Ao longo dos últimos anos, Sr2+ tem sido aplicado em estudos in vitro e in vivo como um importante agente para o estímulo de osteogênese. Dessa forma, a criação de matrizes bioativas contendo Sr2+ é uma tendência na área de modificações de superfícies metálicas para aplicações em implantes de substituição óssea. Nesta dissertação, desenvolvemos sistemas bioinspirados que possam atuar como carreadores de Sr2+ em biomateriais. Na primeira parte, superfícies de Ti foram modificadas com filmes híbridos contendo SrCO3 e ou CaCO3. A formação dos filmes híbridos foi mediada pela deposição de filmes Langmuir-Blodgett sobre superfícies de Ti. Essas matrizes altamente organizadas atuaram como molde para a deposição de filmes híbridos contínuos e homogêneos sobre as superfícies. A resposta biológica desses materiais foi avaliada por cultura de osteoblastos in vitro, indicando que os materiais não são tóxicos e, em especial, que a associação entre SrCO3 e CaCO3 dá origem a recobrimentos com composição e propriedades superficiais otimizadas que induzem melhores respostas osteogênicas. Na segunda parte, foi sintetizado um novo complexo entre morina e Sr2+. A estrutura desse complexo foi inspirada no fármaco ranelato de estrôncio, um dos compostos mais utilizados para o tratamento da osteoporose. Dessa forma, aliamos a propriedade antioxidante da morina, um flavonóide natural, e a atividade osteogênica do Sr2+ para desenvolver um novo composto bioativo. A estrutura do complexo morina-Sr2+ foi caracterizada por diferentes técnicas espectroscópicas, onde determinamos que a complexação ocorre com a estequiometria 1:1. Visando o desenvolvimento de recobrimentos bioativos para superfícies metálicas, estudamos também a complexação entre morina e Sr2+ em monocamadas de Langmuir. Através da caracterização físico-química das monocamadas contendo morina na presença de Sr2+, observamos que é possível formar multicamadas auto-organizadas contendo o complexo morina-Sr2+ sobre superfícies sólidas. Essas matrizes mostram-se promissoras para uso em modificações de superfícies com propriedades osteogênicas. Por fim, o último sistema apresentado nessa dissertação é a criação de matrizes auto-organizadas de colágeno tipo I, mimetizando a organização hierárquica dessa proteína no tecido ósseo. Para isso, a auto-organização das fibrilas de colágeno sobre superfícies sólidas foi mediada por um processo onde o substrato é lentamente emerso de uma solução contendo moléculas de colágeno. Essa emersão faz com que forças competitivas (fricção e tensão superficial) atuem na interface sólido-líquido-ar e promovam o alinhamento das fibrilas de colágeno auto-organizadas no menisco da solução/substrato. A estrutura dos filmes finos assim formados foi caracterizada e mostrou-se ser dependente da concentração, pH e força iônica da solução de colágeno. Filmes de colágeno altamente orientados formados por essa metodologia poderão ser utilizados como sistemas carregadores de Sr2+ através da biomineralização de hidroxiapatita. Por fim, nessa dissertação foram apresentados três sistemas distintos com um ponto comum: a atuação como matrizes carreadoras de Sr2+. Por meio da densa caracterização da composição e das propriedades superficiais, mostramos que esses sistemas são promissores para o uso como recobrimentos bioativos sobre superfícies de Ti / In the past few years, Sr2+ has been described to play a fundamental role on the bone osteogenesis, as demonstrated by in vitro and in vivo studies. Therefore, the design of bioactive coatings containing Sr2+ is an interesting approach to modify metallic implants for bone regeneration. Herein, we described the development of bio-inspired systems to act as carriers of Sr2+ in biomaterials. In the first section, Ti surfaces were modified by hybrid films containing SrCO3 and or CaCO3. The formation of hybrid films was mediated by the deposition of Langmuir-Blodgett films on the Ti surfaces. Those matrices act as a template for the organized nucleation and growth of biominerals. By this