Characterization of the aerosol produced by infrared femtosecond laser ablation of polyacrylamide gels for the sensitive inductively coupled plasma mass spectrometry detection of selenoproteins

A 2D high repetition rate femtosecondlaserablation strategy (2-mm wide lane) previously developed for the detection of selenoproteins in gel electrophoresis by inductively coupled plasma mass spectrometry was found to increase signal sensitivity by a factor of 40 compared to conventional nanosecond ablation (0.12-mm wide lane) [G. Ballihaut, F. Claverie, C. Pécheyran, S. Mounicou, R. Grimaud and R. Lobinski, Sensitive Detection of Selenoproteins in Gel Electrophoresis by High Repetition Rate FemtosecondLaserAblation-Inductively Coupled Plasma Mass Spectrometry, Anal. Chem. 79 (2007) 6874–6880]. Such improvement couldn't be explained solely by the difference of amount of material ablated, and then, was attributed to the aerosol properties. In order to validate this hypothesis, the characterization of the aerosolproduced by nanosecond and high repetition rate femtosecondlaserablation of polyacrylamidegels was investigated. Our 2D high repetition rate femtosecondlaserablation strategy of 2-mm wide lane was found to produce aerosols of similar particle size distribution compared to nanosecond laserablation of 0.12-mm wide lane, with 38% mass of particles < 1 µm. However, at high repetition rate, when the ablated surface was reduced, the particle size distribution was shifted toward thinner particle diameter (up to 77% for a 0.12-mm wide lane at 285 µm depth). Meanwhile, scanning electron microscopy was employed to visualize the morphology of the aerosol. In the case of larger ablation, the fine particles ejected from the sample were found to form agglomerates due to higher ablation rate and then higher collision probability. Additionally, investigations of the plasma temperature changes during the ablation demonstrated that the introduction of such amount of polyacrylamidegel particles had very limited impact on the ICP source (ΔT~ 25 ± 5 K). This suggests that the cohesion forces between the thin particles composing these large aggregates were weak enough to have negligible impact on the ICPMS detection

Elemental fractionation effects in high repetition rate IR femtosecond laser ablation ICP-MS analysis of glasses

An IR-femtosecond laser ablation ICPMS coupling was used to investigate the influence of the high repetition rate on elemental fractionation effects for the analysis of silicate glass SRM NIST 610. First, elemental fractionation inherent to the ICP was minimised by working on wet plasma conditions which had greater tolerance to mass loading and demonstrated a higher robustness compared to dry plasma conditions. Because of the use of a narrow laser beam producing small craters (17 µm in diameter), a special arrangement of pulses was used to perform resulting craters of 100 µm diameter. The ablation strategy developed in this work consisted in a series of concentric circle trajectories ablated at high repetition rates by moving the laser beam rapidly thanks to a scanning beam device. Two scanner speeds (0.25 mm s−1 and 1.5 mm s−1), five laser repetition rates (from 0.1 kHz to 10 kHz) and three fluence values (5 J cm−2, 14 J cm−2, and 25 J cm−2) were investigated in detail. For this purpose, critical elemental ratios (namely 238U/232Th, 208Pb/238U, and 66Zn/65Cu) of aerosols produced by fs-LA of silicate glass were studied to evaluate the impact of the different laser parameters on elemental fractionation . No heating zones or preferential evaporation of elements were found depending on the repetition rate employed. However, particle-size-fractionation was measured during the ablation of the sample surface, and this effect was reduced by using a high repetition rate as well as a high scanner speed which allow the dilution of the large particles coming from the surface layer with finer particles coming to deeper levels. Additionally, the ablation rate induced by the selected ablation strategy had a low influence on fractionation effects due to the high robustness of the ICP plasma and, on the other hand, fractionation indices were not particularly affected by the laser repetition rate although they could be improved by the use of high fluence values. Finally, it could be stressed that no differences on the structure of the aerosol particles collected on membrane filters were found depending on the ablation parameters

Cu fractionation, isotopic analysis, and data processing <i>via</i> machine learning: new approaches for the diagnosis and follow up of Wilson's disease <i>via</i> ICP-MS

