Spring molybdenum enrichment in scallop shells: a potential tracer of diatom productivity in temperate coastal environments (Brittany, NW France)

Skeletal molybdenum/calcium ([Mo]/[Ca])_shell ratios were examined in shells of the Great Scallop <i>Pecten maximus</i> collected in temperate coastal environments of Western Europe (42 to 49&deg; N). These ratios were determined by quantitative LA-ICP-MS analyses of daily striae taken every third day (i.e. a temporal resolution of 3 days) in 36 flat valves (2-years old; 3 shells/year). Variations of ([Mo]/[Ca])_shell ratios were significant and reproducible for scallops from the same population, from different years (1998–2004) and temperate coastal locations (NW France). The [Mo]/[Ca])_shell ratios exhibit typical profiles characterized by a background content, below the detection limit for this method (&lt;0.003 &mu;mol/mol) for most of the shell growth period, which is punctuated by a significant transient enrichment (0.031–2.1 &mu;mol/mol) mainly occurring from May to June. The Bay of Brest (France) was investigated in particular because of its long term observations on scallop communities, environmental variables, and high resolution analyses of dissolved Mo in bottom seawater in 2000. In 2000, dissolved Mo exhibited a significant increase in concentration just preceding the maximum ([Mo]/[Ca])_shell ratio. Both the intense monitoring survey in 2000 and over the 7-year period indicates that the ([Mo]/[Ca])_shell maximum is directly influenced by spring changes of environmental conditions at the sediment water interface (SWI), occurring subsequent to the intense and periodic spring bloom. Spring maxima of ([Mo]/[Ca])_shell ratios are closely correlated to the extent of silicic acid and nitrate depletion in seawater between winter and late spring (<i>r</i>²=0.878 and 0.780, <i>p</i><0.05, <i>n</i>=6) that reflects diatom uptake and productivity in the Bay of Brest. The Mo inputs in bottom waters and subsequent shell enrichment are thus suggested to be directly or indirectly influenced by such biogenic material input at the SWI. The [Mo]/[Ca])_shell records thus reveal unexpected biogeochemical cycles of Mo influenced by coastal spring productivity, faithfully recorded in scallop shells

Determination of Cu in blood: Via direct analysis of dried blood spots using high-resolution continuum source graphite furnace atomic absorption spectrometry

The performance of state-of-the-art high-resolution continuum source graphite furnace atomic absorption spectrometry (HR CS GFAAS) instrumentation and four novel devices to produce dried blood spots of perfectly defined volumes is evaluated with the aim of developing a simple, direct method for the determination of Cu in blood samples. In all cases, it is feasible to obtain accurate quantitative information using any of the four devices tested (Mitra, HemaXis DB10, Capitainer qDBS and HemaPEN) via simple external calibration with aqueous standards. One of the main differences in the performance of such devices is related to the blanks obtained, such that HemaXis DB10 and HemaPEN are preferred when abnormally low Cu levels (500 µg L-1 or lower), associated with some diseases, need to be determined. The results prove that accurate values with RSD values below 10% can be achieved for these devices even for such Cu levels, while for Capitainer qDBS and, to a higher extent, for Mitra, blank variations will ultimately increase the uncertainty. It is important to stress that analysis of four real samples using both venipuncture and all the DBS specimens showed a very good agreement. Thus, the approach proposed could be readily applied, such that patients with disorders requiring Cu control can prepare their own samples and submit them via postal mail to labs for HR CS GFAAS direct and fast analysis. © The Royal Society of Chemistry

A new multimethod approach for dating cave calcite: application to the cave of Trou du Renard (Soyons, France)

