Resting-brain functional connectivity predicted by analytic measures of network communication.

The complex relationship between structural and functional connectivity, as measured by noninvasive imaging of the human brain, poses many unresolved challenges and open questions. Here, we apply analytic measures of network communication to the structural connectivity of the human brain and explore the capacity of these measures to predict resting-state functional connectivity across three independently acquired datasets. We focus on the layout of shortest paths across the network and on two communication measures-search information and path transitivity-which account for how these paths are embedded in the rest of the network. Search information is an existing measure of information needed to access or trace shortest paths; we introduce path transitivity to measure the density of local detours along the shortest path. We find that both search information and path transitivity predict the strength of functional connectivity among both connected and unconnected node pairs. They do so at levels that match or significantly exceed path length measures, Euclidean distance, as well as computational models of neural dynamics. This capacity suggests that dynamic couplings due to interactions among neural elements in brain networks are substantially influenced by the broader network context adjacent to the shortest communication pathways.

A test of Jessor's problem behavior theory in a Eurasian and a Western European developmental context.

PURPOSE: The current study tested the applicability of Jessor's problem behavior theory (PBT) in national probability samples from Georgia and Switzerland. Comparisons focused on (1) the applicability of the problem behavior syndrome (PBS) in both developmental contexts, and (2) on the applicability of employing a set of theory-driven risk and protective factors in the prediction of problem behaviors. METHODS: School-based questionnaire data were collected from n = 18,239 adolescents in Georgia (n = 9499) and Switzerland (n = 8740) following the same protocol. Participants rated five measures of problem behaviors (alcohol and drug use, problems because of alcohol and drug use, and deviance), three risk factors (future uncertainty, depression, and stress), and three protective factors (family, peer, and school attachment). Final study samples included n = 9043 Georgian youth (mean age = 15.57; 58.8% females) and n = 8348 Swiss youth (mean age = 17.95; 48.5% females). Data analyses were completed using structural equation modeling, path analyses, and post hoc z-tests for comparisons of regression coefficients. RESULTS: Findings indicated that the PBS replicated in both samples, and that theory-driven risk and protective factors accounted for 13% and 10% in Georgian and Swiss samples, respectively in the PBS, net the effects by demographic variables. Follow-up z-tests provided evidence of some differences in the magnitude, but not direction, in five of six individual paths by country. CONCLUSION: PBT and the PBS find empirical support in these Eurasian and Western European samples; thus, Jessor's theory holds value and promise in understanding the etiology of adolescent problem behaviors outside of the United States.

Monte Carlo simulation of kilovolt electron transport in solids

A Monte Carlo procedure to simulate the penetration and energy loss of low¿energy electron beams through solids is presented. Elastic collisions are described by using the method of partial waves for the screened Coulomb field of the nucleus. The atomic charge density is approximated by an analytical expression with parameters determined from the Dirac¿Hartree¿Fock¿Slater self¿consistent density obtained under Wigner¿Seitz boundary conditions in order to account for solid¿state effects; exchange effects are also accounted for by an energy¿dependent local correction. Elastic differential cross sections are then easily computed by combining the WKB and Born approximations to evaluate the phase shifts. Inelastic collisions are treated on the basis of a generalized oscillator strength model which gives inelastic mean free paths and stopping powers in good agreement with experimental data. This scattering model is accurate in the energy range from a few hundred eV up to about 50 keV. The reliability of the simulation method is analyzed by comparing simulation results and experimental data from backscattering and transmission measurements.

Preisach modeling of hysteresis for a pseudoelastic Cu-Zn-Al single crystal

Stress-strain trajectories associated with pseudoelastic behavior of a Cu¿19.4 Zn¿13.1 Al (at.%) single crystal at room temperature have been determined experimentally. For a constant cross-head speed the trajectories and the associated hysteresis behavior are perfectly reproducible; the trajectories exhibit memory properties, dependent only on the values of return points, where transformation direction is reverted. An adapted version of the Preisach model for hysteresis has been implemented to predict the observed trajectories, using a set of experimental first¿order reversal curves as input data. Explicit formulas have been derived giving all trajectories in terms of this data set, with no adjustable parameters. Comparison between experimental and calculated trajectories shows a much better agreement for descending than for ascending paths, an indication of a dissymmetry between the dissipation mechanisms operative in forward and reverse directions of martensitic transformation.

