Detection of smuggled cocaine in cargo using MDCT.

OBJECTIVE: Smuggling dissolved drugs, especially cocaine, in bottled liquids is an ongoing problem at borders. Common fluoroscopy of packages at the border cannot detect contaminated liquids. The objective of our study was to develop an MDCT screening method to detect cocaine-containing vessels that are hidden between uncontaminated ones in a shipment. MATERIALS AND METHODS: Studies were performed on three wine bottles containing cocaine solutions that were confiscated at the Swiss border. Reference values were obtained by scans of different sorts of commercially available wine and aqueous solutions of dissolved sugar. All bottles were scanned using MDCT, and data evaluation was performed by measuring the mean peak of Hounsfield units. To verify the method, simulated testing was performed. RESULTS: Using measurements of the mean peak of Hounsfield units enables the detection of dissolved cocaine in wine bottles in a noninvasive and rapid fashion. Increasing opacity corresponds well with the concentration of dissolved cocaine. Simulated testing showed that it is possible to distinguish between cocaine-contaminated and uncontaminated wine bottles. CONCLUSION: The described method is an efficacious screening method to detect cocaine-contaminated bottles that are hidden between untreated bottles in cargo. The noninvasive examination of cargo allows a questionable delivery to be tracked without arousing the suspicion of the smugglers.

Economics of Using Calcium Chloride vs. Sodium Chloride for Deicing/Anti-Icing, TR-488, 2008

The use of chemicals is a critical part of a pro-active winter maintenance program. However, ensuring that the correct chemicals are used is a challenge. On the one hand, budgets are limited, and thus price of chemicals is a major concern. On the other, performance of chemicals, especially at lower pavement temperatures, is not always assured. Two chemicals that are used extensively by the Iowa Department of Transportation (Iowa DOT) are sodium chloride (or salt) and calcium chloride. While calcium chloride can be effective at much lower temperatures than salt, it is also considerably more expensive. Costs for a gallon of salt brine are typically in the range of $0.05 to $0.10, whereas calcium chloride brine may cost in the range of $1.00 or more per gallon. These costs are of course subject to market forces and will thus change from year to year. The idea of mixing different winter maintenance chemicals is by no means new, and in general discussions it appears that many winter maintenance personnel have from time to time mixed up a jar of chemicals and done some work around the yard to see whether or not their new mix “works.” There are many stories about the mixture turning to “mayonnaise” (or, more colorfully, to “snot”) suggesting that mixing chemicals may give rise to some problems most likely due to precipitation. Further, the question of what constitutes a mixture “working” in this context is a topic of considerable discussion. In this study, mixtures of salt brine and calcium chloride brine were examined to determine their ice melting capability and their freezing point. Using the results from these tests, a linear interpolation model of the ice melting capability of mixtures of the two brines has been developed. Using a criterion based upon the ability of the mixture to melt a certain thickness of ice or snow (expressed as a thickness of melt-water equivalent), the model was extended to develop a material cost per lane mile for the full range of possible mixtures as a function of temperature. This allowed for a comparison of the performance of the various mixtures. From the point of view of melting capacity, mixing calcium chloride brine with salt brine appears to be effective only at very low temperatures (around 0° F and below). However, the approach described herein only considers the material costs, and does not consider application costs or other aspects of the mixture performance than melting capacity. While a unit quantity of calcium chloride is considerably more expensive than a unit quantity of sodium chloride, it also melts considerably more ice. In other words, to achieve the same result, much less calcium chloride brine is required than sodium chloride brine. This is important in considering application costs, because it means that a single application vehicle (for example, a brine dispensing trailer towed behind a snowplow) can cover many more lane miles with calcium chloride brine than with salt brine before needing to refill. Calculating exactly how much could be saved in application costs requires an optimization of routes used in the application of liquids in anti-icing, which is beyond the scope of the current study. However, this may be an area that agencies wish to pursue for future investigation. In discussion with winter maintenance personnel who use mixtures of sodium chloride and calcium chloride, it is evident that one reason for this is because the mixture is much more persistent (i.e. it stays longer on the road surface) than straight salt brine. Operationally this persistence is very valuable, but at present there are not any established methods to measure the persistence of a chemical on a pavement. In conclusion, the study presents a method that allows an agency to determine the material costs of using various mixtures of salt brine and calcium chloride brine. The method is based upon the requirement of melting a certain quantity of snow or ice at the ice-pavement interface, and on how much of a chemical or of a mixture of chemicals is required to do that.

Construction mechanisms and thermal evolution of upper crustal intrusions : the Saint-Jean-du-Doigt bimodal intrusion (Brittany, France)