A multimethod approach aimed at characterizing carbonate parietal deposits and at proposing a chronology for these carbonate crusts is described. Dating was performed by radiometric methods (C-14 for recent samples and U series) on samples that had been characterized beforehand using optical and cathodoluminescence microscopy and Fourier transform infrared microspectroscopy. For the U series, high precision on U–Th ages was achieved using liquid phase multicollector inductively coupled plasma mass spectrometry (ICP-MS) applied to large samples, while laser ablation single collector inductively coupled plasma sector field mass spectrometry (ICP-SFMS) provided information on the reliability of the sampling with a high spatial resolution. This methodology, based on the combination of these two techniques reinforced by the information obtained by the calcite characterization methods, was applied to carbonate deposits from the cave of Trou du Renard (Soyons, France). The ages obtained with the two U–Th dating techniques are comparable and illustrate that different laminae were deposited at different rates in the samples. In the future, this procedure, based on the mineralogical and geochemical characterization of the samples and their dating by radiometric methods, will be applied to the layers of parietal carbonates deposited on Palaeolithic decorated walls. When the crystallization is slow, the U/Th dating method by imaging technique is of interest, as well as that by multicollector ICP-MS in liquid phase. The development of robust dating methods on very small quantities of material will make it possible to define the chronological framework of cave rock art.</p

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. Numerous experimental parameters were carefully selected (e.g., carrier gas flow rate, inlet diameter of the ablation cell, sample translation speed, scanner speed, etc.) in order to ensure the complete mixing between the sample and the solid spike aerosols. The proposed in-cell fs-LA-ICP-IDMS method was tested for the analysis of two soil (CRM 142R, GBW-07405) and two sediment (PACS-2, IAEA-405) reference materials, and the analysis of Cu, Zn, Sn, and Pb yielded good agreement of usually not more than 10% deviation from the certified values and precisions of less than 15% relative standard deviation. Furthermore, the concentrations were in agreement not only with the certified values but also with those obtained by ICP-IDMS after the microwave-assisted digestion of the solid samples, demonstrating therefore that in-cell fs-LA-ICP-IDMS opens the possibility for accurate and precise determinations of trace elements in powdered samples reducing the total sample preparation time to less than 5 min. Additionally, scanning electron microscope measurements showed that the aerosol generated by in-cell fs-LA-ICP-IDMS predominantly consisted of linear agglomerates of small particles (in the order of few tens of nanometers) and a few large spherical particles with diameters below 225 nm

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. Here, such an assessment is provided for the first time for the Gulf of Lions, NW Mediterranean, based on a dataset on otolith microchemistry and stable isotopic composition as indicators of the water masses inhabited by individual fish. Specifically, otolith Ba/Ca and Sr/Ca profiles, and delta C-13 and delta O-18 values of adults collected in four areas of the Gulf of Lions were compared with those of young-of-the-year collected in different coastal nurseries. Results showed that a high proportion of adults (>46%) were influenced by river inputs during their larval stage. Furthermore Sr/Ca ratios and the otolith length at one year of age revealed that most adults (similar to 70%) spent their juvenile stage in nurseries with high salinity, whereas the remainder used brackish environments. In total, data were consistent with the use of six nursery types, three with high salinity (marine areas and two types of highly saline lagoons) and three brackish (coastal areas near river mouths, and two types of brackish environments), all of which contributed to the replenishment of adult populations. These finding implicated panmixia in sole population in the Gulf of Lions and claimed for a habitat integrated management of fisherie

Bioinspired material based on femtosecond laser machining of cast sheet micromolding as a pattern transfer process

cited By 4International audienceWe present herein a simple, fast, and easy-to-use process to replicate poly(methyl methacrylate) (PMMA) plates generating surface effects. First, a femtosecond laser has been used to fabricate, with sufficient accuracy, a periodic pattern on a glass plate at the microscale. This glass plate, used as a master, can be structured on a large distance with a good control of its roughness. Then, the polymer plates were obtained by bulk polymerization without any solvents with a good replication from the cast sheet process, which has been industrially performed for years. Thus, the modification of this process, environmentally friendly, lets us foresee new applications for commodity polymers by introducing visual iridescent properties and hydrophobicity exaltation. © 2011 American Chemical Society