The many uses of regulatory impact assessment: A meta-analysis of EU and UK cases

Research on regulation has crossed paths with the literature on policy instruments, showing that regulatory policy instruments contain cognitive and normative beliefs about policy. Thus, their usage stacks the deck in favor of one type of actor or one type of regulatory solution. In this article, we challenge the assumption that there is a predetermined relationship between ideas, regulatory policy instruments, and outcomes. We argue that different combinations of conditions lead to different outcomes, depending on how actors use the instrument. Empirically, we analyze 31 EU and UK case studies of regulatory impact assessment (RIA) - a regulatory policy instrument that has been pivotal in the so-called better regulation movement. We distinguish four main usages of RIA, that is, political, instrumental, communicative, and perfunctory. We find that in our sample instrumental usage is not so rare and that the contrast between communicative and political usages is less stark than is commonly thought. In terms of policy recommendations, our analysis suggests that there may be different paths to desirable outcomes. Policymakers should therefore explore different combinations of conditions leading to the usages they deem desirable rather than arguing for a fixed menu of variables.

Single-hole GPR reflection imaging of solute transport in a granitic aquifer

Identifying transport pathways in fractured rock is extremely challenging as flow is often organized in a few fractures that occupy a very small portion of the rock volume. We demonstrate that saline tracer experiments combined with single-hole ground penetrating radar (GPR) reflection imaging can be used to monitor saline tracer movement within mm-aperture fractures. A dipole tracer test was performed in a granitic aquifer by injecting a saline solution in a known fracture, while repeatedly acquiring single-hole GPR sections in the pumping borehole located 6 m away. The final depth-migrated difference sections make it possible to identify consistent temporal changes over a 30 m depth interval at locations corresponding to fractures previously imaged in GPR sections acquired under natural flow and tracer-free conditions. The experiment allows determining the dominant flow paths of the injected tracer and the velocity (0.4-0.7 m/min) of the tracer front. Citation: Dorn, C., N. Linde, T. Le Borgne, O. Bour, and L. Baron (2011), Single-hole GPR reflection imaging of solute transport in a granitic aquifer, Geophys. Res. Lett., 38, L08401, doi: 10.1029/2011GL047152.

Impact of community structure on information transfer

The observation that real complex networks have internal structure has important implication for dynamic processes occurring on such topologies. Here we investigate the impact of community structure on a model of information transfer able to deal with both search and congestion simultaneously. We show that networks with fuzzy community structure are more efficient in terms of packet delivery than those with pronounced community structure. We also propose an alternative packet routing algorithm which takes advantage of the knowledge of communities to improve information transfer and show that in the context of the model an intermediate level of community structure is optimal. Finally, we show that in a hierarchical network setting, providing knowledge of communities at the level of highest modularity will improve network capacity by the largest amount.

Preparing Tomorrow's Transportation Workforce: A Midwest Summit, 2010

regional transportation workforce development summits held across the United States in 2009 and 2010 as part of a coordinated initiative to ultimately develop a national strategy to address future transportation workforce issues. The initiative is being led by the U.S. Department of Transportation’s (DOT) Research and Innovative Technology Administration (RITA). This particular summit was hosted by Iowa State University’s Midwest Transportation Consortium (MTC) and Institute for Transportation (InTrans). The purpose of the Midwest summit was to assess the educational and training needs of the future transportation workforce and identify strategies to address those needs across various career paths. It addressed a broad spectrum of topics including strategies to attract women and under-represented minority groups, pre-college opportunities and strategies, post-secondary education, post-college continuing education, professional licensure, and specific industry perspectives. The goals of the summit were (1) to gain an improved understanding of the transportation workforce needs of Iowa and the surrounding states and (2) to identify best practices in addressing the workforce development needs. This event had two tracks: one focused on pre-college education and the other focused primarily on college education and practitioners. Attendees provided a good cross-section of the larger transportation industry. From what was learned at the summit, Iowa State University, like other regional hosts, can develop a “profile of needs” for Iowa including specific job categories over specific time horizons. The summit was also successful in identifying best practices in addressing the workforce needs that can be utilized by us and others as potential tools or in a “national-level list of attributes.” Each regional summit has provided some guidance in developing statewide profiles. The collection of best practices or tools from all the regional summits can be shared and applied to address state (or regional) needs profiles to attract, develop, and retain an effective workforce.

