Unsupervised estimation of the age at sea departure of Atlantic salmon using magnesium, manganese, and zinc otolith chemistry.

Investigating the age at sea departure of returning Atlantic salmon is critical to better understand the role of emigration timing in survival. Among the methods available, the use of otolith chemistry can be challenging in anadromous fish, as the elements frequently used (i.e.

Quantifying larval dispersal portfolio in seabass nurseries using otolith chemical signatures.

The temporal asynchronies in larvae production from different spawning areas are fundamental components for ensuring stability and resilience of marine metapopulations. Such a concept, named portfolio effect, supposes that diversifying larval dispersal histories should minimize the risk of recruitment failure by increasing the probability that at least some larvae successfully settle in nursery. Here, we used a reconstructive approach based on otolith chemistry to quantify the larval dispersal portfolio of the European seabass, Dicentrarchus labrax, across six estuarine nursery areas of the northeast Atlantic Ocean.

Juvenile downstream migration patterns of an anadromous fish, allis shad (Alosa alosa), before and after the population collapse in the Gironde system, France.

Diadromous fish have exhibited a dramatic decline since the end of the 20th century. The allis shad (Alosa alosa) population in the Gironde-Garonne-Dordogne (GGD) system, once considered as a reference in Europe, remains low despite a fishing ban in 2008. One hypothesis to explain this decline is that the downstream migration and growth dynamics of young stages have changed due to environmental modifications in the rivers and estuary.

Effect of metabolic rate on time-lag changes in otolith microchemistry: an experimental approach using Salmo trutta.

Ecologists have long been interested in relevant techniques to track the field movement patterns of fish. The elemental composition of otoliths represents a permanent record of the growing habitats experienced by a fish throughout its lifetime and is increasingly used in the literature. The lack of a predictive and mechanistic understanding of the individual kinematics underlying ion incorporation/depletion limits our fine-scale temporal interpretation of the chemical signal recorded in the otolith.

Comparison of the fluctuations of the signals measured by ICP-MS after laser ablation of powdered geological materials prepared by four methods.

Sample preparation is a crucial point for quantitative multi-elemental analses by LA-ICP-MS of powdered geological materials. Four different methods are compared in this study with respect to signal stability and intensity as follows: the preparation of glass beads (GlassB) by alkaline fusion method and three grinding and pelletizing methods relying on the use of an organic binder (VanBind, vanillic acid), an adhesive binder (MixGlue, methyl methacrylate) and a sol-gel process for glass formation (SolGel, chemical reaction of tetraethoxysilane), respectively. Sixty elements were analyzed by means of a ns-UV (213 nm) laser ablation system coupled to a single collector sector field ICP-MS with a low or medium mass resolution.

Chemical signatures in fin spine edge of Atlantic bluefin tuna () can serve as habitat markers of geographically distinct marine environments.

Chemical fingerprints in otoliths are commonly used as natural habitat markers in fishes. Alternatively, the first dorsal fin spine can provide valuable chemical information and may be more suitable for studying (i) endangered fish species that cannot be sacrificed for their otoliths or (ii) fishes for which otoliths might not be available because of management or commercial reasons. Here, we studied multi-element chemistry of fin spine edges collected from Atlantic bluefin tuna (ABFT; ) (Linnaeus, 1758) to investigate the utility of the fin spine edge as a natural habitat marker.

European flounder foraging movements in an estuarine nursery seascape inferred from otolith microchemistry and stable isotopes.

Despite the importance of estuarine nurseries in the regulation of many fish stocks, temporal and spatial movements and habitat use patterns of juvenile fish remain poorly understood. Overall, combining several movement metrics allowed us to characterize dispersal patterns of juvenile flounder, Platichthys flesus, along an estuarine seascape. Specifically, we investigated otolith microchemistry signatures (Sr:Ca and Ba:Ca ratios) and stable isotope ratios (δC and δN) in muscles of these juveniles, during three consecutive years to assess inter-annual fluctuations in their home range and isotopic niches.

Isotopic Imaging Using fsLA Single-Collector ICP-SFMS for Direct U/Th Dating of Small Archaeological Carbonates.

