Regional-scale paleofluid system across the Tuscan Nappe–Umbria–Marche Apennine Ridge (northern Apennines) as revealed by mesostructural and isotopic analyses of stylolite–vein networks

We report the results of a multiproxy study that combines structural analysis of a fracture–stylolite network and isotopic characterization of calcite vein cements and/or fault coating. Together with new paleopiezometric and radiometric constraints on burial evolution and deformation timing, these results provide a first-order picture of the regional fluid systems and pathways that were present during the main stages of contraction in the Tuscan Nappe and Umbria–Marche Apennine Ridge (northern Apennines). We reconstruct four steps of deformation at the scale of the belt: burial-related stylolitization, Apenninic-related layer-parallel shortening with a contraction trending NE–SW, local extension related to folding, and late-stage fold tightening under a contraction still striking NE–SW. We combine the paleopiezometric inversion of the roughness of sedimentary stylolites – that constrains the range of burial depth of strata prior to layer-parallel shortening – with burial models and U–Pb absolute dating of fault coatings in order to determine the timing of development of mesostructures. In the western part of the ridge, layer-parallel shortening started in Langhian time (∼15 Ma), and then folding started at Tortonian time (∼8 Ma); late-stage fold tightening started by the early Pliocene (∼5 Ma) and likely lasted until recent/modern extension occurred (∼3 Ma onward). The textural and geochemical (δ18O, δ13C, Δ47CO2 and 87Sr∕86Sr) study of calcite vein cements and fault coatings reveals that most of the fluids involved in the belt during deformation either are local or flowed laterally from the same reservoir. However, the western edge of the ridge recorded pulses of eastward migration of hydrothermal fluids (>140 ∘C), driven by the tectonic contraction and by the difference in structural style of the subsurface between the eastern Tuscan Nappe and the Umbria–Marche Apennine Ridge

Laser bidezko ablazioaren egungo egoera eta aplikazioak

80ko hamarkadaz geroztik, laser bidezko ablazioa eta akoplamendu induktibozko plasma-masa espektrometria (LA-ICPMS) konbinatzen dituen teknika analitikoa sakonki ikertu eta garatu da, eta, gaur egun, lagin solidoen analisi elemental zein isotopiko zuzena egiteko erreferentziazko teknika bilakatu da. Ezaugarri bereizgarrienak hauexek dira: erabilpen erraza, analisi-denbora laburra, laginari eragindako kalte urriak, sentsibilitate handia eta elementu nagusi zein minoritarioen eta ratio isotopikoen aldibereko neurketa ahalbidetzen duen tarte dinamiko zabala. Lan honetan, LA-ICPMS teknikaren oinarriak eta konfigurazio orokorra azaldu eta femtosegundo/ nanosegundo laser bidezko ablazioaren erabileraren arteko desberdintasun nagusiak nabarmentzen dira. Azkenik, teknika honen egungo egoeraz jabetzeko, jatorri askotariko laginen analisi elementala laburbildu eta berrikusten da biologian eta ingurumenean, osasunean, geokimikan zein auzitegi zientzien alorretan.; Since the early 80s, laser-ablation inductively-coupled-plasma mass spectrometry (LA-ICPMS) has been widely explored and nowadays is considered to be one of the most versatile analytical techniques for the direct trace elemental and isotopic analyses of solid samples. The most remarkable features are ease of use, fast sample throughput, limited sample damages, high sensitivity and wide dynamic range which allows the simultaneous acquisition of major and trace elements, as well as the measurement of isotope ratios. Throughout this manuscript, the principles and general setup of LA-ICPMS will be extensively explained and the performance of femtosecondLA in comparison to nanosecond-LA discussed. In order to show the state of the art in this field a variety of examples for elemental analysis of solid samples in biological/environmental science, geochemistry and forensic science applications will be presented

Inputs from microchemistry to the understanding of three Sicydiinae species\u27 life cycle

Amphidromous fish species contribute most to the diversity of fish communities  in the tropical insular rivers. Hence, their biological life cycle remains poorly known. The oto-lith elemental composition of three Sicydiinae species Sicyopus zosterophorum, Smilosicyopus chloe, Akihito vanuatu was investigated to describe their biological life cycle for the first time. The otolith analysis using a femtosecond laser ablation – inductively coupled plasma mass spec-trometer (fs-LA-ICP-MS) revealed an amphidromous life history for the three species as it sug-gested a habitat shift from a marine habitat to a freshwater environment. Also, several types of elemental profiles were observed in the adult stage suggesting a diversity of behaviors and/or habitats. Water chemistry analyses would help understanding the origin of the ratios variations in the adult stage and would push forward our general understanding of Sicydiinae life cycle

New analytical approaches for copper diagnosis, prognosis and follow up of Wilson disease