Evaluation of Rumble Stripes on Low-Volume Rural Roads in Iowa—Phase II Final Report, November 2011

Single-vehicle run-off-road crashes are the most common crash type on rural two-lane Iowa roads. Rumble strips have proven effective in mitigating these crashes, but the strips are commonly installed in paved shoulders on higher-volume roads that are owned by the State of Iowa. Lower-volume paved rural roads owned by local agencies do not commonly feature paved shoulders but frequently experience run-off-road crashes. This project involved installing rumble stripes, which are a combination of conventional rumble strips with a painted edge line placed on the surface of the milled area, along the edge of the travel lanes, but at a narrow width to avoid possible intrusion into the normal vehicle travel paths. The research described in this report was part of a project funded by the Federal Highway Administration, Iowa Highway Research Board, and Iowa Department of Transportation to evaluate the effectiveness of edge-line rumble strips in Iowa. The project evaluated the effectiveness of rumble stripes in reducing run-off-road crashes and in improving the longevity and wet-weather visibility of edge-line markings. This project consisted of two phases. The first phase was to select pilot study locations, select a set of test sites, install rumble stripes, summarize lessons learned during installation, and provide a preliminary assessment of the rumble stripes’ performance. The purpose of this report was to document results from Phase II. A before and after crash analysis was conducted to assess whether use of the treatment had resulted in fewer crashes. However, due to low sample size, results of the analysis were inconclusive. Lateral position was also evaluated before and after installation of the treatment to determine whether vehicles engaged in better lane keeping. Pavement marking wear was also assessed.

Mineralization of the recalcitrant oxalic and oxamic acids by electrochemical advanced oxidation processes using a boron-doped diamond anode

Oxalic and oxamic acids are the ultimate and more persistent by-products of the degradation of N-aromatics by electrochemical advanced oxidation processes (EAOPs). In this paper, the kinetics and oxidative paths of these acids have been studied for several EAOPs using a boron-doped diamond (BDD) anode and a stainless steel or an air-diffusion cathode. Anodic oxidation (AO-BDD) in the presence of Fe2+ (AO-BDD-Fe2+) and under UVA irradiation (AO-BDD-Fe2+-UVA), along with electro-Fenton (EF-BDD), was tested. The oxidation of both acids and their iron complexes on BDD was clarified by cyclic voltammetry. AO-BDD allowed the overall mineralization of oxalic acid, but oxamic acid was removed much more slowly. Each acid underwent a similar decay in AO-BDD-Fe2+ and EFBDD, as expected if its iron complexes were not attacked by hydroxyl radicals in the bulk. The faster and total mineralization of both acids was achieved in AO-BDD-Fe2+-UVA due to the high photoactivity of their Fe(III) complexes that were continuously regenerated by oxidation of their Fe(II) complexes. Oxamic acid always released a larger proportion of NH4 + than NO3- ion, as well as volatile NOx species. Both acids were independently oxidized at the anode in AO-BDD, but in AO-BDD-Fe2+-UVA oxamic acid was more slowlydegraded as its content decreased, without significant effect on oxalic acid decay. The increase in current density enhanced the oxidation power of the latter method, with loss of efficiency. High Fe2+ contents inhibited the oxidation of Fe(II) complexes by the competitive oxidation of Fe2+ to Fe3+. Low current densities and Fe2+ contents are preferable to remove more efficiently these acids by the most potent AO-BDD-Fe2+-UVA method.

Patterns of cannabis use and prospective associations with health issues among young males.