Information about Cu fractionation and Cu isotopic composition can be paramount when investigating Wilson's disease (WD). This information can provide a better understanding of the metabolism of Cu. Most importantly, it may provide an easy way to diagnose and to follow the evolution of WD patients. For such purposes, protocols for Cu determination and Cu isotopic analysis via inductively coupled plasma mass spectrometry were investigated in this work, both in bulk serum and in the exchangeable copper (CuEXC) fractions. The CuEXC protocol provided satisfactory recovery values. Also, no significant mass fractionation during the whole analytical procedure (CuEXC production and/or Cu isolation) was detected. Analyses were carried out in controls (healthy persons), newborns, patients with hepatic disorders, and WD patients. While the results for Cu isotopic analysis are relevant (e.g., δ65Cu values were lower for both WD patients under chelating treatment and patients with hepatic problems in comparison with those values obtained for WD patients under Zn treatments, controls, and newborns) to comprehend Cu metabolism and to follow up the disease, the parameter that can help to better discern between WD patients and the rest of the patients tested (non-WD) was found to be the REC (relative exchangeable Cu). In this study, all the WD patients showed a REC higher than 17%, while the rest showed lower values. However, since establishing a universal threshold is complicated, machine learning was investigated to produce a model that can differentiate between WD and non-WD samples with excellent results (100% accuracy, albeit for a limited sample set). Most importantly, unlike other ML approaches, our model can also provide an uncertainty metric to indicate the reliability of the prediction, overall opening new ways to diagnose WD

Chemical signatures in fin spine edge of Atlantic bluefin tuna (Thunnus thynnus) 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; Thunnus thynnus) (Linnaeus, 1758) to investigate the utility of the fin spine edge as a natural habitat marker. We determined stable isotopic δ18O and δ13C ratios, as well as concentrations of the tracer elements Mg, Mn, Li, Ba, and Sr, at the edge of ABFT fin spines, and then we used these measures to discriminate ABFT individuals among capture regions (i.e., the eastern Atlantic Ocean or Mediterranean Sea). Isotope ratios and tracer element concentrations, and especially a combined multi-element approach, were able to effectively discriminate individuals by capture region. The Mg, Mn, Li, and δ18O concentrations were the strongest variables driving this discrimination. Overall, our results demonstrate that chemical signatures are consistently retained in the ABFT fin spine edge and support the use of fin spine edges for discerning habitat use. The fin spine chemistry as a minimally invasive sampling method, combined with otolith chemistry, genetic markers, and tagging efforts can help us to reconstruct fish movements, providing a deeper understanding of the spatial population dynamics of this iconic fish species.The authors also wish to thank the many people who were involved in the collection of the fin spine samples used for this study under the provision of the ICCAT Atlantic Wide Research Programme for Bluefin Tuna (GBYP), which an ICCAT special research program funded by the European Union, several ICCAT CPCs, the ICCAT Secretariat, and other entities (see https://www.iccat.int/gbyp/en/overview.asp). The content of this paper does not necessarily reflect ICCAT's point of view or that of any of the other sponsors, who carry no responsibility. In addition, it does not indicate the Commission's future policy in this area. Special thanks to Pedro Lino and Ruben Muñoz-Lechuga from IPMA - Portuguese Institute for the Ocean and Atmosphere (Portugal), as provider of samples from the South of Portugal. Fulvio Garibaldi from UNIG - University of Genoa, Dept. of Earth, Life and Environment Sciences, for samples collected in the Ligurian Sea (Italy); Piero Addis and Rita Cannas from UNIC - Department of Life Science and Environment, University of Cagliari, for samples collected around Sardinian coast; F. Saadet Karakulak from ISTA - Department of Fisheries Technology and Management, Faculty of Aquatic Sciences, Istanbul University, for provider samples collected in the Levantine sea (Turkey); Antonio Celona from NECT - Necton Marine Research Society, for samples collected around Sicily (Italy), and Leif Nottestad from IMR - Institute of Marine Research, for providing samples collected in the Norwegian waters. We are so grateful for their efforts in collecting biological samples. Femtosecond Laser Ablation (fs-LA) analyses at the Institut des Sciences Analytiques et de Physico-Chimie pour l’Environnement et les Matériaux, Université de Pau et des Pays de l’Adour/CNRS (Pau, France) were conducted by Gaelle Barbotin as the engineer and under the supervision of Research engineer Dr. Christophe Pécheyran. We thank them for their help and assistance with technical issues. Stable Isotopes Analysis were conducted at the Japan Agency for Marine-Earth Science and Technology (JAMSTEC) and we are grateful for their assistance. The contents of this manuscript do not necessarily reflect the point of view of ICCAT or of the other funders, neither do they necessarily reflect the views of the funders and in no ways anticipate the Commission's future policy in this area. Editing help was provided by Science Journal Editors, Inc