methodology, continuous and homogeneous thin films were formed on the Ti surfaces. The biological response was accessed by in vitro osteoblasts culture. The hybrid films were nontoxic to the osteoblasts and we observed that the association of SrCO3 and CaCO3 resulted in a coating displaying a synergic composition and surface properties that induced better metabolic responses on the cultured osteoblasts. In the second section, we described the synthesis of a new Sr2+-morin complex. The structure of the complex was inspired by the strontium ranelate, one of the most used drugs for osteoporosis treatment. This way, we aimed to ally the antioxidant properties of morin, a natural flavonoid compound, and the osteogenic behavior of Sr2+ to design a new bioactive compound. The chemical structure of the complex was determined by spectroscopic techniques and we observed that the complexation happens at the stoichiometry 1:1. To design bioactive coatings on Ti surfaces, we also performed the complexation between the strontium and morin directly on Langmuir monolayers. By physicochemical characterization, we identified that multilayers containing the Sr2+-morin complex can be built on solid supports. These results show that Sr2+-morin can be a promising approach to design biofunctional coatings on metallic surfaces. In the last section, we described the creation of hierarchical collagen thin films, mimetizing the structure found on bone tissue. To this, solid supports were pulled out from collagen solution at a controlled rate. In this approach, the self-templating is mediated by competing forces (i.e. surface tension and friction) that act in the meniscus placed between the solution and the support. This process allows the deposition of self-aligned collagen fibers on surfaces. The film\'s structure was characterized and is dependent on pH, pulling rate, ionic and collagen concentration of the solution. In the future, these films will be applied to create mineralized functional coatings containing Sr2+. In conclusion, the materials developed herein has an important point in common: they are different matrices to carry Sr2+ ions. By the composition and surface characterization performed herein, we believe that these materials can be applied in the design of biofunctional coatings for metallic implant surfaces

This analysis of faunal bones from Wolf Village focuses on large game and its utility, as evidenced by what is known as the modified general utility index (MGUI). The MGUI proposes that bones at sites reflect transportation and butchering choices made by hunters at kill-butchering sites. According to the assumptions associated with the MGUI, hunters should select animal portions with high food value. The MGUI has been used in Fremont archaeology to provide a rough measure of site function. The expectation is that faunal bones would accompany the prized cuts of large game meat at habitation sites – and the animal parts with little food value would remain at kill-butchering sites because they are not worth the cost to carry them to the village. My analysis of large game animal bones found in excavations at Wolf Village counter these expectations. Fremont hunters at Wolf Village were returning to the site with low-caloric portions of large game, at least part of the time. Results from strontium isotope analysis suggest that many of the large game individuals hunted by the Fremont were not local to the immediate area. This suggests that hunters saw utility in low-caloric elements not related only to food value. Some low-caloric skeletal elements were used by the Fremont to construct bone tools and other objects, and as possible symbolic objects used in abandonment rituals. The results of this research suggests that the MGUI is not appropriate for measuring the utility of animal portions to the Fremont. Only when considering the social and non-caloric economic reasons for transporting low caloric elements, can archaeologists discover the true utility of large game animal parts to Fremont hunters.