El cobre es un metal esencial involucrado en muchas reacciones metabólicas. En particular, está relacionada con la enfermedad de Wilson (WD), causada por una mutación del gen ATP7B que provoca una acumulación de cobre en los órganos (hígado, cerebro, riñones, ojos, etc.). Esta enfermedad puede ser mortal si no se trata. Aunque el tratamiento es relativamente sencillo y eficaz, el problema es poder diagnosticar la enfermedad con suficiente antelación, antes de que aparezcan los síntomas.Habitualmente, el biomonitoreo se lleva a cabo mediante muestras de sangre extraídas mediante punción venosa. Sin embargo, para compensar este método relativamente invasivo (especialmente para los recién nacidos) y que generalmente requiere una visita a un laboratorio de análisis médicos, han surgido nuevos dispositivos de micromuestra que permiten tomar sólo unos pocos microlitros, inicialmente desarrollados para el seguimiento de biomarcadores ( En esta tesis se utilizaron anticuerpos, ADN, proteínas, etc.).En este contexto, en el marco de esta tesis se han desarrollado diferentes métodos analíticos para la determinación elemental del cobre y su composición isotópica, basados en técnicas de micromuestreo.En particular, se han desarrollado y evaluado dos métodos para el análisis elemental del cobre. El primero, dedicado al análisis directo de sólidos mediante HR CS GFAAS, permitió la evaluación de diferentes dispositivos de toma de muestras de sangre seca. Se desarrolló y aplicó al análisis de muestras líquidas y sólidas un nuevo algoritmo de corrección de interferencias basado en el perfil de absorbancia resuelto en el tiempo (TAP). El segundo método se aplicó al análisis de muestras líquidas mediante ICP-MS utilizando solo 1 µl de muestra.También se desarrollaron y evaluaron tres métodos para el análisis isotópico del cobre, el primero mediante láser de femtosegundo, el segundo mediante vaporización electrotérmica (ETV) y el último mediante microinyección directa de líquido.Estos métodos se utilizaron para estudiar el diagnóstico, pronóstico y seguimiento de la enfermedad de Wilson.Finalmente, se observó que el cobre intercambiable relativo (REC) parece ser un buen parámetro para diferenciar a los pacientes con enfermedad de Wilson de otros grupos. Los demás parámetros, especialmente la composición isotópica del cobre, pueden utilizarse para el seguimiento de la enfermedad.Copper is an essential metal involved in many metabolic reactions. In particular, it is linked to Wilson's disease (WD) caused by a mutation of the ATP7B gene which leads to an accumulation of copper in the organs (livers, brains, kidneys, eyes, etc.). This disease can be fatal if left untreated. Although the treatment is relatively simple and effective, the problem is to be able to diagnose the disease early enough, before the symptoms appear. Usually, biomonitoring is carried out using blood samples taken by venipuncture. However, in order to compensate for this relatively invasive method (especially for newborns) and which generally requires a trip to a medical analysis laboratory, new micro-sampling devices allowing only a few microlitres to be taken, initially developed for the monitoring of biomarkers (antibodies, DNA, protein, etc.) were used in this thesis. In this context, different analytical methods have been developed in the framework of this thesis for the elemental determination of copper and its isotopic composition, based on micro-sampling techniques. In particular, two methods have been developed and evaluated for the elemental analysis of copper. The first one, dedicated to the direct analysis of solids by HR CS GFAAS, allowed the evaluation of different dried blood spot sampling device. A new interference correction algorithm based on the time resolved absorbance profile (TAP) was developed and applied to the analysis of liquid and solid samples. The second method was applied to the analysis of liquid samples by ICP-MS using only 1 µl of sample. Three methods were also developed and evaluated for the isotopic analysis of copper, the first using a femtosecond laser, the second using Electro Thermal Vaporisation (ETV) and the last using direct liquid micro-injection. These methods were used to study the diagnosis, prognosis and follow-up of Wilson's disease. Finally, it was observed that relative exchangeable copper (REC) seems to be a good parameter to differentiate Wilson's disease patients from other groups. The other parameters, especially copper isotopic composition, can be used for the follow-up of the disease.<br /

Coupling natural and electronic tags to explore spawning site fidelity and natal homing in northeast Atlantic European seabass

The structure and connectivity of European seabass (Dicentrarchus labrax) populations remain poorly known and ecological evidence is missing to support the current delineation between the northern (southern North Sea, English Channel and Celtic Sea) and southern French stocks (Bay of Biscay). Adult spawning site fidelity and natal homing were analysed by coupling Data Storage Tag (DST) information and otolith microchemistry of recaptured fish to investigate, within the study area, the population structure and connectivity in European seabass. Trajectory reconstructions inferred from DST data were used to assign a spawning area (English Channel or Bay of Biscay) to each spawning winter record. In addition, otolith composition (Mg, P, Mn, Zn, Sr, Ba and δ18O) was measured in both larvae and adults otolith increments corresponding to a winter spawning event. We built a training dataset using coupled spawning area assignments and otolith elemental signatures (Mg, P, Mn, Zn, Sr and Ba) for winters with DST data. The training dataset was used to calibrate a Random Forest model and assign spawning areas based on otolith winter signatures outside the DST recording period. Results revealed that 64% of the seabass expressed spawning site fidelity. We also found a geographical gradient of site fidelity, with the highest proportions of spawning site fidelity found in seabass tagged at the northern and southern limits of the studied area. Significant ontogenetic effects were observed for trace elements and δ18O with ratios significantly lower in the larval stage than in the adult stage. These biases and the variability across cohorts prevented us to use the assignment model fitted on adults to study natal homing. At the larval stage, the analysis of spatio-temporal effects on otolith trace elements did not reveal any significant difference between spawning areas. However, the patterns of difference were similar for larval and adult Zn, Sr and Ba between the two spawning areas, suggesting a homing behaviour