Understanding the emplacement and growth of intrusive bodies in terms of mechanism, duration, ther¬mal evolution and rates are fundamental aspects of crustal evolution. Recent studies show that many plutons grow in several Ma by in situ accretion of discrete magma pulses, which constitute small-scale magmatic reservoirs. The residence time of magmas, and hence their capacities to interact and differentiate, are con¬trolled by the local thermal environment. The latter is highly dependant on 1) the emplacement depth, 2) the magmas and country rock composition, 3) the country rock thermal conductivity, 4) the rate of magma injection and 5) the geometry of the intrusion. In shallow level plutons, where magmas solidify quickly, evi¬dence for magma mixing and/or differentiation processes is considered by many authors to be inherited from deeper levels. This work shows however that in-situ differentiation and magma interactions occurred within basaltic and felsic sills at shallow depth (0.3 GPa) in the St-Jean-du-Doigt (SJDD) bimodal intrusion, France. This intrusion emplaced ca. 347 Ma ago (IDTIMS U/Pb on zircon) in the Precambrian crust of the Armori- can massif and preserves remarkable sill-like emplacement processes of bimodal mafic-felsic magmas. Field evidence coupled to high precision zircon U-Pb dating document progressive thermal maturation within the incrementally built ioppolith. Early m-thick mafic sills (eastern part) form the roof of the intrusion and are homogeneous and fine-grained with planar contacts with neighboring felsic sills; within a minimal 0.8 Ma time span, the system gets warmer (western part). Sills are emplaced by under-accretion under the old east¬ern part, interact and mingle. A striking feature of this younger, warmer part is in-situ differentiation of the mafic sills in the top 40 cm of the layer, which suggests liquids survival in the shallow crust. Rheological and thermal models were performed in order to determine the parameters required to allow this observed in- situ differentiation-accumulation processes. Strong constraints such as total emplacement durations (ca. 0.8 Ma, TIMS date) and pluton thickness (1.5 Km, gravity model) allow a quantitative estimation of the various parameters required (injection rates, incubation time,...). The results show that in-situ differentiation may be achieved in less than 10 years at such shallow depth, provided that: (1) The differentiating sills are injected beneath consolidated, yet still warm basalt sills, which act as low conductive insulating screens (eastern part formation in the SJDD intrusion). The latter are emplaced in a very short time (800 years) at high injection rate (0.5 m/y) in order to create a "hot zone" in the shallow crust (incubation time). This implies that nearly 1/3 of the pluton (400m) is emplaced by a subsequent and sustained magmatic activity occurring on a short time scale at the very beginning of the system. (2) Once incubation time is achieved, the calculations show that a small hot zone is created at the base of the sill pile, where new injections stay above their solidus T°C and may interact and differentiate. Extraction of differentiated residual liquids might eventually take place and mix with newly injected magma as documented in active syn-emplacement shear-zones within the "warm" part of the pluton. (3) Finally, the model show that in order to maintain a permanent hot zone at shallow level, injection rate must be of 0.03 m/y with injection of 5m thick basaltic sills eveiy 130yr, imply¬ing formation of a 15 km thick pluton. As this thickness is in contradiction with the one calculated for SJDD (1.5 Km) and exceed much the average thickness observed for many shallow level plutons, I infer that there is no permanent hot zone (or magma chambers) at such shallow level. I rather propose formation of small, ephemeral (10-15yr) reservoirs, which represent only small portions of the final size of the pluton. Thermal calculations show that, in the case of SJDD, 5m thick basaltic sills emplaced every 1500 y, allow formation of such ephemeral reservoirs. The latter are formed by several sills, which are in a mushy state and may interact and differentiate during a short time.The mineralogical, chemical and isotopic data presented in this study suggest a signature intermediate be¬tween E-MORB- and arc-like for the SJDD mafic sills and feeder dykes. The mantle source involved produced hydrated magmas and may be astenosphere modified by "arc-type" components, probably related to a sub¬ducting slab. Combined fluid mobile/immobile trace elements and Sr-Nd isotopes suggest that such subduc¬tion components are mainly fluids derived from altered oceanic crust with minor effect from the subducted sediments. Close match between the SJDD compositions and BABB may point to a continental back-arc setting with little crustal contamination. If so, the SjDD intrusion is a major witness of an extensional tectonic regime during the Early-Carboniferous, linked to the subduction of the Rheno-Hercynian Ocean beneath the Variscan terranes. Also of interest is the unusual association of cogenetic (same isotopic compositions) K-feldspar A- type granite and albite-granite. A-type granites may form by magma mixing between the mafic magma and crustal melts. Alternatively, they might derive from the melting of a biotite-bearing quartz-feldspathic crustal protolith triggered by early mafic injections at low crustal levels. Albite-granite may form by plagioclase cu¬mulate remelting issued from A-type magma differentiation.

Trace element chemistry and U-Pb dating of zircons from oceanic gabbros and their relationship with whole rock composition (Lanzo, Italian Alps)

The U-Pb ages and the trace element content of zircon U-Pb along with major and trace element whole rock data on gabbroic dikes from the Lanzo lherzolitic massif, N-Italy, have been determined to constrain crustal accretion in ocean-continent transition zones. Three Fe-Ti gabbros were dated from the central and the southern part of the massif providing middle Jurassic ages of 161 +/- 2, 158 +/- 2 and 163 +/- 1 Ma, which argue for magmatic activity over few millions of years. Zircon crystals are characterized by high but variable Th/U ratios, rare earth element patterns enriched in heavy rare earths, pronounced positive Ce and negative Eu-anomalies consistent with crystallization after substantial plagioclase fractionation. The zircon trace element composition coupled with whole rock chemistry was used to reconstruct the crystallization history of the gabbros. A number of gabbros crystallized in situ, and zircon precipitated from trapped, intercumulus liquid, while other gabbros represent residual liquids that were extracted from a cumulus pile and crystallized along syn-magmatic shear zones. We propose a model in which the emplacement mechanism of gabbroic rocks in ocean-continent transition zones evolves from in situ crystallization to stratified crystallization with efficient extraction of residual liquid along syn-magmatic shear zones. Such an evolution of the crystallization history is probably related to the thermal evolution of the underlying mantle lithosphere.

Epidote in hydrous mafic magmas : near solidus phase relations in the lower crust

