Elemental Analysis of Biological Matrices by Laser Ablation High Resolution Inductively Coupled Plasma Mass Spectrometry (LA-HR-ICP-MS) and High Resolution Inductively Coupled Plasma Mass Spectrometry (HR-ICP-MS)

The need for elemental analysis of biological matrices such as bone, teeth, and plant matter for sourcing purposes has emerged within the forensic and geochemical laboratories. Trace elemental analyses for the comparison of aterials such as glass by inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS has been shown to offer a high degree of discrimination between different manufacturing sources. Unit resolution ICP-MS instruments may suffer from some polyatomic interferences including 40Ar16O+, 40Ar16O1H+, and 40Ca16O+ that affect iron measurement at trace levels. Iron is an important element in the analysis of glass and also of interest for the analysis of several biological matrices. A comparison of the nalytical performance of two different ICP-MS systems for iron analysis in glass for determining the method detection limits (MDLs), accuracy, and precision of the measurement is presented. Acid digestion and laser ablation methods are also compared. Iron polyatomic interferences were reduced or resolved by using dynamic reaction cell and high resolution ICP-MS. MDLs as low as 0.03 ìg g-1 and 0.14 ìg g-1 for laser ablation and solution based analyses respectively were achieved. The use of helium as a carrier gas demonstrated improvement in the detection limits of both iron isotopes (56Fe and 57Fe) in medium resolution for the HR-ICP-MS and with a dynamic reaction cell (DRC) coupled to a quadrupole ICP-MS system. The development and application of robust analytical methods for the quantification of trace elements in biological matrices has lead to a better understanding of the potential utility of these measurements in forensic chemical analyses. Standard reference materials (SRMs) were used in the development of an analytical method using HR-ICP-MS and LA-HR-ICP-MS that was subsequently applied on the analysis of real samples. Bone, teeth and ashed marijuana samples were analyzed with the developed method. Elemental analysis of bone samples from 12 different individuals provided discrimination between individuals, when femur and humerus bones were considered separately. Discrimination of 14 teeth samples based on elemental composition was achieved with the exception of one case where samples from the same individual were not associated with each other. The discrimination of 49 different ashed plant (cannabis)samples was achieved using the developed method.

Elemental Analysis of Glass and Ink by Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) and Laser Induced Breakdown Spectroscopy (LIBS)

The necessity of elemental analysis techniques to solve forensic problems continues to expand as the samples collected from crime scenes grow in complexity. Laser ablation ICP-MS (LA-ICP-MS) has been shown to provide a high degree of discrimination between samples that originate from different sources. In the first part of this research, two laser ablation ICP-MS systems were compared, one using a nanosecond laser and another a femtosecond laser source for the forensic analysis of glass. The results showed that femtosecond LA-ICP-MS did not provide significant improvements in terms of accuracy, precision and discrimination, however femtosecond LA-ICP-MS did provide lower detection limits. In addition, it was determined that even for femtosecond LA-ICP-MS an internal standard should be utilized to obtain accurate analytical results for glass analyses. In the second part, a method using laser induced breakdown spectroscopy (LIBS) for the forensic analysis of glass was shown to provide excellent discrimination for a glass set consisting of 41 automotive fragments. The discrimination power was compared to two of the leading elemental analysis techniques, µXRF and LA-ICP-MS, and the results were similar; all methods generated >99% discrimination and the pairs found indistinguishable were similar. An extensive data analysis approach for LIBS glass analyses was developed to minimize Type I and II errors en route to a recommendation of 10 ratios to be used for glass comparisons. Finally, a LA-ICP-MS method for the qualitative analysis and discrimination of gel ink sources was developed and tested for a set of ink samples. In the first discrimination study, qualitative analysis was used to obtain 95.6% discrimination for a blind study consisting of 45 black gel ink samples provided by the United States Secret Service. A 0.4% false exclusion (Type I) error rate and a 3.9% false inclusion (Type II) error rate was obtained for this discrimination study. In the second discrimination study, 99% discrimination power was achieved for a black gel ink pen set consisting of 24 self collected samples. The two pairs found to be indistinguishable came from the same source of origin (the same manufacturer and type of pen purchased in different locations). It was also found that gel ink from the same pen, regardless of the age, was indistinguishable as were gel ink pens (four pens) originating from the same pack.