We present a new methodology for the U/Th dating of carbonate materials using femtosecond laser ablation single-collector inductively coupled plasma sector field mass spectrometry (fsLA single-collector ICP-SFMS), isotopic mappings, and image processing. This approach allows working on samples at very low U levels (ng·g). One of the major advantages of this imaging method is that it allows us to exploit deteriorated samples that could not be analyzed by conventional bulk U/Th dating methods, thanks to the identification of contaminated or leached areas at the scale of a few tens of microns and the subsequent correction for detrital Th incorporation.

Otolith chemical fingerprints of skipjack tuna (Katsuwonus pelamis) in the Indian Ocean: First insights into stock structure delineation.

The chemical composition of otoliths (earbones) can provide valuable information about stock structure and connectivity patterns among marine fish. For that, chemical signatures must be sufficiently distinct to allow accurate classification of an unknown fish to their area of origin. Here we have examined the suitability of otolith microchemistry as a tool to better understand the spatial dynamics of skipjack tuna (Katsuwonus pelamis), a highly valuable commercial species for which uncertainties remain regarding its stock structure in the Indian Ocean.

Does trace element composition of bivalve shells record utra-high frequency environmental variations?

Saint-Pierre and Miquelon (SPM) is a small archipelago where instrumental measures based on water column velocity and temperature profiles compiled comprehensive evidence for strong near-diurnal (25.8h) current and bottom temperature oscillations (up to 11.5 °C) which is possibly the largest ever observed - at any frequency - on a stratified mid-latitude continental shelf.

Differential uses of coral reef habitats by a poorly-known cryptic fish predator.

This study used otolith microchemistry to evaluate whether the moray eel Gymnothorax chilospilus uses different habitats throughout its life (mainly juvenile and adult phases). Of the most informative trace elements within otoliths (the twelve isotopes Na, Mg, Ca, Mn, Co, Ni, Cu, Zn, Sr, Cd, Ba and Pb) only three ratios of Ca (Na:Ca, Sr:Ca and Ba:Ca) were informative and therefore used in a multivariate regression-tree analysis. Using a multivariate partitioning, three main phases were described from profiles, including the larval life phase (leptocephali), the intermediate phase (longest section between the larval life phase and the terminal phase) and the terminal phase (final section i.

Direct Online Determination of Laser-Induced Particle Size Distribution by ICPMS.

The characterization of the aerosol (size, composition, and concentration) generated by Laser Ablation is of great interest due to its impact on the analytical performances when coupled to Inductively Coupled Plasma Mass Spectrometry (ICPMS). The capabilities of High Resolution ICPMS as a direct tool to characterize nanoparticles produced by femtosecond Laser Ablation of pure copper are presented. An analytical protocol, similar to the "single particle ICPMS" technique used to characterize the size distribution of nanoparticles in solution, was developed in order to observe the signals of individual particles produced by a single ablation shot.

Improving Precision and Accuracy of Isotope Ratios from Short Transient Laser Ablation-Multicollector-Inductively Coupled Plasma Mass Spectrometry Signals: Application to Micrometer-Size Uranium Particles.

The isotope drift encountered on short transient signals measured by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) is related to differences in detector time responses. Faraday to Faraday and Faraday to ion counter time lags were determined and corrected using VBA data processing based on the synchronization of the isotope signals. The coefficient of determination of the linear fit between the two isotopes was selected as the best criterion to obtain accurate detector time lag.

Can analysis of Platichthys flesus otoliths provide relevant data on historical metal pollution in estuaries? Experimental and in situ approaches.

Despite recent efforts to manage them more efficiently, estuaries are natural sinks for a wide range of metal contaminants, many of which accumulate at potentially toxic concentrations for fish populations, posing a threat to recruitment and stocks. While analysis of metal concentrations in soft tissue and water samples calls for continuous and long-term sampling operations, the use of otoliths to study metal pollution may be one way of providing a historical record of pollutant exposure. In this study, we examine the potential use of otoliths as natural tracers of metal contamination.

The great melting pot. Common sole population connectivity assessed by otolith and water fingerprints.

Quantifying the scale and importance of individual dispersion between populations and life stages is a key challenge in marine ecology. The common sole (Solea solea), an important commercial flatfish in the North Sea, Atlantic Ocean and the Mediterranean Sea, has a marine pelagic larval stage, a benthic juvenile stage in coastal nurseries (lagoons, estuaries or shallow marine areas) and a benthic adult stage in deeper marine waters on the continental shelf. To date, the ecological connectivity among these life stages has been little assessed in the Mediterranean.