Crystallisation of hydrous mafic magmas at high pressure is a subject of numerous petrologic and experimental studies since the last century and is mainly related to the process of continental crust formation and the possible link between mantle derived melts and low pressure granitoids. Albeit the sequence of crystallization is well constrained by experimental studies, the origin of exposed lower crustal rocks exposed on the earth surface is controversial. Ones line of argument is favouring high pressure crystallization of dry or wet mafic magmas, whereas others invoke partial melting of pre-existing crust. Therefore studies involving field, textural and chemical observations of exposed lower crust such as in Kohistan (Pakistan) or Talkeetna (Alaska) are crucial to understand the continental crust formation processes via arc magmatism. Epidote-bearing gabbros are very sparse and always associated with the deep part of continental crust (>30 km) as in the Kohistan Arc Complex (Pakistan) or in the Chelan Complex (western U.S.). Magmatic epidote is restricted to a small temperature interval above the water-saturated solidus of MORB and represent the last crystallizing liquids in lower crustal regions. However, epidote and melt stability at lower crustal pressures are not clearly established.¦The Chelan complex (western U.S.) at the base of the Cascadian Arc is composed mainly by peraluminous tonalité associated with gabbroic and ultramafic rocks and was traditionally interpreted as a migmatitic terrain. However field, chemical and mineralogical observations rather suggest a magmatic origin and point to a protracted crystallization at intermediate to high pressure ~ 1.0 GPa dominated by amphibole fractionation and followed by isobaric cooling down to 650°C. Crystal fractionation modelling using whole rock composition and field constraints is able to generate peraluminous tonalité. The modelled crystallisation sequence and the volume proportions are in agreement with experimental studies performed at these pressures. The Chelan complex was thus not formed during a partial melting event, but represent the sequence of crystallisation occurring at the base of the crust. Massive fractionation of hornblende is able to generate peraluminous tonalité without significant assimilation of crustal rock.¦Similarly to the Chelan complex, the base of the Kohistan arc is composed of cumulates derived by high pressure crystallization of hydrous magma. In garnet gabbros, epidote occurs as magmatic phase, crystallising from hydrous interstitial melt trapped between grain boundaries at lower crustal pressures (Ρ ~ 1.2 GPa) for temperature of (650-700 °C). Trace and REE signature in epidote indicate that epidote was formed through peritectic reaction involving garnet, clinopyroxene and plagioclase. At the beginning of the crystallisation epidote signature is dominated by REE content in the melt, whereas at the end the signature is dominated by reacting phases. Melt in equilibrium with epidote inferred from the partition coefficients available is similar to intrusive tonalité up the section indicating that hydrous melt was extracted from the garnet gabbros. In some gabbros epidote shows single homogeneous compositions, while in others coexisting epidote have different compositions indicating the presence of solvi along the Al-Fe3+ join. The overgowths are only observed in presence of paragonite in the assemblage, suggesting high water content. At high water content, the hydrous solidus is shift to lower temperature and probably intersects the solvi observed along the Al-Fe3+ join. Therefore, several compositions of epidote is stable at high water content.¦-¦La composition chimique de la croûte continentale est considérée comme similaire à celle du magmatisme calco-alcalin de marge continentale active (enrichissement en éléments mobiles dans les fluides, anomalies négatives en Nb, Ta et éléments à haut potentiel électronique, etc...). Cependant la nature andésitique de la croûte continentale (Si02 > 60 wt%), résultant des nombreuses intrusions de granitoïdes dans la croûte supérieure, est sujette à polémique et le lien entre les magmas dérivés du manteau et les roches évoluées de faible profondeur n'est pas clairement établi (fusion partielle de croûte basaltique, cristallisation fractionnée à haute pression, etc...).¦Les affleurements de croûte profonde sont rares mais précieux, car ils permettent d'observer les phénomènes se passant à grande profondeur. Le complexe de Chelan (Washington Cascades) en est un exemple. Formé à environ 30 km de profondeur, il est composé de roches gabbroïques et ultramafiques, ainsi que de tonalités, qui furent souvent interprétés comme le produit de la fusion partielle de la croûte. Cependant, les relations de terrain, la chimie des éléments majeurs et des éléments traces sont cohérentes avec l'évolution d'un complexe magmatique mafique dans la croûte profonde ou moyenne ( 1.0 GPa), dominée par le fractionnement de l'amphibole. Après son emplacement, le complexe a subi un refroidissement isobare jusqu'à des températures de l'ordre de 650 °C, déduit de la composition chimique des minéraux. Un bilan de masse contraint pax les observations de terrain permet de calculer la séquence et les volumes de fractionnement. Les faciès évolués légèrement hyperalumineux observés sur le terrain peuvent être générés par la cristallisation de 3 % de websterite à olivine, 12 % d'hornblendite à pyroxène 33 % d'hornblendite, 19 % de gabbros, 15 % de diorite et 2 % de tonalité. Nous montrons ainsi qu'une série de fractionnement contrôlée par l'amphibole permet de générer des tonalités sans assimilation de matériel crustal et l'exemple de Chelan illustre la viabilité de ce processus dans la formation de croûte continentale.¦Les réactions proches du solidus saturé en H20 dans les systèmes basaltiques à des pressions élevées restent énigmatiques. Diverses expériences tendent à montrer que l'épidote est stable dans ces conditions, mais rarement observée (décrite ?) comme phase primaire dans les systèmes naturels. Les épidotes trouvées dans les gabbros de Jijal (nord-Pakistan) montrent des textures de type .magmatique telles qu'observées dans les roches évoluées. Le contenu en terres rares de ces épidotes est très variable allant de signatures enrichies en terres rares légères impliquant la présence de liquide interstitiel à des signatures complètement déprimées en ces mêmes éléments, évoquant une cristallisation en coexistence avec du grenat. Ces diverses signatures reflètent un chemin de cristallisation en présence de liquide interstitiel et enregistrent des réactions péritectiques impliquant grenat, clinopyroxene et plagioclase à des pressions de ~ 1.2 GPa pour des températures de 650-700 °C. Cependant dans quelques échantillons deux ou trois compositions d'épidotes coexistent démontrant la présence de lacunes d'immiscibilité le long de la solution solide épidote-clinozoïsite. La forte teneur en H20 du liquide magmatique est certainement à l'origine de la coexistence de deux compositions distinctes.

Study of isotopic variations in black powder: reflections on the use of stable isotopes in forensic science for source inference.

Isotope ratio mass spectrometry (IRMS) has recently made its appearance in the forensic community. This high-precision technology has already been applied to a broad range of forensic fields such as illicit drugs, explosives and flammable liquids, where current, routinely used techniques have limited powers of discrimination. The conclusions drawn from the majority of these IRMS studies appear to be very promising. Used in a comparative process, as in food or drug authentication, the measurement of stable isotope ratios is a new and remarkable analytical tool for the discrimination or the identification of a substance with a definite source or origin. However, the research consists mostly of preliminary studies. The significance of this 'new' piece of information needs to be evaluated in light of a forensic framework to assess the actual potential and validity of IRMS, considering the characteristics of each field. Through the isotopic study of black powder, this paper aims at illustrating the potential of the method and the limitations of current knowledge in stable isotopes when facing forensic problems.

