Capabilities of laser ablation—inductively coupled plasma mass spectrometry for (trace) element analysis of car paints for forensic purposes

Deconinck, Isolde; Latkoczy, Christopher; Günther, Detlef; Govaert, Filip; Vanhaecke, Frank

doi:10.1039/b514007b

Cited by 52 publications

(42 citation statements)

References 28 publications

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“…36 In particular, the flat-top beam profile of the 193 nm ArF excimer laser used in this work is ideal for this kind of application, as documented in previous works. [37][38][39] In principle, by using an output energy significantly exceeding the threshold and a sufficiently wide laser beam diameter, it is possible to obtain representative compositional data throughout the process of ablation, as long as a value of 6 for the depth/ diameter ratio is not exceeded, 34 although for this particular laser system it has been recommended not to exceed a depth/diameter ratio of 1.5, in order to achieve uniform flat-bottomed craters. 40 The examination of the craters obtained after ablation of the samples by SEM permitted us to estimate that the penetration depth obtained after firing 600 pulses varied between 21 and 27 µm, corresponding to approximately 40 nm of penetration per pulse.…”

Section: Resultsmentioning

confidence: 99%

Laser Ablation-Inductively Coupled Plasma Mass Spectrometry for the Characterization of Pigments in Prehistoric Rock Art

et al. 2007

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In this work, several red-colored paintings of post-Paleolithic schematic style found in 10 different shelters in the vicinity of the Vero River (Huesca) were sampled and subjected to analysis by means of scanning electron microscopy-energy-dispersive X-ray spectrometry (SEM-EDX), Raman spectroscopy, and laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS). The goal of this research was to obtain meaningful information on the samples composition, in order to establish differences or similarities among them. The combined use of these techniques proved beneficial, as Raman data permitted structural information on the compounds present (hematite was identified as the main pigment, whereas calcite and gypsum are the main components of the substrate layer, as well as of the accretions that covered the pigments) to be obtained, while the quantitative values obtained by SEM were suitable for the use of Ca as internal reference during LA-ICPMS analysis. However, it was this latter technique that provided the most relevant data for fingerprinting purposes. The potential of this technique for obtaining spatially resolved information allowed the multielement quantitative analysis of the pigment layer, in spite of the presence of superficial accretions. The sensitivity of the technique permitted the determination of more than 40 elements present in a wide concentration range (from microgram per gram to 10% level) with minimum sample consumption (approximately 900 ng for each sample, corresponding to five replicates). Finally, in order to establish significant differences, only those elements showing a high correlation with Fe (As, Co, Mo, Sb, Tl, and Zr, in this case) were selected, as it is expected that these were truly present in the original pigment, while others could have migrated into the pigment layer throughout time. By using this information, it seems feasible to discriminate between various paint pots, as demonstrated for the samples under investigation.At the end of the Ice Age, the great herds that had provided sustenance for the Paleolithic hunters disappeared from France and Spain. In the large forest areas that flourished owing to the warmer climate, groups of deer and related species lived. These animals were fast and elusive and, thus, much harder to hunt. As a consequence, man had to modify his hunting techniques, as well as forage for the seeds and fruits that the forest provided or the fish that were available in rivers or on the coast. Cooperation was essential, and this change was reflected in the art of this postPaleolithic period. 1 Bands of such hunter-gatherers left a record of their activities in shelters scattered throughout the Iberian Peninsula, among other regions. The differences with Paleolithic paintings are evident, as a simpler silhouette technique emerges. Moreover, the new paintings seem to have a clear narrative meaning, featuring a higher proportion of hominine figures. 2 Investigation of these paintings can provide relevant hints about the technological level as ...