The aim of this study is to establish the provenance of the elephant and hippopotamus ivory recovered from the 14th century B.C. Uluburun shipwreck in order to reconstruct the trade mechanisms and associated social relationships (e.g. diplomacy) operating in the eastern Mediterranean during the Late Bronze Age (LBA). Elephant ivory came either from Northeastern Libya, Southeastern Sudan via Egypt or northwestern Syria during this period. Hippopotamus ivory likewise was obtained from Syria, Palestine, or Egypt. The Uluburun's cargo is reconstructed by the excavator, George Bass, as "royal," and primarily originates from Cyprus and Syro-Palestine. Indeed, LBA trade is largely understood as gift-exchange between ruling elites, thereby reflecting a trade system organized by and for a centralized authority. With the transition to the Iron Age, an identifiable merchant class developed and decentralized trade (relative to the preceding era) under a system of cabotage shipping. If the ivory is shown to derive from several regions instead of a single location, a revision of LBA trade must be fashioned to include ruling elites acting as "merchants" to a larger degree than previously assumed, or the web of social relationships involved in "international" diplomacy as much more intricate. Indeed, the mechanisms of the LBA trade must be established to provide a complete picture of trade, especially since the import and historical data is biased towards a simplistic, centralized trade system. The δ13C, δ15N, and δ18O reflect the climate and vegetation of the area in which a population dwells, so that areas with similar climate/vegetation will produce similar isotopic signatures, though these areas may be geographically seperated. Nevertheless, examining 87Sr/86Sr ratios will distinguish between populations because 87Sr/86Sr mirrors the isotopic signature of the underlying rock, and is sufficiently unique to each region to warrant differentiation. Isotopic ratio analysis (carbon, nitrogen, oxygen, and/or strontium) was conducted on the collagen and apatite components of the ivory using mass spectrometry to differentiate between regions and therefore provide the provenance. Ultimately a source determination utilizing HR-ICP-MS for 87Sr/86Sr was not successful. Future provenance research on ivory should employ TIMS, and consider triangulating 87Sr/86Sr against lead and neodymium isotopes.

Monthly δ18O and Sr/Ca records generated from modern and fossil corals from Southwestern Pacific Ocean sites in the Republic of Vanuatu are used to assess the differences in mean climate state, seasonality, and interannual variability between a glacial and interglacial period. The modern coral contains a well-defined annual signal in δ18O and Sr/Ca. The top 40 cm of the coral used in this study has a mean δ18O value of -4.99+/-0.13%VPDB (2σ) and a mean Sr/Ca value of 8.691+/-0.015mmol/mol (2σ). El Nino-Southern Oscillation (ENSO) events are characterized by positive δ18O and Sr/Ca anomalies, consistent with cooler temperatures and reduced rainfall that typifies ENSO at Vanuatu. The ~12cm long fossil coral is dated to 346 ka + 25, - 9, based on uranium-series analysis and stratigraphic forward modeling, indicating that the fossil coral grew during MIS10 - a glacial period. X-ray diffraction, petrographic inspection, SEM analysis, and geochemical considerations indicate excellent preservation. The mean δ18O value is enriched by 0.74%, and the mean Sr/Ca value is equivalent, compared to the modern coral. Mathematical modeling of Pleistocene mean SST and SSS results in temperature estimates up to ~2˚C warmer and salinity up to ~2 psu saltier than present-day conditions, if seawater Sr/Ca were 1-2% higher in MIS10. Our fossil coral data and modeling results preclude colder SST and lower SSS at Vanuatu during MIS10. Accurate estimates of past values of seawater Sr/Ca remain the largest obstacle to accurately reconstructing past tropical SST using pristine fossil corals. The fossil coral Sr/Ca annual range is similar to the modern range, indicating that seasonal SST ranges were similar, whereas the δ18O annual range is about half that of the modern coral, indicating weaker past seasonal salinity variations. The reduced seasonal SSS variations and increased SSTs near Vanuatu are interpreted as evidence that the SPCZ was displaced from its present location while the fossil coral lived. The geochemical response to El Niño events in the modern coral is observed twice in the fossil coral record, indicating that ENSO-like processes are not unique to interglacial time periods, but characterize the tropical Pacific at least back to MIS 10.