Fast and precise method for Pb isotope ratio determination in complex matrices using GC-MC-ICPMS: application to crude oil, kerogen, and asphaltene samples.

A new method to determine Pb isotope ratio without ion-exchange-matrix separation is proposed. After acid digestion, Pb was ethylated to Et(4)Pb, separated from the digested solution (black shale, asphaltene, crude oil and kerogen) by extraction in isooctane, and then injected into a gas chromatograph coupled to a multicollector inductively coupled plasma mass spectrometer. Seven isotopes ((202)Hg, (203)Tl, (204)Pb, (205)Tl, (206)Pb, (207)Pb, (208)Pb) were monitored simultaneously with peak duration of 23 s.

Specific pathways for the incorporation of dissolved barium and molybdenum into the bivalve shell: an isotopic tracer approach in the juvenile Great Scallop (Pecten maximus).

Dissolved barium and molybdenum incorporation in the calcite shell was investigated in the Great Scallop Pecten maximus. Sixty six individuals were exposed for 16 days to two successive dissolved Ba and Mo concentrations accurately differentiated by two different isotopic enrichments (⁹⁷Mo, ⁹⁵Mo; ¹³⁵Ba, ¹³⁷Ba). Soft tissue and shell isotopic composition were determined respectively by quantitative ICP-MS (Inductively Coupled Plasma Mass Spectrometer) and laser ablation--ICP-MS.

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

This 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.

Direct analysis of trace elements in crude oils by high-repetition-rate femtosecond laser ablation coupled to ICPMS detection.

IR-femtosecond pulses were used at high repetition rates (up to 10 kHz) to ablate viscous crude oils for the determination of trace elements by ICPMS. A special internal glass cap was fitted into the ablation cell to minimise oil splashes and remove big particles that would be otherwise spread into the cell. Laser ablation in static and dynamic conditions (i.

Approach to measure isotopic ratios in species using multicollector-ICPMS coupled with chromatography.

A new approach was demonstrated for the isotope ratio measurement in different elemental species of Hg using transient signal obtained by chromatography coupled with multicollector-inductively coupled plasma mass spectrometry (MC-ICPMS). The method based on the slope of linear regression by transient intensities of different isotopes shows improved accuracy and reproducibility (0.2-0.

Direct determination of trace elements in powdered samples by in-cell isotope dilution femtosecond laser ablation ICPMS.

A method has been developed for the direct and simultaneous multielement determination of Cu, Zn, Sn, and Pb in soil and sediment samples using femtosecond laser ablation inductively coupled plasma mass spectrometry (fs-LA-ICPMS) in combination with isotope dilution mass spectrometry (IDMS). The in-cell isotope dilution fs-LA-ICPMS method proposed in this work was based on the quasi-simultaneous ablation of the natural abundance sample and the isotopically enriched solid spike, which was performed using a high repetition rate laser and a fast scanning beam device in a combined manner. Both the sample preparation procedure and the total analysis time have been drastically reduced, in comparison with previous approaches, since a unique multielement isotopically enriched solid spike was employed to analyze different powdered samples.

Sensitive detection of selenoproteins in gel electrophoresis by high repetition rate femtosecond laser ablation-inductively coupled plasma mass spectrometry.

A laser ablation-ICPMS method using an infrared (1030 nm), low-energy (39 microJ/pulse), high repetition rate (10 kHz), femtosecond laser was developed to improve the sensitivity of detection of heteroatom-containing proteins in 1D polyacrylamide gels. A 2-mm-wide lane was ablated by ultrafast (10 cm s(-1)) back-and-forth movement of a 20-microm laser beam parallel to the protein bands while the gel advanced perpendicularly. This procedure resulted in a considerable increase in detection sensitivity (>40-fold) compared to the nanosecond 266-nm laser ablation-ICPMS, mainly because of the much larger amount of ablated material introduced into the plasma on the time scale of the dwell time of the mass spectrometer.

New approach of solid-phase microextraction improving the extraction yield of butyl and phenyltin compounds by combining the effects of pressure and type of agitation.

A new methodology for the simultaneous and fast solid-phase microextraction (SPME) of butyl- and phenyltin compounds, as ethylated derivates, is proposed in this paper. The effects of pressure and type of agitation during headspace SPME sampling are evaluated and discussed on the basis of thermodynamic considerations. Quantitative structure-activity relationships were used to estimate analytes partition coefficients allowing to explain the different behaviours experimentally observed.