A fit-for purpose procedure for lead isotopic ratio determination in crude oil, asphaltene and kerogen samples by MC-ICPMS

cited By 7International audienceLead isotopic ratios have been used extensively in geological, geochronological, and archaeological studies. However, the classical anion exchange method for Pb isolation/purification using AG1-X8 resin cannot be directly adopted for high content organic samples such as crude oils, due to the fact that the sample matrices probably interact with the active sites in the resin. This results in low percentages of Pb being recovered during column separation and low-level sample purity, therefore affecting the precision of the MC-ICPMS isotopic ratio. For Pb isolation/purification from crude oil samples, at least 0.5 mL of the resin AG1-X8 is required to obtain high Pb recovery without fractioning during the analysis of crude oil. After evaluation of 5 different mass bias correction methods, the combination of Tl normalisation (exponential law) and standard bracketing was selected, providing a precision of 0.0039, 0.0014 and 0.0012 and accuracies (‰) of 0.001, 0.001 and 0.004 for 208/204Pb, 207/204Pb and 206/204Pb isotope ratios, respectively, in the analysis of a solution of 10 ng mL -1 SRM NIST 981 (n = 18). The proposed procedure allows the reliable determination of Pb isotope ratio in crude oil, asphaltene and kerogen samples, important in geochronological studies. © 2012 The Royal Society of Chemistry

Femtosecond laser ablation ICP-MS measurement of otolith Sr:Ca and Ba:Ca composition reveal differential use of freshwater habitats for three amphidromous Sicyopterus (Teleostei: Gobioidei: Sicydiinae) species

cited By 17International audienceThe use of freshwater habitats was examined in three amphidromous goby species of the genus Sicyopterus using otolith microchemistry. Two species were endemic to either New Caledonia or Vanuatu whilst the other was widely distributed. Depositional patterns of strontium (Sr) and barium (Ba) in the otolith of adults were analysed with femtosecond laser ablation inductively coupled plasma mass spectrometry (ICP-MS). The Sr:Ca and Ba:Ca results uncovered three different adult behaviours within the freshwater habitat. Some fishes stayed in elevated locations (square profile); others undertook back-and-forth migrations between higher and lower reaches (up-and-down profile), and finally, others stayed in the lower reaches (constant profile). The consequences of these movements to larval survival or competition for food and territory are discussed. This work brings new knowledge on amphidromous behaviour, and it highlights the necessity of multi-elemental analysis to study amphidromy in freshwater systems. © 2011 The Authors. Journal of Fish Biology © 2011 The Fisheries Society of the British Isles

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

cited By 6International audienceA new method to determine Pb isotope ratio without ion-exchange-matrix separation is proposed. After acid digestion, Pb was ethylated to Et 4Pb, 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 (202Hg, 203Tl, 204Pb, 205Tl, 206Pb, 207Pb, 208Pb) were monitored simultaneously with peak duration of 23 s. GC elution was operated under wet plasma conditions where a thallium standard solution was introduced to the mass spectrometer for mass bias correction. The total time of the procedure (sample preparation and analysis, after acid digestion) was reduced by a factor of 15 compared to conventional-continuous sample introduction. Data treatment was carried out using the linear regression slope method. Mass bias was corrected using the double correction method (first thallium normalization followed by classical bracketing). For the 208/206Pb and 207/206Pb ratios, precision (2RSD EXT, n = 21) was 49 and 69 ppm, and the bias between experimental results and reference values was better than 0.0033 and 0.0007 %, when injecting 1.2 ng of ethylated Pb SRM NIST 981 solution. Results obtained by this method were validated by comparison with those obtained via conventional-continuous sample introduction. The applicability of this approach was demonstrated with the analysis of black shale, asphaltene, crude oil and kerogen samples. © 2012 American Chemical Society