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Section: Resultsmentioning

confidence: 99%

Laser Ablation-Inductively Coupled Plasma Mass Spectrometry for the Characterization of Pigments in Prehistoric Rock Art

et al. 2007

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“…7 However, in LA-ICP-MS, high mass resolution MS was needed to eliminate the polyatomic spectroscopic interferences that originated from the complex matrix of car paints, which would have otherwise masked the analyte signal profile, thereby degrading the discriminating power of the technique. 4 This problem arises because, in ICP-MS, each analyte possesses only one or a few isotopes, which is in contrast to ICP-OES, where a large number of emission lines are usually available for each analyte, enabling the selection of one or more interference-free emission lines in each case.…”

Section: Introductionmentioning

confidence: 99%

Solid sampling electrothermal vaporization inductively coupled plasma optical emission spectrometry for discrimination of automotive paint samples in forensic analysis

Asfaw

Wibetoe

Beauchemin

2012

J. Anal. At. Spectrom.

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Pieces of automotive paint often constitute trace evidence at crime scenes, especially in hit-and-run cases. As minute amounts of sample generally are available for forensic analysis, sensitive direct analysis methods are preferable to multi-step methods that may lead to sample contamination and/or analyte loss. Such a simple method was developed for discrimination of automotive paint samples. It involves solid sampling electrothermal vaporization (ETV) coupled to inductively coupled plasma optical emission spectrometry (ICP-OES) and multivariate analysis. A total of 18 automotive paint fragments were collected by scraping six red-colored car wrecks from three sides (front, side and back). Two replicates of each paint fragment were analysed. In each case, 0.8-2.0 mg paint was directly weighed onto an ETV graphite boat, which was then inserted into the ETV furnace for vaporization at 2200 C. The vaporization products were carried into the ICP by Ar carrier gas containing dichlorodifluoromethane reactant gas. For classification of paint samples according to their sources, several elements were simultaneously monitored. No sample pretreatment or quantification of the elements was needed. Point-by-point normalization of the emission signal of each analyte to an Ar emission line was carried out, followed by integration of the resulting transient signal. The data matrices composed of the integrated areas (divided by sample mass) for the different elements were then subjected to principal component analysis (PCA), cluster analysis and linear discriminant analysis (LDA). After identifying the major contributing variables by PCA, LDA was performed and showed that a combination of three/four variables from Cr, Pb, Sn, and Zn correctly assigned each of 18 red paint samples to the correct source car. Hence, solid sampling ETV-ICP-OES, which only requires a very small amount of sample, is a simple technique for forensic automotive paint analysis, i.e. for the identification of the make and model of a car in question.

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“…Fast transient multielement analysis is performed at a fixed resolution mode setting. Deconinck et al 114 used laser ablation with quadrupole-based ICP-MS and ICP-SFMS for element analysis of car paint fragments found at crime scenes for forensic purposes. It was observed that the complex matrix composition of some of the layers -organic components, kaolin, talc, barite and/or Fe-containing pigments -resulted in spectral interferences, significantly affecting the signal profiles, especially for the transition metals when using the quadrupole-based instrument.…”

Section: Ceramics Glass and Paintsmentioning

confidence: 99%

Inductively Coupled Plasma Mass Spectrometry

Jakubowski

Horsky

Roos

et al. 2014

Sector Field Mass Spectrometry for Elemental and Isotopic Analysis

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ICP-MS is based on the formation of (preferentially monovalent positively) charged atomic ions in an inductively coupled Ar plasma at almost 10 000 K. The ions formed are transferred from the plasma source at ambient pressure into a mass separator operated at high vacuum via a set of cones. The ions are separated according to their mass/charge ratio in the mass separator (quadrupole, magnetic sector field or time-of-flight mass separator). In most cases, the ions are detected using a secondary electron multiplier; in some set-ups (also) a Faraday cup can be used. Single-collector (scanning mass spectrometer usually used for quantitative elemental analysis) or multicollector (static operation of mass spectrometer for precise isotope ratio analysis) configurations can be found (Figures 12.1 and 12.2).

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Capabilities of laser ablation—inductively coupled plasma mass spectrometry for (trace) element analysis of car paints for forensic purposes

Cited by 52 publications

References 28 publications

Laser Ablation-Inductively Coupled Plasma Mass Spectrometry for the Characterization of Pigments in Prehistoric Rock Art

Laser Ablation-Inductively Coupled Plasma Mass Spectrometry for the Characterization of Pigments in Prehistoric Rock Art

Solid sampling electrothermal vaporization inductively coupled plasma optical emission spectrometry for discrimination of automotive paint samples in forensic analysis

Inductively Coupled Plasma Mass Spectrometry

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