Activity concentrations of radionuclides in 5 short cores taken in 2007-2008 measured by ICP-MS and HPGe gamma spectrometry

Natural radionuclides and man-made 137Cs were analyzed in five short sediment cores taken in northern part of the Gulf of Eilat (Gulf of Aqaba) in order to provide information on sedimentation and mixing rates and sediment sources. The maximum estimates of sedimentation rates based on excess 210Pb were found to vary between 0.105 ± 0.020 and 0.35 ± 0.23 cm · year**-1. Even the lowest estimates are significantly higher than those expected from dust deposition, suggesting other sources and processes being responsible for most of the allochthonous material accumulation, including periodical floods following heavy rain events, internal erosion or triggers, like earthquakes. In 137Cs depth profiles no 1963 related nuclear weapon test maxima were found; instead, the activities decrease monotonically, suggesting that a major process leading to radionuclides' depth distribution might be mixing. The mixing rates calculated from 137Cs, excess 210Pb and excess 228Th reach values up to 2.18 ± 0.69 cm**2 · year**-1.

Appendix A: LA-ICP-MS results (Laser-ablation inductively coupled plasma mass spectrometer) from monazite Moacir standard

Three samples of garnet-kyanite paragneiss from the Variscan Ulten Zone (Northern Italy) were studied in detail for U-Th-Pb monazite dating. Monazite in these gneisses is abundant, shows highly variable grain size and occupies different textural positions: within the matrix, as inclusion in garnet and kyanite, within apatite aggregates. Monazite shows different deformation features as a function of the textural position: enclosed (shielded) monazite is generally more fractured than matrix (unshielded) monazite. The integration of textural information with deformation features and in situ U-Th-Pb analyses by LA-ICP-MS indicates that there is no direct correlation between textural site and monazite ages. Old ages of 351-343 Ma, determined on portions of large matrix (unshielded) monazite and on rare domains of monazite shielded by garnet, have been related to a prograde stage of the Variscan metamorphic evolution of the Ulten Zone. Ages of 330-326 Ma, which are related to the thermal peak, are recorded by small matrix monazite, external domains of large matrix monazite, and by (domains of) fractured monazite enclosed in garnet and kyanite. Large, old unshielded grains formed as blasts during the prograde metamorphic history and survived the peak metamorphism during which crystallisation/re-crystallisation partially occurred.

In situ Lithium and Boron isotope determinations in mica, pyroxene, and serpentine by LA-MC-ICP-MS