Kinetics of selective oxidation of lactose to lactobionic acid over Pd-active carbon catalyst

Laktoosi eli maitosokeri on tärkein ainesosa useimpien nisäkkäiden tuottamassa maidossa. Sitä erotetaan herasta, juustosta ja maidosta. Laktoosia käytetään elintarvike- ja lääketeollisuuden raaka-aineena monissaeri tuotteissa. Lääketeollisuudessa laktoosia käytetään esimerkiksi tablettien täyteaineena. Hapettamalla laktoosia voidaan valmistaa laktobionihappoa, 2-keto-laktobionihappoa ja laktuloosia. Laktobionihappoa käytetään biohajoavien pintojen ja kosmetiikkatuotteiden valmistuksessa, sekä sisäelinten säilöntäliuoksissa, joissa laktobionihappo estää happiradikaalien aiheuttamien kudosvaurioiden syntymistä. Tässä työssä laktoosia hapetettiin laktobionihapoksi sekoittimella varustetussa laboratoriomittakaavaisessa panosreaktorissa käyttäenkatalyyttinä palladiumia aktiivihiilellä. Muutamissa kokeissa katalyytin promoottorina käytettiin vismuttia, joka hidastaa katalyytin deaktivoitumista. Työn tarkoituksena oli saada lisää tietoa laktoosin hapettamisen kinetiikasta. Laktoosin hapettumisessa laktobionihapoksi havaittiin selektiivisyyteen vaikuttavan muunmuassa reaktiolämpötila, paine, pH ja käytetyn katalyytin määrä. Katalyyttiä kierrättämällä eri kokeiden välillä saatiin paremmat konversiot, selektiivisyydet ja saannot. Parhaat koetulokset saatiin hapetettaessa synteettisellä ilmalla 60 oC lämpötilassa ja 1 bar paineessa. Tehdyissä kokeissa pH:n säätö tehtiin manuaalisesti, joten pH ei pysynyt koko ajan haluttuna. Laktoosin konversio oli parhaimmillaan 95 %. Laktobionihapon suhteellinen selektiivisyys oli 100% ja suhteellinen saanto 100 %. Kinetiikan matemaattinen mallinnus tehtiin Modest-ohjelmalla käyttäen kokeista saatuja mittaustuloksia.Ohjelman avulla estimoitiin parametreja ja saatiin matemaattinen malli reaktorille. Tässä työssä tehtiin kineettinen mallinnus myös ravistelureaktorissa tehdyille laktoosin hapetuskokeille, missä pH pysyi koko ajan haluttuna 'in-situ' titrauksen avulla. Työn yhteydessä selvitettiin myös mahdollisuutta käyttää monoliittikatalyyttejä laktoosin hapetusreaktiossa.

The Paleozoic magmatic history of the Maggia and Sambuco nappes, Lower Penninic, Central Lepontine Alps