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

ICP-AES and ICP-MS: Trends at Pittcon'98 [Tendances en spectrometries ICP-AES et ICP-MS]

International audienc

Ablation laser femtoseconde à haute cadence de tir et basse energie couplée à une détection ICPMS: Résultats préliminaires

cited By 10International audienceRecent advances in the field of ultra short pulse laser (femtosecond) allow now to integrate such sources in compact structures dedicated to laser ablation/ICPMS. We present a new infrared femtosecond laser device operating at low energy ( <100 μJ) and high repetition rate ( <10 kHz) providing a new analytical approach for laser ablation. Our results show that signal stability is improved when using the femtosecond laser. Combining the high repetition rate and the low energy features of this laser, a flash ablation approach was developed and was found to drastically enhance the signal to background ratio of the LA/ICPMS. This flash ablation consists in removing a large amount of material in a very short period of time and in transferring the resulting thin particles to the ICPMS. The process was found to be reproducible and quantitative. Detection limits obtained on glass samples could then be improved by a factor within 10 to 40 compared to a 266 nm nanosecond laser ablation. Conversely, the low energy femtosecond ablation can be adjusted to ablate very small amount of material. Depth profile analysis on Cr/Ni multilayer revealed a depth profile resolution better than 20 nm per pulse

Determination of volatile species of metals and metalloids in an urban atmosphere

cited By 0International audienceThe distribution of different volatile metal species after three campaigns during September 1995, April 1996, and May 1996 detected in the vicinity of Bordeaux, France, was studied. Thirteen sites were selected including indoor and outdoor locations. The sampling sites represented industrial activities and evaluated the magnitude of the automotive emissions. Volatile species identified by comparing the isotopic match and retention time from injection of standards were tetraethyllead compounds, elemental mercury Hg°, dimethylselenide, and tetramethyltin. The total alkyl lead (TAL) concentrations were 0.3-2.9 ng/cu m in industrial or suburban areas, 2.0-43.8 ng/cu m in the urban samples, and 110.4-341.3 ng/cu m in the underground car park. The average TAL values measured during September 1995 yielded higher TAL concentrations compared to those of May 1996 with similar traffic density conditions

Volatile metal and metalloid species (Pb, Hg, Se) in a European urban atmosphere (Bordeaux, France)

cited By 43International audienceAmbient air measurements of volatile metal and metalloid compounds were conducted in a European urban environment (Bordeaux, France). Air samples were collected with a cryogenic trap and analyzed by low-temperature gas chromatography with ICP/MS detection. Indoor and outdoor sites were studied. Tetraalkyllead compounds (Me(4-n)Et(n)Pb, n = 0-4) and elemental mercury were found to be the major volatile metal species. Average concentrations of 15.5 and 2.7 ng/m3 as metal have been reported respectively for total alkyllead species and elemental mercury in open area. These results illustrate the general phasing out of atmospheric lead initiated in the past decade. Accumulation of dimethyl selenide has been recorded in a building probably originating from human breath. Volatile metal species distribution in the different sites is discussed with regards to meteorological conditions and automotive traffic parameters. Occurrence of unknown volatile metal and metalloid species likely to occur in urban environment is also reported and discussed

Field determination of volatile selenium species at ultra trace levels in environmental waters by on-line purging, cryofocusing and detection by atomic fluorescence spectroscopy

cited By 31International audienceThe field determination of selenium species was obtained after stripping 1 l of water, removal of the water vapour by a water trap, and cryofocusing in a small packed chromatographic column hyphenated to a non dispersive atomic fluorescence detector. Water trap and purging conditions were carefully studied. Under routine operating conditions, absolute detection limits of 4 and 4.5 pg of Se for Me2Se and Me2Se2 were obtained, respectively. Under routine conditions, linearity extended up to 1 ng as Se for the different species studied. The selectivity of the system is discussed in the presence of carbon-containing species. This system was applied to the determination of volatile selenium species in the Gironde estuarine environment (France). Me2Se was found to be the main volatile selenium species in concentrations ranging from 0.8 to 6.3 pmol l-1. Seasonal variations have been observed and commented upon. Correlation with water temperature and salinity is also discussed