A sequence stratigraphic study was conducted on the Mendi and Darai Limestone Megasequences in the foreland area of the Papuan Basin in Papuan New Guinea. It involved the integrated use of seismic, wireline log, well core and cuttings, strontium isotope age and biostratigraphic data. This study enhanced the understanding of the structure, stratigraphy and depositional architecture of the limestones, and the morphology of the basin at the time of deposition. The results of the study were integrated with published geological and tectonic models for the Papuan Basin to develop a consistent and coherent model for the depositional history of the limestones. Eleven third-order sequences were delineated within the Mendi and Darai Limestone Megasequences. Eight depositional facies were interpreted across these sequences, namely deep-shelf, shallow-shelf, backreef, reef, shoal, forereef, basin margin and submarine fan facies. Each facies was differentiated according to seismic character and geometry, well core and cuttings descriptions, and its position in the depositional framework of the sequence. Deposition of the Mendi Limestone Megasequence commenced in the Eocene in response to thermal subsidence and eustatic sea-level rise. Sedimentation comprised open-marine, shallow-water, shelfal carbonates. During the middle of the Oligocene, the carbonate shelf was exposed and eroded in response to the collision of the Australian and Pacific Plates, or a major global eustatic sea-level fall. Sedimentation recommenced in the Late Oligocene, however, in response to renewed extensional faulting and subsidence associated with back-arc extension. This marked the onset of deposition of the Darai Limestone Megasequence in the study area. The KFZ, OFZ and Darai Fault were reactivated during this time, resulting in the oblique opening of the Omati Trough. Sedimentation was initially restricted to the Omati Trough and comprised deep and shallow-marine shelfal carbonates. By the Early Miocene, however, movement on the faults had ceased and an extensive carbonate platform had developed across the Gulf of Papua. Carbonate reef growth commenced along topographic highs associated with the KFZ, and led to the establishment of a rimmed carbonate shelf margin. Shallow to locally deeper-marine, shelfal carbonates were deposited on this shelf, and forereef, submarine fan and basin margin carbonates were deposited basinward of the shelf margin. The Uramu High and parts of the Pasca High became submerged during this time and provided sites for pinnacle reef development. During the middle of the Early Miocene, a major global eustatic sea-level fall or flexure of the Papuan Basin associated with Early Miocene ophiolite obduction subaerially exposed the carbonate shelf. This resulted in submarine erosion of the forereef and basin margin sediments. Towards the end of the Early Miocene, however, sedimentation recommenced. Shallow-marine, undifferentiated wackestones and packstones were deposited on the shelf; forereef, submarine fan and basin margin sediments were deposited basinward of the shelf margin; and reef growth recommenced along the shelf margin and on the Pasca and Uramu Highs. By the end of the Early Miocene, however, the pinnacle reef on the Pasca High had drowned. During the middle of the Middle Miocene, subtle inversion associated with ophiolite obduction subaerially exposed the carbonate shelf, and resulted in submarine erosion of the forereef and basin margin sediments. Sedimentation recommenced towards the end of the Middle Miocene, however, in response to eustatic sea-level rise and flexure of the crust associated with foreland basin development. Shallow marine, undifferentiated wackestones, packstones and grainstones were deposited on the shelf; carbonate shoals were deposited along the shelf margin; and forereef, submarine fan and basin margin carbonates were deposited basinward of the shelf margin. Carbonate production rapidly outpaced accommodation space on the shelf during this time, resulting in highstand shedding and the development of a large prograding submarine fan complex basinward of the shelf margin. By the Late Miocene, carbonate deposition had ceased across the majority of the study area in response to a major global eustatic sea-level fall or inversion associated with terrain accreation events along the northern Papuan margin. Minor carbonate deposition continued on parts of the Uramu High, however, until the middle of the Late Miocene. During the latest Miocene, clastic sediments prograded across the carbonate shelf, infilling parts of the foreland basin. Plio-Pleistocene compression resulted in inversion and erosion of the sedimentary package in the northwestern part of the study area. In the southeastern part of the Papuan Basin, however, clastic sedimentation continued to the present day.