Résumé : Les corps magmatiques sont des indicateurs essentiels dans toute reconstitution paléogéographique et/ou géodynamique d'un cycle orogénique, en particulier en contexte polycyclique, où la plupart des autres indices ont été oblitérés. Ils sont aisément datables et leurs caractéristiques géochimiques permettent de contraindre leur contexte tectonique de mise en place. Cette approche a été appliquée aux socles pré-mésozoïques des nappes penniques inférieures de Sambuco et de la Maggia, dans les Alpes centrales lepontines. Plusieurs événements magmatiques ont été identifiés dans le socle de Sambuco et datés par la méthode U-Pb sur zircon couplée à la technique LA-ICPMS. La suite calco-alcaline mafique rubanée de Scheggia est datée du Cambrien inférieur à 540-530 Ma ; le métagranite alumineux oeillé de Sasso Nero a un âge de 480-470 Ma, tout comme bien d'autres «older orthogneisses» des socles alpins. Il contient des zircons hérités d'âge panafricain à 630-610 Ma, indicateur d'une affiliation gondwanienne de ces terrains. Le pluton calco-alcalin du Matorello est daté à environ 300-310 Ma, et les filons lamprophyriques qu'il abrite à 300 Ma. La granodiorite de Cocco et le leucogranite de Ruscada, tous deux intrudés dans le socle de la nappe adjacente de la Maggia, ont des âges similaires à celui du Matorello. Ceci ajouté aux similitudes magmatiques observées entre Cocco et Matorello suggère une proximité paléogéographique des deux nappes au Permien-Carbonifère. Or ces dernières sont actuellement considérées appartenir à deux domaines paléogéographiques mésozoïques distincts : helvétique pour Sambuco et briançonnais pour Maggia, séparés par un bassin océanique. Si tel fut le cas, aucun mouvement décrochant ne doit avoir décalé les marges continentales de l'océan, retrouvées en parfaite coïncidence lors de sa fermeture. Le Matorello est un pluton recristallisé en faciès amphibolite et plissé par cinq phases successives de déformation non-coaxiales, qui ont conduit à son renversement complet, attesté par des indicateurs de paléogravité. Il préserve de spectaculaires phénomènes de coexistence liquide de magmas (essaims d'enclaves et Bills composites). Ce pluton était originellement tabulaire, construit par l'accumulation de multiples injections de magma en feuillets d'épaisseur métrique à décamétrique. Suivant le rythme de mise en place, les injections successives ont rapidement cristallisé avec des contours nets et bien définis (Bills composites) ou se sont mélangées avec les précédentes pour former une couche non consolidée de plusieurs dizaines de mètres d'épaisseur (granodiorite principale). Les injections individuelles sont délimitées par de subtils contrastes en granulométrie, proportions modales ou ségrégation de minéraux (schlieren), ou par des phénomènes d'érosion le long des surfaces de contact. Deux couches métriques à contour sinueux consistent en une accumulation compacte d'enclaves mafiques arrondies dans une matrice granodioritique fine. Le granoclassement des enclaves, la présence de figures de charge et de phénomènes érosifs en base de couche, ainsi que des schlieren de biotite entrecroisés évoquent l'injection de coulées de magma chargé d'enclaves et de faible viscosité en régime hydrodynamique turbulent dans un encaissant granodioritique encore largement liquide. La nature hybride des roches implique une chambre magmatique sous-jacente, en cours de différenciation et périodiquement réalimentée. Les magmas sont des liquides mafiques dérivés du manteau et des liquides anatectiques d'origine crustale, comme l'indique la gamme mesurée des rapports isotopiques initiaux du Sr (0.704 à 0.709) et des valeurs epsilon Nd (-2.1 à -4.7). Ces données montrent également que la contribution crustale est dominante, en accord avec les isotopes du plomb. Les phénomènes d'hybridation ont vraisemblablement eu lieu en base de croûte et dans la chambre magmatique sous-jacente au laccolite du Matorello. Les indicateurs de paléogravité du Matorello contribuent accessoirement à la compréhension de l'architecture actuelle de la nappe de Sambuco. Des plis isoclinaux à surface axiale verticale peuvent être mis en évidence par le contact entre les faciès dioritique et granodioritique. L'antiforme dont le Matorello forme le coeur est un synclinal, ce qui le positionne dans le Flanc inverse du grand pli couché que forme la nappe de Sambuco. Par ailleurs, des blocs de gneiss retrouvés dans le wildflysch sommital de la couverture de la nappe d'Antigorio ont été affiliés dans cette étude au pluton du Matorello. Ceci implique que le front de la nappe de Sambuco chevauchait déjà la partie est du bassin d'Antigorio au moment de sa fermeture. Par conséquent, ce n'est qu'en position externe que la nappe du Lebendun chevauche directement la nappe d'Antigorio. Abstract Magmatic bodies are important markers in paleo-geographic or geodynamic reconstructions of orogenic cycles, even more so in the case of polycyclic events where many of the other markers have been overwritten or destroyed. Plutons are relatively easy to date and their geochemical properties help constrain the tectonic context in which they were emplaced. This study focuses on the pre-mesozoic basement in the Sambuco and Maggia lower Penninic nappes located in the central Lepontine domain of the Alps. A number of magmatic events have been identified in the Sambuco basement. These events were dated using LA-ICPMS U/Pb on zircon grains. The mafic calc-alkaline banded Scheggia suite is dated as lower Cambrian, 540-530 Ma. The Al-rich Sasso-Nero lenticular gneiss is 480-470 Ma old (similarly to many older orfhogneisses of the Alpine basement) and contains 630-610 Ma old pan-African inherited zircons that illustrate the Gondwanian origin of these terranes.The calc-alkaline Matorello pluton is dated as 310-300 Ma whereas the lamprophyric bodies it contains are of 300 Ma. The Cocco granodiorite and the Ruscada leucogranite both intrude the basement of the adjacent Maggia nappe and are of similar ages to the Matorello. The ages as well as the geochemical similarities between the Cocco, Rucada and Matorello plutons suggest their paleo-geographic proximity at the Permian-Carboniferous boundary. However, these nappes are currently considered as belonging to two different Mesozoic paleo-geographic domains. Indeed, the Sambuco is considered as Helvetic whereas the Maggia is said to be Briançonnais, both separated by an oceanic basin. If this is the case, then it is essential that nostrike-slip movement has misaligned both continental margins since these coincide perfectly now that the oceanic domain closed. The Matorello pluton was originally a tabular intrusion, built up by the accumulation of multiple, several meter-thick, subhorizontal sheet-like injections of magma. Depending on their emplacement rate, the successive magma injections either solidified rapidly with sharp and rather well-defined boundaries (like the composite sills) or mingled with previous injections generating a thick molten layer up to several tens to hundred meters thick, like in the main granodioritic facies. These coalesced injections are hardly distinguishable, however subtle contrasts in granulometry, mineral modal proportions or mineral sorting (cross-bedded biotite-rich schlieren), as well as erosional features and/or crystal entrapment along contact surfaces allow to distinguish between the different injections. Two exceptional meter-thick layers display sinuous boundaries with the host granodiorite and consist of a densely packed accumulation of mafic enclaves in a granodioritic matrix. Gravitational sorting of the enclaves with load cast features at the base of the layers and sinuous biotite schlieren point to injection of low viscosity turbulent composite magma flows in the still largely molten granodiorite host. The hybrid nature of these rocks implies the existence of á periodically replenished and differentiated underlying magma chamber. Magmas are mafic liquids derived from the mantle and anatectic liquids of crustal origin, as shown by the (87Sr/86Sr), and epsilon Nd values (0.704-0.709 and -2.1 to -4.7 respectively. These data show that the crustal contribution is important, as confirmed by the Pb isotopes. The hybridisation processes seem to have occurred in the lower crust in magma chambers underlying the Matorello laccolith. The paleo-gravity markers in the Matorello help understand the architecture of the Sambuco nappe. Isoclinal folds with a vertical axial plane can be seen at the contact between dioritic and granodioritic facies. The antiform structure of which the Matorello is the heart is in fact a syncline. This places it in the inverse flanc of the large recumbent fold that constitutes the Sambuco nappe. The gneiss blocs found in the summital wildflysh cover of the Antigorio nappe have been linked to the Matorello pluton. This means that the front of the Sambuco nappe already overlapped the Antigorio basin when it closed. This implies that the Lebendun nappe can only overlap the Antigorio nappe in it's external position. Résumé grand public La chaîne alpine est la conséquence de la collision tertiaire entre deux masses continentales, l'Europe au nord et la péninsule apulienne africaine au sud, originellement séparées par l'océan mésozoïque téthysien. Cette collision a fermé un espace large de plusieurs centaines de km avec pour résultat l'écaillage de la croûte terrestre en unités tectoniques de dimensions variables, qui se sont empilées, imbriquées, éventuellement replissées en nappes de géométrie complexe. Cet amoncellement de 40 km d'épaisseur a vu sa température et sa pression lithostatique internes augmenter jusqu'à des valeurs de l'ordre de 680 °C et 6000 bars, induisant une recristallisation métamorphique des roches. L'un des objectifs de la géologie alpine est de reconstituer la géographie de la région aux temps mésozoïques de l'océan téthysien, en d'autres termes, de replacer chacune des unités tectoniques identifiées au sein de l'empilement alpin dans sa position originelle. Le défi est de taille et peut être comparé à celui de la reconstitution d'un vaste puzzle, dont certaines pièces seraient endommagées au niveau de leur contour ou leurs couleurs (métamorphisme), dissimulées par d'autres (enfouissement), voire tombées de la table de jeu (subduction, échappement latéral). Plusieurs approches ont été mises en oeuvre au cours du siècle écoulé. On citera en particulier la stratigraphie, la tectonique et le paléomagnétisme. Dans ce travail, nous avons essentiellement utilisé des techniques de datation isotopique absolue des roches (U/Pb sur zircon) qui, sur la base des connaissances acquises par l'ensemble des autres disciplines géologiques, nous ont permis de mieux contraindre ta paléogéographie mésozoïque du domaine «pennique inférieur » des Alpes centrales lépontines. Et au-delà? Nous savons tous que la disposition des continents à la surface de la Terre évolue constamment. Il est donc tentant d'essayer de remonter plus loin encore dans le temps et de reconstituer la physionomie de la marge sud européenne, tout au moins certains éléments de son histoire, au cours de l'ère paléozoïque. Les traces de ces événements très anciens sont naturellement ténues et dans ce contexte, les techniques de datation mentionnées ci-dessus deviennent les outils les plus performants. Ainsi, des datations u/Pb sur zircon nous ont permis de recenser plusieurs intrusions magmatiques, attribuées à quatre événements orogéniques anté-alpins. Des âges néoprotérozoïques (630-610 millions d'années ou Ma), cambrien inférieur (540-530 Ma), ordovicien inférieur (480-470 Ma) et carbonifère supérieur-permien inférieur (310-285 Ma) ont été obtenus dans le socle de la nappe de Sambuco. Des âges similaires à 300 Ma ont été obtenus dans la nappe voisine de la Maggia, qui permettent de relier ces deux unités. Aujourd'hui côte à côte, ces deux nappes devaient également se trouver proches l'une de l'autre il y a 300 Ma, lors de l'extension post-varisque. Les structures magmatiques spectaculaires préservées dans le pluton du Matorello (300 Ma) contraignent la géométrie actuelle de la nappe de Sambuco dans laquelle l'intrusion s'est mise en place. La forme originelle du pluton, aujourd'hui retourné et replissé plusieurs fois, s'avère être tabulaire, faite d'intrusions de faible épaisseur (1-300 m) s'étalant en forme de disque (30m à 2 km de diamètre). Les injections successives de magma se sont accumulées sous un toit dioritique précoce; elles sont issues, par le refais de fractures, d'une chambre magmatique plus profonde, périodiquement réalimentée par des magmas calco-alcalins d'origine mantellique contaminés parla croûte continentale profonde (εNd = -2.1 à -4.7). Des accumulations d'enclaves magmatiques arrondies et granoclassées dans des paléo-chenaux à fond érosif témoignent de conditions de mise en place hydrodynamiques à haute énergie. Ces enclaves sont emmenées de la chambre magmatique sous-jacente à la faveur d'épisodes de fracturation hydraulique liés à l'injection de magmas matelliques chauds dans des liquides différenciés riches en eau. Cette hypothèse est étayée par l'existence de filons composites. Une paléohorizontale a pu être déduite au sein du pluton, indiquant que cette partie de la nappe de Sambuco est verticalisée et isoclinalement replissée par la déformation alpine. Finalement, des blocs érodés du socle Sambuco ont été retrouvés dans le wildflysch sommital de la couverture sédimentaire mésozoïque de la nappe d'Antigorio sous-jacente. Ceci suggère que les blocs ont été fournis parle front de la nappe de Sambuco en train de chevaucher sur la nappe d'Antigorio au moment de la fermeture du bassin sédimentaire de cette dernière.