BACKGROUND AND AIMS: To test prospective associations between cannabis disorder symptoms/frequency of cannabis use and health issues and to investigate stability versus transience in cannabis use trajectories. DESIGN: Two waves of data collection from the longitudinal Cohort Study on Substance Use Risk Factors (C-SURF). SETTING: A representative sample of young Swiss men in their early 20s from the general population. PARTICIPANTS: A total of 5084 young men (mean age 19.98 ± 1.19 years at time 1). MEASUREMENTS: Cannabis use (life-time use, frequency of use, cannabis disorder symptoms) and self-reported measures of health issues (depression, mental/physical health, health consequences) were assessed. Significant changes in cannabis use were tested using t-test/Wilcoxon's rank test for paired data. Cross-lagged panel models provided evidence regarding longitudinal associations between cannabis use and health issues. FINDINGS: Most of the participants (84.5%) remained in the same use category and cannabis use kept to similar levels at times 1 and 2 (P = 0.114 and P = 0.755; average of 15 ± 2.8 months between times 1 and 2). Cross-lagged panel models showed that cannabis disorder symptoms predicted later health issues (e.g. depression, β = 0.087, P < 0.001; health consequences, β = 0.045, P < 0.05). The reverse paths from health issues to cannabis disorder symptoms and the cross-lagged panel model between frequency of cannabis use and health issues were non-significant. CONCLUSIONS: Patterns of cannabis use showed substantial continuity among young Swiss men in their early 20s. The number of symptoms of cannabis use disorder, rather than the frequency of cannabis use, is a clinically important measure of cannabis use among young Swiss men.

Iowa Plan for Brain Injury, 2007-2010

Traumatic Brain Injury (TBI) impacts the lives of thousands of Iowans every year. TBI has been described as the “Silent Epidemic” because so often the scars are not visible to others. The affects of brain injury are cognitive, emotional, social, and can result in physical disability. In addition to the overwhelming challenges individuals with brain injury experience, families also face many difficulties in dealing with their loved one’s injury, and in navigating a service delivery system that can be confusing and frustrating. In 1998, the Iowa Department of Public Health (IDPH) conducted a comprehensive statewide needs assessment of brain injury in Iowa. This assessment led to the development of the first Iowa Plan for Brain Injury, “Coming Into Focus.” An updated state plan, the Iowa Plan for Brain Injuries 2002 – 2005, was developed, which reported on progress of the previous state plan, and outlined gaps in service delivery in Iowa. Four areas of focus were identified by the State Plan for Brain Injuries Task Force that included: 1) Expanding the Iowa Brain Injury Resource Network (IBIRN); 2) Promoting a Legislative and Policy Agenda, While Increasing Legislative Strength; 3) Enhancing Data Collection; and, 4) Increasing Funding. The IDPH utilized “Coming Into Focus” as the framework for an application to the federal TBI State Grant Program, which has resulted in more than $900,000 for plan implementation. Iowa continues to receive grant dollars through the TBI State Grant Program, which focuses on increasing capacity to serve Iowans with brain injury and their families. Highlighting the success of this grant project, in 2007 the IDPH received the federal TBI Program’s “Impacting Systems Change” Award. The Iowa Brain Injury Resource Network (IBIRN) is the product of nine years of TBI State Grant Program funding. The IBIRN was developed to ensure that Iowans got the information and support they needed after a loved one sustained a TBI. It consists of a hospital and service provider pre-discharge information and service linkage process, a resource facilitation program, a peer-to-peer volunteer support network, and a service provider training and technical assistance program. Currently over 90 public and private partners work with the IDPH and the Brain Injury Association of Iowa (BIA-IA) to administer the IBIRN system and ensure that families have a relevant and reliable location to turn for information and support. Further success was accomplished in 2006 when the Iowa legislature created the Brain Injury Services Program within the IDPH. This program consists of four components focusing on increasing access to services and improving the effectiveness of services available to individuals with TBI and their families, including: 1) HCBS Brain Injury Waiver-Eligible Component; 2) Cost Share Component; 3) Neuro-Resource Facilitation; and, 4) Enhanced Training. The Iowa legislature appropriated $2.4 million to the Brain Injury Services Program in state fiscal year (SFY) 2007, and increased that amount to $3.9 million in SFY 2008. The Cost Share Component models the HCBS Brain Injury Waiver menu of services but is available for Iowans who do not qualify functionally or financially for the Waiver. In addition, the Neuro-Resource Facilitation program links individuals with brain injury and their families to needed supports and services. The Iowa Plan for Brain Injury highlights the continued need for serving individuals with brain injury and their families. Additionally, the Plan outlines the paths of prevention and services, which will expand the current system and direct efforts into the future.