Regions of surface water and groundwater exchange are major sites for the transfer and transformation of solutes and nutrients between stream and subsurface environments. Conventional stream and groundwater exchange investigations are limited by methodologies that require intensive field investigations and/or the set-up of expensive infrastructure. These difficulties are exacerbated where hydraulic gradients are very low and stream discharge highly variable. This thesis uses a suite of environmental tracers (Cl-, Rn-222, H-2 & O-18, Sr-87/Sr-86) to characterise the extent of stream and groundwater exchange between a sand bed stream and adjacent alluvial aquifer in a subtropical catchment (the Wollombi Brook) of eastern Australia. The aims were to identify sources and relative contributions of different sources of groundwater to stream discharge and specifically to improve the methodology of using Rn-222 to obtain quantitative estimate of groundwater fluxes. The sensitivity of the Rn-222 technique for identifying groundwater discharge based on the Rn-222 concentration in stream water was improved via an iterative numerical approach to account for Rn-222 loss from stream water via turbulent gas exchange and radioactive decay. Optimal distances between stream sampling points for defining the magnitude of groundwater discharge to stream flow based on Rn-222 concentrations in stream water is a function of average stream velocity and water depth. The maximum allowable distance between sampling points for determining the magnitude of groundwater discharge to the Wollombi Brook was 2 km. This work showed that groundwater discharged to all reaches of the Wollombi Brook during baseflow and flood recession conditions. Alluvial groundwater contributed less than 30% of water to stream flow in the mid Wollombi Brook catchment. Dilution of steady-state Rn-222 concentrations measured in transects from the stream to the alluvial sediments showed that significant surface water and groundwater exchange occurs even when gradients between surface water and groundwater are low. Lateral stream water influx to the adjacent alluvial aquifer was more extensive in the lowland areas of the Wollombi Catchment during low flow than flood recession conditions. Extensive stream water influx to the adjacent alluvial aquifer occurs contrary to the net direction of surface water and groundwater flux (as indicated by hydraulic gradients toward the stream channel). The rate of stream and groundwater exchange within the adjacent alluvial aquifer appears to be greatest during baseflow conditions. Fresh alluvial groundwater appeared to provide a buffer against higher salinity regional groundwater discharge to the alluvial aquifer in some reaches of the Wollombi Brook catchment. Pumping of the alluvial aquifer and diversions of surface water may jeopardise the water quality and volume of the alluvial aquifer and induce water flow from the regional aquifer toward the stream, potentially salinising the fresh alluvial aquifer and subsequently the stream. The change in the Cl- concentration and the variation in slope of the deuterium � oxygen-18 line between consecutive stream sampling points could be used to differentiate between regional and alluvial groundwater discharge to stream flow. Incorporating this information with three-component end-member mixing using [Sr2+] and Sr-87/Sr-86 showed that stream and alluvial groundwater exchange within the stream channel was highest in the lowland floodplains during low flow conditions. The least stream and alluvial groundwater exchange occurred in the low streambed gradient mid reaches of the Wollombi Brook regardless of stream stage. The greatest difference in the degree of stream and alluvial groundwater exchange between high and low stream stages occurred in the lowland floodplains of the Wollombi Brook.

There has been unprecedented growth in wireless technologies in recent years; wireless devices such as cellular telephones and wireless local area network (WLAN) transceivers are becoming ubiquitous. It is now common for a single hardware device, such as a cellular telephone, to be capable of multi-band operation. Implementing a dedicated radio frequency (RF) front-end for each frequency band increases the component count and therefore the cost of the device. Consequently, there is now a requirement to design RF and microwave circuits that can be reconfigured to operate at different frequency bands, as opposed to switching between several fixed-frequency circuits. Barium strontium titanate (BST) thin films show great promise for application in reconfigurable microwave circuits. The material has a high dielectric constant which can be controlled by the application of a quasi-static electric field, combined with relatively low losses at microwave frequencies. Tunable microwave components based on BST-thin films have the potential to replace several fixed components, thereby achieving useful size and cost reductions. This thesis is concerned with the growth and microwave circuit applications of BST thin films on c- and r-plane sapphire substrates. Sapphire is an ideal substrate for microwave integrated circuit fabrication due to its low cost and low loss. Electronically tunable capacitors (varactors) were fabricated by patterning interdigital electrode structures on top of the BST films. High capacitance tunabilities of 56% and 64% were achieved for the films grown on c-plane and r-plane sapphire, respectively, at 40 V bias. A novel electronically tunable 3 dB quadrature hybrid circuit was also developed. Prototypes of this circuit were initially implemented using commercial varactor diodes, in order to validate the design. An integrated version of the coupler was then fabricated using BST varactors on c-plane sapphire. The results achieved demonstrate the potential of sapphire-based BST thin films in practical microwave circuits.

