is a few information about the risk associated with firing ranges, especially when heavy weapons are used in a hard training seasons with hard physical work and elevated number of rounds, the security forces might be under risk of intoxication. Other types of exposure with less frequency and intensity, but using a high lead containing ammunition and different types of weapons, like in the ballistics forensic cases are not yet sufficiently studied. Data from these types of occupational exposure in these environments are important in order to establish safety working procedures. The goal in this research is to study the occupational exposure in the police department and the ballistics laboratories in personal who are under the risk of this exposure in their routinely daily work and during the training courses in the Sao Paulo´s Military Police Department. In order to reach this, some biological materials were sampled (blood, urine and saliva) as well as air samples from the environment in the firing ranges during routinely daily work. In the two studied cases the monitored airborne lead varied in accordance with the type of weapon and ammunition used, and was ultra passed the limit of exposure established in the norm NR-15 (100 &mu;g/m3) after the shot gun was used during the training season (216 &mu;g/m3). The average and standard deviation of lead content in blood before (3,3 &mu;g/dL ± 0,7) and after (18,2 &mu;g/dL ± 5,1) de training season shows a significant rise of the lead levels in a very short period of time. An increment of the lead and antimony levels in urine was demonstrated. The other studied case, in the ballistics laboratory showed minor increments of lead in blood and airborne residues when compared with the limits established in the norm NR- 7 (60 &mu;g/dL) but when compared in a cohort study the data lead to establish a significant difference between the exposed group from the ballistics and the control group. These results let us to design a proposal to safely work in these environments and to give the recommendations in the engineering design of the indoor ranges. The implemented changes will lead to minimize the risk associated with the use of weapons and lead containing ammunitions. The conclusions of the present work contribute to adequateness of the related legislation and the tolerance limits of exposure used in the occupational health practice.