Assessing the pH and DP of canvasses with NIR spectroscopy

The canvas support in easel paintings is composed mainly of cellulose. One of the maindegradation paths of cellulose is acid-catalysed hydrolysis, which means that in an acidic environment (low pH), its degradation proceeds at a faster rate (Strlič et al., 2005).The main effect of acid-catalysed hydrolysis is the breaking up of the polymer chains,measured by the “Degree of Polymerisation” (DP). The lowering of the DP value impliesa lower mechanical strength of the textile (Scicolone, 1993), and thus this parameter canbe used to monitor degradation. Knowing these two parameters can, therefore, be veryinformative regarding the condition of the canvas support.

Elemental and isotopic zoning in natural alpine quartz

THESIS ABSTRACT : Stable isotope geochemistry is used to help resolve a large number of geological questions. In order to do this, it is essential to understand the different mechanisms that govern isotopic fractionation processes between different phases and to identify the conditions required to reach equilibrium fractionation. However, at low temperatures, these processes are poorly constrained and many factors can induce differential partitioning of the isotopes between sectors of a mineral species and the fluid during mineral growth. This can result in so-called 'sector zoning' of a mineral species. The aim of this thesis is to evaluate the occurrence of sector zoning of the oxygen isotopes and trace elements in natural α-quartz crystals and to identify the reasons for such zoning. The implications for the fluid-mineral interactions are studied in the context of the Alpine metamorphism. The approach chosen has focused on examining the crystal structure, cathodoluminescence appearance (CL), and on relating elemental (e.g. Li, Na, Al, P, K, Ca, Ge, Ti, Fe) to stable oxygen isotope compositions between and along different growth sectors. Low temperature quartz samples were selected from Alpine veins in different localities, where growth conditions have already been well constrained. The mineralogy as well as the isotopic compositions of the host rocks were also investigated, in order to interpret the variations obtained between the different growth stages in the framework of fluid-rock interaction during Alpine metamorphism. Depending on the growth conditions, most of the studied quartz is strongly zoned in CL, and it reveals corresponding zonations in the trace element content (e.g. growth zoning). Aluminium, substituting for Si in the lattice, was found in concentrations up to 1000's ppma, and its distribution is strongly related to Li and H and to a lesser extent, to Ge. Elemental sector zoning is evident from the distribution of these three elements since they exhibit differences in their respective concentrations between faces for distinct growth zones, with prismatic faces having the lowest Al contents. Quartz from veins in magmatic rocks, for example, tend to have lower Al concentrations and similar concentrations of Li and Ti suggesting also a contribution of these elements from the host rock. The relationship between Al and Li is still correlated. Only Alpine crystals grown at higher temperatures (~400°C) without any CL zoning feature are free of these impurities and do not show such zoning characteristics. Differences in the δ18O values were measured between different faces principally in the AIenriched growth zones or stages. These results were confirmed by the means of two different methods (in situ/non in situ). However, it was determined that the Al concentrations do not affect significantly oxygen isotope fractionations at 300°C. The results altogether suggest that the presence of sector zoning in quartz crystals is real, but not universal, and henceforth should be taken into consideration for any use of these systems. The occurrence of disequilibrium partitioning has been enhanced and is possibly related to kinetic processes as well as structural effects that do not affect similarly trace element incorporation and isotopic fractionation. In situ measurements also revealed fine scale δ18O zonations along growth paths that are useful to constrain fluid-rock interactions during Alpine metamorphism. Variations in the δ18O values present along growth vectors indicate changes in the fluid composition and origin. Association with oxygen isotope composition of the host rock allows for the deduction of interactions between rocks, veins and consequently fluids, as well as fluid regimes. RESUME DE LA THESE : A basses températures, (i.e. <400°C) les différents mécanismes qui régissent le fractionnement isotopique ainsi que les conditions nécessaires pour établir un état d'équilibre sont peu connus et nombre de paramètres peuvent entraîner un partitionnement chimique différentiel entre différents secteurs d'un minéral et le fluide en contact. Ainsi, ce travail de thèse a pour but d'évaluer la possible présence de zonages sectoriels en isotopes de l'oxygène mais