La Spectrométrie de Masse à source Plasma à Couplage Inductif s'impose, de par ses multiples avantages, dont sa sensibilité et ses temps d'analyse réduits, comme la technique de spectrométrie de masse la plus répandue en analyse inorganique pour déterminer la concentration d'un isotope donné ou mesurer des rapports isotopiques. Le problème des interférences spectroscopiques, inhérent à cette technique, trouve une solution dans l'utilisation de dispositifs de collision-réaction. Une résolution in situ des interférences est en effet rendue possible par l'injection, dans la cellule de collision-réaction, d'un gaz judicieusement choisi. Les étapes de séparation chimiques, habituellement réalisées en amont de la mesure, et très pénalisantes dès lors que les échantillons manipulés sont radioactifs, peuvent ainsi être supprimées. La compréhension de la chimie des interactions « ions-molécules » en phase gazeuse est cependant primordiale pour optimiser l'efficacité de tels dispositifs. Pour cela, une connaissance précise des conditions expérimentales dans la zone de réaction s'avère cruciale, afin de pouvoir interpréter les réactivités observées.<br /><br />Deux ICP-MS de conception différente, l'ICP-MS Quadripolaire X7 (Thermo-Fisher Scientific) et l'ICP-MS Multi-Collection Isoprobe (GV Instruments), sont utilisés dans cette étude. Les conditions expérimentales, existant dans la cellule de collision-réaction de chacun de ces deux instruments, sont déterminées en fonction des paramètres instrumentaux. Cette étude préliminaire est ensuite mise à profit dans le cadre de la résolution de deux interférences, caractéristiques au domaine du nucléaire. Une approche théorique par calculs de chimie quantique permet d'interpréter la formation des oxydes de zirconium, responsable de la suppression de l'ion interférent 90Zr+, suite à l'utilisation d'O2 dans la cellule de collision-réaction pour permettre la mesure du radionucélide 90Sr. Le cas de la réactivité de cinq cations lanthanides (Nd, Sm, Eu, Gd, Dy) avec plusieurs gaz (O2, N2O, CO2, NH3) est par ailleurs étudié expérimentalement. L'efficacité de l'ammoniaque pour résoudre les interférences isobariques Eu/Gd est mise en évidence. Une périodicité de la réactivité sur la série des lanthanides, due à la configuration électronique de l'état fondamental des cations Ln+, est proposée pour expliquer les différences de comportements observées.