Growth and functionalization of carbon nanotubes on quartz filter for environmental applications

Background: Air pollution has become an important issue worldwide due to its adverse health effects. Among the different air contaminants, volatile organic compounds (VOCs) are liquids or solids with a high vapor pressure at room temperature that are extremely dangerous for human health. Removal of these compounds can be achieved using nanomaterials with tailored properties such as carbon nanotubes. Methods: Vertically-aligned multiwall carbon nanotubes (CNTs) were successfully grown on quartz filters by means of plasma enhanced chemical vapor deposition (PECVD). Furthermore, a plasma treatment was performed in order to modify the surface properties of the CNTs. The adsorption/desorption processes of three chlorinated compounds (trichloroethylene, 1,2-dichlorobenzene and chloroform) on the CNTs were studied using mass spectrometry measurements with a residual gas analyzer. Results: The adsorption capability of the CNTs increased after functionalization of their surface with a water plasma treatment. In addition, it was found that the presence of aromatic rings, water solubility and polarity of the VOCs play an important role on the adsorption/desorption kinetics at the CNTs surface. Conclusions: This study demonstrates the applicability of CNTs deposited on quartz filters for the removal or selective detection of volatile organic compounds (VOCs). The presence of aromatic rings in VOCs results in π -stacking interactions with a significant increase of their adsorption. On the other hand, it was found that CNTs surface interactions increase with water solubility and polarity of the VOC.

The Mont Collon mafic complex (Austroalpine Dent Blanche nappe) : permian evolution of the Western European mantle