aussi en éléments traces dans des cristaux naturels de quartz-α de basses températures, ainsi que les raisons d'un tel phénomène et enfin ses implications sur les interactions fluide-roche, principalement dans le cadre du métamorphisme Alpin. La structure et l'apparence en cathodoluminescence (CL) des échantillons ont été caractérisées avant de retracer en détail les compositions en élément traces (Li, Na, Al, P, K, Ca, Ge, Ti, Fe) et en isotopes de l'oxygène, le long et entre différents secteurs. Les échantillons de quartz sélectionnés proviennent majoritairement de veines Alpine de différentes localités, où les conditions de croissance ont été déjà bien caractérisées. Les compositions minéralogiques et isotopiques de la roche encaissante ont aussi été examinées, pour contraindre les variations obtenues dans un contexte Alpin. Selon leurs conditions de croissance, la plupart des cristaux étudiés sont fortement zonés, ce qui est souligné par un zonage des concentrations en éléments traces (e.g. zonage de croissance). L'Aluminium, qui peut se substituer à la Silice dans le réseau cristallin, a été retrouvé jusqu'en très grandes concentrations dans certaines zones (plusieurs milliers de ppma). De plus, la distribution en Al est fortement liée à celles de Li et H, ainsi que dans une moindre mesure à Ge. La présence de zonage sectoriel est évidente au niveau de ces éléments qui montrent de larges différences de concentrations entre différentes faces pour une même zone de croissance, avec les concentrations les plus basses retrouvées dans les faces prismatiques. Les quartz de veines situées dans des roches magmatiques par exemple possèdent des concentrations en Li et Ti de même ordre de grandeur, confirmant le rôle de la composition de la roche encaissante. La relation Li/Al est toujours fortement présente, mais ce rapport est fonction de la face mesurée. Seuls les cristaux Alpins de plus hautes températures (400°C) ne possédant pas de zones en CL ne présentent aucune de ces caractéristiques. Des différences dans les valeurs de δ18O de zones identiques enrichies en Al ont clairement été mesurées entre les différentes faces r, z, et m, mais aussi au sein d'une même seule zone, indiquant que le fractionnement a probablement eu lieu en déséquilibre. Il a été déterminé que la présence d'Al dans ces teneurs n'avait qu'un faible effet sur le fractionnement isotopique de l'oxygène. L'utilisation de deux méthodes différentes a permis d'obtenir des résultats in situ et non in situ concordants. La comparaison des résultats obtenus permet de démontrer que le zonage sectoriel est bien présent dans certains cristaux de quartz, et dépend des conditions de formation. La présence d'un partitionnement différentiel des éléments traces peut être due à des effets cinétiques aussi bien que structuraux, alors que le zonage sectoriel des isotopes de l'oxygène aurait d'autres origines. Il est alors évident que la possibilité de zonage sectoriel doit être désormais pris en considération avant toute interprétations de données isotopiques de cristaux zonés. Les mesures in situ ont de plus permis de distinguer de fines variations des valeurs δ18O au cours de la croissance, qui peuvent aider à retracer la circulations des fluides dans les Alpes durant cette période. En association avec les compositions des roches encaissantes, ii est possible de déduire les interactions entre roches, veines, et par conséquent fluides, au cours de différentes étapes. RESUME GRAND PUBLIC : La géochimie des isotopes stables a pris beaucoup d'importance depuis ces dernières années pour aider à résoudre nombre de questions géologiques, en se basant sur les caractéristiques du fractionnement isotopiques pour différents systèmes. Il est donc nécessaire d'avoir une connaissance approfondie des mécanismes qui s'appliquent au fractionnement isotopique entre les minéraux et les fluides à partir desquels ils se forment. Ces mécanismes ont été bien approchés par différents types de calibrations pour des systèmes à hautes températures, cependant cela n'est pas aussi évident pour les systèmes à des températures inférieures à 400-500°C. Ce travail de thèse a pour but d'aider à la description et la compréhension des phénomènes qui peuvent affecter le fractionnement isotopique à basses températures, ainsi que leurs implications, à partir de l'étude de cristaux de quartz. Le choix des échantillons s'est porté sur des cristaux naturels formés à des températures inférieures ou égales à 400°C, provenant majoritairement de fissures hydrothermales Alpines dont les conditions de formation ont déjà été déterminées. L'étude des cristaux Alpin permet de plus de replacer les résultats obtenus dans le contexte du métamorphisme Alpin au cours du Miocène (21-13 Ma). Après examen de la structure et de la morphologie des cristaux, et leur caractérisation par cathodoluminescence (CL), des analyses chimiques détaillées sur les éléments en traces pouvant entrer dans le réseau cristallin du quartz comme impuretés (i.e. Li, Na, Al, P, K, Ca, Ge, Ti), et des isotopes stables de l'oxygène, ont été menées. En fonction des conditions de croissance, la plupart des cristaux présentent des zonations, qui peuvent être facilement reliées à la distribution des éléments traces analysés par microsonde électronique, sonde ionique (SIMS) et LA-ICPMS. De fortes concentrations d'Aluminium (plusieurs milliers de parties par million atomique) ont pu être observées dans les zones les plus externes des cristaux. De plus, les concentrations en Al et en Li sont toujours corrélées; la présence d'Hydrogène déduite à partir d'analyses par FTIR suit cette même tendance. Les différentes faces des cristaux présentent des concentrations distinctes d'Al, Li et H pour des mêmes zones de croissance, avec par exemple les concentrations les plus faibles dans les zones des faces prismatiques. Cela implique la présence d'un zonage sectoriel, qui a déjà été observé principalement dans des carbonates mais jamais décrit auparavant pour des quartz. Seuls les cristaux alpins homogènes en CL dont la croissance s'est faite à plus haute température (400°C) ne présentent aucune de ces caractéristiques. Par analogie avec le zonage sectoriel en Al, élément qui se substitue au Si dans le réseau cristallin du quartz, il est possible de penser qu'un zonage sectoriel pourrait aussi s'appliquer aux isotopes de l'oxygène. Des précédentes études avaient en effet émis cette hypothèse. Nos résultats ont été obtenus à partir d'analyses à la fois in- situ par SIMS, et par extraction assistée par laser-CO2 sur des parties de quartz soigneusement séparées, et sont en accord entre les deux méthodes. Un zonage sectoriel est en effet bien présent pour les cristaux alpins, mais principalement au niveau des zones très riches en Aluminium. Cependant, il a été déterminé que la présence d'Al dans ces teneurs avait un effet plus que minimal sur le fractionnement isotopique de l'oxygène. Des différences importantes ont été observées entre les faces r & z mais aussi au sein d'une même et seule zone, indiquant que le fractionnement a pu avoir lieu en déséquilibre, ce qui est aussi visible au niveau des valeurs totalement opposées entre faces pour la dernière phase de croissance de certains cristaux. Ainsi l'association de ces résultats laisse suggérer que la présence d'un zonage sectoriel peut être liée à différents paramètres tels que le taux de croissance ou la structure de surface du cristal, mais qui n'affectent pas de la même façon l'incorporation des éléments traces et le fractionnement isotopique. La possibilité d'un zonage sectoriel est importante à prendre en compte lors de toute interprétation de données isotopiques. Les analyses des isotopes de l'oxygène effectuées par SIMS ont aussi permis de distinguer des variations importantes à petite échelle au cours de la croissance. Des mesures faites par laser CO2 sur certaines roches encaissantes, ont permis distinguer plusieurs étapes dans la croissance des minéraux et de déduire le rôle de l'encaissant et le type de fluide. En association avec de précédentes études, il a été ainsi possible de mieux contraindre la formation de ces cristaux dans le contexte alpin et la circulation de fluide au cours du métamorphisme alpin durant le Miocène.

Using spatially distributed parameters and multi-response objective functions to solve parameterization of complex applications of semi-distributed hydrological models

Application of semi-distributed hydrological models to large, heterogeneous watersheds deals with several problems. On one hand, the spatial and temporal variability in catchment features should be adequately represented in the model parameterization, while maintaining the model complexity in an acceptable level to take advantage of state-of-the-art calibration techniques. On the other hand, model complexity enhances uncertainty in adjusted model parameter values, therefore increasing uncertainty in the water routing across the watershed. This is critical for water quality applications, where not only streamflow, but also a reliable estimation of the surface versus subsurface contributions to the runoff is needed. In this study, we show how a regularized inversion procedure combined with a multiobjective function calibration strategy successfully solves the parameterization of a complex application of a water quality-oriented hydrological model. The final value of several optimized parameters showed significant and consistentdifferences across geological and landscape features. Although the number of optimized parameters was significantly increased by the spatial and temporal discretization of adjustable parameters, the uncertainty in water routing results remained at reasonable values. In addition, a stepwise numerical analysis showed that the effects on calibration performance due to inclusion of different data types in the objective function could be inextricably linked. Thus caution should be taken when adding or removing data from an aggregated objective function.