High-resolution 87/86Sr analyses in freshwater mussels : time-series and cartography using femto-laser MC-ICP-MS [résumé]

Goldschmidt 2019, Barcelone, ESP, 18-/08/2019 - 23/08/201

Species-specific stable isotope analysis by the hyphenation of chromatographic techniques with MC-ICPMS

International audienceThis work reviews the basis and all the existing publications on the hyphenation of chromatography-based techniques to MC-ICPMS for isotopic studies that were published until the end of 2010. A brief historical retrospective of the measurement of isotope ratios from transient signals by ICPMS with different sample introduction techniques is also included. The most important experimental parameters and data reduction strategies affecting the accurate and precise measurement of compound-specific isotope ratios by either HPLC or GC coupled to MC-ICPMS are discussed. All the applications are reported and critically reviewed in terms of analytical characteristics, performances, optimization, advantages and disadvantages and future applicability to the environmental, geochemical, or bioinorganic studies

Coupling genetic and otolith trace element analyses to identify river-born fish with hatchery pedigrees in stocked Atlantic salmon (Salmo salar) populations

This study combines otolith trace element and genetic analyses to explore the origin of individuals when hatcheryreared fish are released into wild populations. We sampled 90 juvenile Atlantic salmon (Salmo salar) in four rivers in Normandy (France) and in the hatchery stock. Individuals were analyzed at six microsatellite markers and their otolith elemental concentrations (14 elements) were measured using femto-second laser ablation inductively-coupled plasma mass spectrometry. Wild populations were genetically differentiated from the hatchery strain (F(ST) approximate to 0.06). Significant differences in elemental concentrations were found among otoliths of juveniles from the four rivers and the hatchery, allowing the identification of their geographic origin (83%-100% correct assignment). Coupling genetic and trace element analyses on the same individuals provided formal evidence that hatchery-born juveniles released into the wild can migrate to the sea and return as adul! ts to breed on natural spawning grounds. Their progeny have pure hatchery pedigrees but have otoliths typical of river-born juveniles, meaning that they can be mistaken for hatchery-raised juveniles if only genetic data are considered. The presence of hybrids also confirmed that individuals with hatchery pedigrees can breed with wild conspecifics

Specific gravity and migratory patterns of amphidromous gobioid fish from Okinawa Island, Japan

International audienceAmphidromy is a diadromous life history pattern where fish spawn in freshwater, and their larvae drift downstream to the sea; the larvae develop in marine environments then migrate back in rivers to grow and reproduce. Two amphidromous types with different life history characteristics, such as egg and larval sizes, exist. To understand the ecology and early life history of amphidromous gobioid fish, six species from Okinawa Island were selected—two large egg-type species (Rhinogobius similis and Tridentiger kuroiwae) and four small egg-type species (Stiphodon percnopterygionus, Stenogobius sp., Sicyopterus lagocephalus, and Eleotris acanthopoma). The migratory pattern of four of these species was confirmed using otolith Sr:Ca and Ba:Ca ratios combined with water chemistry analysis. Although these species showed amphidromous migratory patterns, the timing of migration from estuarine to freshwater habitats was species-specific. The large egg-type, R. similis, showed three different migratory patterns: a long marine larval phase with a relatively fast migration from estuarine to freshwater habitats, a short marine larval phase with a relatively fast migration, and a gradual migration. Similar patterns of a long and fast migration or a gradual migration were seen in T. kuroiwae; however, the two small egg-type species, Sti. percnopterygionus and Stenogobius sp., showed rapid migration to freshwater after entering the river. To estimate larval ecology in the sea, ontogenetic changes in specific gravity (SG) were examined in all species. The SG was measured day and night for 1–5 days until settlement in R. similis and T. kuroiwae, and until 10 days after hatching in the other species. The SG of all species ranged from 1.0138 to 1.0488, and varied among ontogenetic stages and between day and night and species. Larval SG was relatively similar between R. similis and T. kuroiwae, with low SG in the early stages and high SG after yolk absorption. During the late larval stages and until settlement, T. kuroiwae showed diel changes in SG, with higher SG during the day, whereas R. similis had a relatively constant pattern. The diel changes of T. kuroiwae larvae suggest different activity during the day and at night (e.g. diel vertical migration). In the four small egg-type species, SG was high at hatching and decreased thereafter, not showing large diel changes. The results suggest that sympatric amphidromous gobioid species have various early life histories that may be influenced by several larval traits, including SG