Résumé: Le complexe du Mont Collon (nappe de la Dent Blanche, Austroalpin) est l'un des exemples les mieux préservés du magmatisme mafique permien des Alpes occidentales. Il est composé d'affleurements discontinus et d'une stratification magmatique en son centre (Dents de Bertol) et est composé à 95% de roches mafiques cumulatives (gabbros à olivine et/ou cpx, anorthositiques, troctolites, wehrlites et wehrlites à plagioclase) et localement de quelques gabbros pegmatitiques. Ces faciès sont recoupés par de nombreux filons acides (aphtes, pegmatites quartziques, microgranodiorites et filons anorthositiques) et mafiques tardifs (dikes mélanocrates riches en Fe et Ti). Les calculs thermométriques (équilibre olivine-augite) montrent des températures de 1070-1120 ± 6°C, tandis que le thermomètre amphibole-plagioclase indique une température de 740 ± 40°C à 0.5 GPa pour les amphiboles magmatiques tardives. La geobarométrie sur pyroxène donne des pressions moyennes de 0.3-0.6 GPa, indiquant un emplacement dans la croûte moyenne. De plus, les températures obtenues sur des amphiboles coronitiques indiquent des températures de l'ordre de 700 ± 40°C confirmant que les réactions coronitiques apparaissent dans des conditions subsolidus. Les âges concordants U/Pb sur zircons de 284.2 ± 0.6 et 282.9 ± 0.6 Ma obtenus sur un gabbro pegmatitique et une pegmatitique quartzique, sont interprétés comme des âges de cristallisation. Les datations 40Ar/39Ar sur amphiboles des filons mélanocrates donnent un âge plateau de 260.2 ± 0.7 Ma, qui est probablement très proche de l'âge de cristallisation. Ainsi, cet age 40Ar/39Ar indique un second évènement magmatique au sein du complexe. Les compositions des roches totales en éléments majeurs et traces montrent peu de variations, ainsi que le Mg# (75-80). Les éléments traces enregistrent le caractère cumulatif des roches (anomalie positive en Eu) et révèlent des anomalies négatives systématiques en Nb, Ta, Zr, Hf et Ti dans les faciès basiques. Le manque de corrélation entre éléments majeurs et traces est caractéristique d'un processus de cristallisation in situ impliquant une quantité variable de liquide interstitiel (L) entre les phases cumulus. Les distributions des éléments traces dans les minéraux sont homogènes, indiquant une rééquilibration .subsolidus entre cristaux et liquide interstitiel. Un modèle quantitatif basé sur les équations de cristallisation in situ de Langmuir reproduisent correctement les concentrations en terres rares légères des minéraux cumulatifs montrant la présence de 0 à 35% de liquide interstitiel L pour des degrés de différenciation F de 0 à 45%, par rapport au faciès les moins évolués du complexe. En outre, les valeurs de L sont bien corrélées avec les proportions modales d'amphibole interstitielle et les concentrations en éléments incompatibles des roches (Zr, Nb). Le liquide parental calculé des cumulats du Mont Collon est caractérisé par un enrichissement relatif en terres rares légères et Th, un appauvrissement en terres rares lourdes typique d'une affinité transitionnelle (T-MORB) et une forte anomalie négative en Nb-Ta. Les roches cumulatives montrent des compositions isotopiques en Nd-Sr proches de la terre globale silicatée (BSE), soit 0.6<εNdi<+3.2, 0.7045<87Sr/86Sri<0.7056. Les rapports initiaux en Pb indiquent une source dans le manteau enrichi subcontinental lithosphérique, préalablement contaminé par des sédiments océaniques. Les dikes mélanocrates Fe-Ti sont représentatifs de liquides et ont des spectres de terres rares enrichis, une anomalie positive en Nb-Ta et des εNdi de +7, des 87Sr/86Sri de 0.703 et des rapports initiaux en Pb, similaires à ceux des basaltes d'île océanique, indiquant une source asthénosphérique modérément appauvrie. Ainsi, la fusion partielle du manteau lithosphérique subcontinental est induite par l'amincissement post-orogénique et la remontée de l'asthénosphère. Les filons mélanocrates proviennent, après délamination du manteau lithosphérique, de la fusion de l'asthénosphère. Abstract The early Permian Mont Collon mafic complex (Dent Blanche nappe, Austroalpine nappe system) is one of the best preserved examples of the Permian mafic magmatism in the Western Alps. It is composed of discontinuous exposures and a well-preserved magmatic layering (the Dents de Bertol cliff) crops out in the center part of the complex. It mainly consists of cumulative mafic rocks, which represent 95 vol-% of the mafic complex (ol- and cpx-bearing gabbros and rare anorthositic layers, troctolites, wehrlites and plagioclase-wehrlites) and locally pegmatitic gabbros. All these facies are crosscut by widespread acidic (aplites, quartz-rich pegmatites, microgranodiorites) and late mafic Fe-Ti melanocratic dikes. Olivine-augite thermometric calculations yield a range of 1070-1120 ± 6°C, while amphibole-plagioclase thermometer yields a temperature of 740 ± 40°C at 0.5 GPa. Pyroxene geobarometry points to a pressure of 0.3-0.6 GPa, indicating a middle crustal level of emplacement. Moreover, temperature calculations on the Mont Conon coronitic amphiboles indicate temperatures of 700 ± 40°C, close to those calculated for magmatic amphiboles. These temperatures confirm that coronitic reactions occurred at subsolidus conditions. ID-TIMS U/Pb zircon ages of 284.2 ± 0.6 and 282.9 ± 0.6 Ma obtained on a pegmatitic gabbro and a quartz-pegmatitic dike, respectively, were interpreted as the crystallization ages of these rocks. 40Ar/39Ar dating on amphiboles from Fe-Ti melanocratic dikes yields a plateau age of 260.2 ± 0.7 Ma, which is probably very close to the crystallization age. Consequently, this 40Ar/P39Ar age indicates a second magmatic event. Whole-rock major- and trace-element compositions show little variation across the whole intrusion and Mg-number stays within a narrow range (75-80). Trace-element concentrations record the cumulative nature of the rocks (e.g. positive Eu anomaly) and reveal systematic Nb, Ta, Zr, Hf and Ti negative anomalies for all basic facies. The lack of correlation between major and trace elements is characteristic of an in situ crystallization process involving variable amounts of interstitial liquid (L) trapped between the cumulus mineral phases. LA-ICPMS measurements show that trace-element distributions in minerals are homogeneous, pointing to subsolidus re-equilibration between crystals and interstitial melts. A quantitative modeling based on Langmuir's in situ crystallization equation successfully reproduced the Rare Earth Element (REE) concentrations in cumulitic minerals. The calculated amounts of interstitial liquid L vary between 0 and 35% for degrees of differentiation F of 0 to 45%, relative to the least evolved facies of the intrusion. Furthermore, L values are well correlated with the modal proportions of interstitial amphibole and whole-rock incompatible trace-element concentrations (e.g. Zr, Nb) of the tested samples. The calculated parental melt of the Mont Collon cumulates is characterized by a relative enrichment in Light REE and Th, a depletion in Heavy REE, typical of a transitional affinity (T-MORB), and strong negative Nb-Ta anomaly. Cumulative rocks display Nd-Sr isotopic compositions close to the BSE (-0.6 < εNdi < +3.2, 0.7045 < 87Sr/86Sri < 0.7056). Initial Pb ratios point to an origin from the melting of an enriched subcontinental lithospheric mantle source, previously contaminated at the source by oceanic sediments. The contrasted alkaline Fe-Ti melanocratic dikes are representative of liquids. They display enriched fractionated REE patterns, a positive Nb-Ta anomaly and εNdi of +7, 87Sr/86Sri of 0.703 and initial Pb ratios, all reminiscent of Ocean Island Basalt-type rocks, pointing to a moderately