We test the fidelity of shallow-water gastropod skeletons as multi-proxy archives of seasonal paleo-environmental change by performing isotopic and trace-metal analyses on specimens of Conus ermineus from the Gulf of Mexico. Four adult specimens were collected from Stetson Bank in the Flower Garden Banks National Marine Sanctuary during the summer of 2002. Shell samples were milled along axes of growth to produce time-series profiles spanning up to eight years. We corrected the profiles for growth rate effects and compared the tuned results with in situ temperature and salinity records at the reef surface and temperature profiles from nearby surface buoys. Examination of sample densities in δ18O cycles shows that shell growth is faster during summers and slower during winters. Tuning the profiles versus time yields δ18O values that co-vary closely with seasonal temperatures to a high degree of coherency (R2 = 0.84). The δ13C profiles show cyclic variation modified by ontogenetic decreases in δ13C. These ontogenetic trends are attributable to decreasing metabolic efficiency, while seasonal cycles reflect hydrographic changes in the gastropods’ habitat. Salinity and δ13C of dissolved inorganic carbon show a strong correlation at Stetson Bank (R2 = 0.80), and early summer shell δ13C minima coincide with local salinity minima during times of peak river discharge. The terminations of these δ13C minima occur during annual upcoast reversals of shelf currents in this area. These effects are augmented by summer stratification and productivity minima that further decrease seawater δ13C. Sr/Ca ratios increase through ontogeny, most likely due to decreasing metabolic efficiency. However, seasonal variations in Sr/Ca profiles show strong similarity with δ18O profiles, confirming the temperature dependence of Sr/Ca and minimal influence of salinity on shell δ18O at Stetson Bank. The results of this study show that tuned δ18O and Sr/Ca profiles can be used to reconstruct seasonal paleotemperatures. Carbon isotope profiles and environmental data also demonstrate the utility of Conus δ13C as a proxy for freshwater flux and shelf circulation.

This thesis deals with the diffusion of ions in compactedbentonite clay. Laboratory experiments were performed toexamine in detail different processes that affect thediffusion. To demonstrate that the results obtained from thelaboratory investigations are valid under in situ conditions,two different kinds of in situ experiments were performed. Laboratory experiments were performed to better understandthe impact of ionic strength on the diffusion of Sr2+ and Cs+ions, which sorb to mineral surfaces primarily by ion exchange.Furthermore, surface related diffusion was examined anddemonstrated to take place for Sr2+ and Cs+ but not for Co2+,which sorbs on mineral surfaces by complexation. The diffusion of anions in bentonite clay compacted todifferent dry densities was also investigated. The resultsindicate that anion diffusion in bentonite clay consists of twoprocesses, one fast and another slower. We ascribe the fastdiffusive process to intralayer diffusion and the slow processto diffusion in interparticle water, where anions are to someextent sorbed to edge sites of the montmorillonite. Two different types of in situ experiments were performed,CHEMLAB and LOT. CHEMLAB is a borehole laboratory, where cation(Cs+, Sr2+ and Co2+) and anion (I- and TcO4-) diffusionexperiments were performed using groundwater from a fracture inthe borehole. In the LOT experiments cylindrical bentoniteblocks surrounding a central copper rod were placed in a 4 mdeep vertical borehole. The borehole was then sealed and theblocks are left for 1, 5 or&gt;&gt;5 years. When the bentonitewas water saturated the central copper rod is heated tosimulate the temperature increase due to radioactive decay ofthe spent fuel. Bentonite doped with radioactive Cs and Co wasplaced in one of the lower blocks. Interestingly, the redox-sensitive pertechnetate ion (TcO4-)which thermodynamically should be reduced and precipitate asTcO2·nH2O, travelled unreduced through the bentonite.However, at some spots in the clay, the Tc activity wasconsiderably higher. We ascribe these activity peaks toiron-containing minerals in the bentonite, by which Tc(VII) hasbeen reduced to Tc(IV) and precipitated. The cations Sr2+, Cs+and Co2+, as well as the anion I-, behaved in the CHEMLABexperiments as expected from laboratory studies. Three experiments in the LOT series are completed. The firsttwo diffusion experiments in LOT were less successful, thefirst due to the fact that saturation of the bentonite was notobtained during the experimental period and the radionuclidesdid not move at all. In the second, the uptake of the bentoniteparcel was less successful. Water from the drilling flushedaway large pieces of the top part of the bentonite and thelower part of the test parcel was super-saturated with waterand expanded when released from the rock. The activity distribution in the second experiment wasanalysed. The Co2+ profile looked as we had expected, while Cs+had spread more than our calculations indicated. However, thethird experiment was successful from emplacement, watersaturation and heating to uptake. The activity distribution forboth cations was as expected from laboratory studies. Altogether the three different types of experiments give auniform picture of radionuclide diffusion in bentonite clay forthe ions investigated. / QC 20100621