Ion-exchange resins as stationary phase in reactive chromatography

Dynamic behavior of bothisothermal and non-isothermal single-column chromatographic reactors with an ion-exchange resin as the stationary phase was investigated. The reactor performance was interpreted by using results obtained when studying the effect of the resin properties on the equilibrium and kinetic phenomena occurring simultaneously in the reactor. Mathematical models were derived for each phenomenon and combined to simulate the chromatographic reactor. The phenomena studied includes phase equilibria in multicomponent liquid mixture¿ion-exchange resin systems, chemicalequilibrium in the presence of a resin catalyst, diffusion of liquids in gel-type and macroporous resins, and chemical reaction kinetics. Above all, attention was paid to the swelling behavior of the resins and how it affects the kinetic phenomena. Several poly(styrene-co-divinylbenzene) resins with different cross-link densities and internal porosities were used. Esterification of acetic acid with ethanol to produce ethyl acetate and water was used as a model reaction system. Choosing an ion-exchange resin with a low cross-link density is beneficial inthe case of the present reaction system: the amount of ethyl acetate as well the ethyl acetate to water mole ratio in the effluent stream increase with decreasing cross-link density. The enhanced performance of the reactor is mainly attributed to increasing reaction rate, which in turn originates from the phase equilibrium behavior of the system. Also mass transfer considerations favor the use ofresins with low cross-link density. The diffusion coefficients of liquids in the gel-type ion-exchange resins were found to fall rapidly when the extent of swelling became low. Glass transition of the polymer was not found to significantlyretard the diffusion in sulfonated PS¿DVB ion-exchange resins. It was also shown that non-isothermal operation of a chromatographic reactor could be used to significantly enhance the reactor performance. In the case of the exothermic modelreaction system and a near-adiabatic column, a positive thermal wave (higher temperature than in the initial state) was found to travel together with the reactive front. This further increased the conversion of the reactants. Diffusion-induced volume changes of the ion-exchange resins were studied in a flow-through cell. It was shown that describing the swelling and shrinking kinetics of the particles calls for a mass transfer model that explicitly includes the limited expansibility of the polymer network. A good description of the process was obtained by combining the generalized Maxwell-Stefan approach and an activity model that was derived from the thermodynamics of polymer solutions and gels. The swelling pressure in the resin phase was evaluated by using a non-Gaussian expression forthe polymer chain length distribution. Dimensional changes of the resin particles necessitate the use of non-standard mathematical tools for dynamic simulations. A transformed coordinate system, where the mass of the polymer was used as a spatial variable, was applied when simulating the chromatographic reactor columns as well as the swelling and shrinking kinetics of the resin particles. Shrinking of the particles in a column leads to formation of dead volume on top of the resin bed. In ordinary Eulerian coordinates, this results in a moving discontinuity that in turn causes numerical difficulties in the solution of the PDE system. The motion of the discontinuity was eliminated by spanning two calculation grids in the column that overlapped at the top of the resin bed. The reactive and non-reactive phase equilibrium data were correlated with a model derived from thethermodynamics of polymer solution and gels. The thermodynamic approach used inthis work is best suited at high degrees of swelling because the polymer matrixmay be in the glassy state when the extent of swelling is low.

[BMIM][PF6] Promotes the synthesis of halohydrin esters from diols using potassium halides

Haloesterification of diverse diols with various carboxylic acids was achieved using potassium halides (KX) as the only halide source in ionic liquids. The best yield was obtained in [BMIM][PF6] when 1,2-octanediol, palmitic acid and KBr were used. This yield was 85% and the regioisomer with the bromine in primary position was present in a 75:25 ratio. The regioisomeric ratio could be improved using either KCl or some phenylcarboxylic acids. [BMIM][PF6] acts as both reaction media and catalyst of the reaction. To the best of our knowledge, this type of combined reaction using an ionic liquid is unprecedented. The other solvents tested did not lead either to the same yield or to the same regioisomeric ratio.

Isotope ratio mass spectrometry as a tool for source inference in forensic science: a critical review

Isotope ratio mass spectrometry (IRMS) has been used in numerous fields of forensic science in a source inference perspective. This review compiles the studies published on the application of isotope ratio mass spectrometry (IRMS) to the traditional fields of forensic science so far. It completes the review of Benson et al. [1] and synthesises the extent of knowledge already gathered in the following fields: illicit drugs, flammable liquids, human provenancing, microtraces, explosives and other specific materials (packaging tapes, safety matches, plastics, etc.). For each field, a discussion assesses the state of science and highlights the relevance of the information in a forensic context. Through the different discussions which mark out the review, the potential and limitations of IRMS, as well as the needs and challenges of future studies are emphasized. The paper elicits the various dimensions of the source which can be obtained from the isotope information and demonstrates the transversal nature of IRMS as a tool for source inference.

Research and development, where people are exposed to nanomaterials

OBJECTIVES: Many nanomaterials (materials with structures smaller than 100 nm) have chemical, physical and bioactive characteristics of interest for novel applications. Considerable research efforts have been launched in this field. This study aimed to study exposure scenarios commonly encountered in research settings. METHODS: We studied one of the leading Swiss universities and first identified all research units dealing with nanomaterials. After a preliminary evaluation of quantities and process types used, a detailed analysis was conducted in units where more than a few micrograms were used per week. RESULTS: In the investigated laboratories, background levels were usually low and in the range of a few thousand particles per cubic centimeter. Powder applications resulted in concentrations of 10,000 to 100,000 particles/cm(3) when measured inside fume hoods, but there were no or mostly minimal increases in the breathing zone of researchers. Mostly low exposures were observed for activities involving liquid applications. However, centrifugation and lyophilization of nanoparticle-containing solutions resulted in high particle number levels (up to 300,000 particles/cm(3)) in work spaces where researchers did not always wear respiratory protection. No significant increases were found for processes involving nanoparticles bound to surfaces, nor were they found in laboratories that were visualizing properties and structure of small amounts of nanomaterials. CONCLUSIONS: Research activities in modern laboratories equipped with control techniques were associated with minimal releases of nanomaterials into the working space. However, the focus should not only be on processes involving nanopowders but should also be on processes involving nanoparticle-containing liquids, especially if the work involves physical agitation, aerosolization or drying of the liquids.

Friedman's Excess energy and the McMillan-Mayer theory of solutions:Thermodynamics

In his version of the theory of multicomponent systems, Friedman used the analogy which exists between the virial expansion for the osmotic pressure obtained from the McMillan-Mayer (MM) theory of solutions in the grand canonical ensemble and the virial expansion for the pressure of a real gas. For the calculation of the thermodynamic properties of the solution, Friedman proposed a definition for the"excess free energy" that is a reminder of the ancient idea for the"osmotic work". However, the precise meaning to be attached to his free energy is, within other reasons, not well defined because in osmotic equilibrium the solution is not a closed system and for a given process the total amount of solvent in the solution varies. In this paper, an analysis based on thermodynamics is presented in order to obtain the exact and precise definition for Friedman"s excess free energy and its use in the comparison with the experimental data.