Boron and Li are light, incompatible elements that preferentially partition into the liquid phase, whether melt or aqueous fluid, and thus are useful for tracking fluid-related processes in rocks. Most of the Li isotopic data presently available on subduction-related rocks are from whole-rock analyses; and the B isotopic analyses of subduction material have been carried out either on whole-rocks or in-situ on an accessory phase, such as tourmaline. The new method presented here couples an ESI New Wave UP-193-FX ArF* (193 nm) excimer laser-ablation microscope with a Neptune Plus (Thermo Scientific) MC-ICP-MS aiming to measure both Li and B isotopes in situ with good spatial resolution (metamorphic minerals are commonly chemically zoned, and whole-rock analyses lose this detail). The data thus obtained are compared with SIMS analyses on the same mineral samples for B, and with MC-ICP-MS analyses on whole-rock or mineral separates from the same sample for Li. Additionally, data acquired on tourmaline standards were compared to SIMS values. The results show that for B concentrations above 5 μg/g, the data obtained by LA-MC-ICP-MS and by SIMS are identical within error, for mica (phengitic muscovite), pyroxene (jadeite), serpentine (antigorite), and tourmaline. For Li concentrations above 10 μg/g, the data obtained by LA-MC-ICP-MS and by MC-ICP-MS are also identical, within error, for mica (phengitic muscovite), and pyroxene (jadeite). However, analyses of tourmaline standards have shown significant differences with reference values, so LA-MC-ICP-MS does not yet appear to be an appropriate method to analyze Li isotopes in tourmalines. Thus, LA-MC-ICP-MS is a suitable method to measure Li and B isotopes with good spatial resolution in major rock-forming silicates from subduction-related rocks where concentrations exceed 10 μg/g and 5 μg/g, respectively, with an error on individual measurements equal to or less than previously used methods, but obtainable in a significantly shorter amount of time. The external reproducibility is ± 2.88 to 3.31 ‰ for B and ± 1.50 to 1.75 for Li, which is lower than or equal to the variations encountered within a given chemically zoned sample (up to 10 ‰ of variation within a given natural sample).

Elemental Analysis and Forensic Comparison of Soils by Laser-Induced Breakdown Spectroscopy (LIBS) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS)

The elemental analysis of soil is useful in forensic and environmental sciences. Methods were developed and optimized for two laser-based multi-element analysis techniques: laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and laser-induced breakdown spectroscopy (LIBS). This work represents the first use of a 266 nm laser for forensic soil analysis by LIBS. Sample preparation methods were developed and optimized for a variety of sample types, including pellets for large bulk soil specimens (470 mg) and sediment-laden filters (47 mg), and tape-mounting for small transfer evidence specimens (10 mg). Analytical performance for sediment filter pellets and tape-mounted soils was similar to that achieved with bulk pellets. An inter-laboratory comparison exercise was designed to evaluate the performance of the LA-ICP-MS and LIBS methods, as well as for micro X-ray fluorescence (μXRF), across multiple laboratories. Limits of detection (LODs) were 0.01-23 ppm for LA-ICP-MS, 0.25-574 ppm for LIBS, 16-4400 ppm for µXRF, and well below the levels normally seen in soils. Good intra-laboratory precision (≤ 6 % relative standard deviation (RSD) for LA-ICP-MS; ≤ 8 % for µXRF; ≤ 17 % for LIBS) and inter-laboratory precision (≤ 19 % for LA-ICP-MS; ≤ 25 % for µXRF) were achieved for most elements, which is encouraging for a first inter-laboratory exercise. While LIBS generally has higher LODs and RSDs than LA-ICP-MS, both were capable of generating good quality multi-element data sufficient for discrimination purposes. Multivariate methods using principal components analysis (PCA) and linear discriminant analysis (LDA) were developed for discriminations of soils from different sources. Specimens from different sites that were indistinguishable by color alone were discriminated by elemental analysis. Correct classification rates of 94.5 % or better were achieved in a simulated forensic discrimination of three similar sites for both LIBS and LA-ICP-MS. Results for tape-mounted specimens were nearly identical to those achieved with pellets. Methods were tested on soils from USA, Canada and Tanzania. Within-site heterogeneity was site-specific. Elemental differences were greatest for specimens separated by large distances, even within the same lithology. Elemental profiles can be used to discriminate soils from different locations and narrow down locations even when mineralogy is similar.

Avaliação da composição mineral de vinhos de talha do Alentejo usando ICP-MS

Os Vinhos de Talha do Alentejo representam uma herança da presença romana na península ibérica e a sua compreensão e análise são muito importantes para a sua preservação. O trabalho que aqui se apresenta, representa uma parte de um estudo alargado sobre vinhos de talha que procura compreender a influência do método de vinificação em talha na composição química destes vinhos, de modo a poder caracterizá-los num contexto mais abrangente de preservação de um património cultural. Com este trabalho procurou-se saber se as características únicas destes vinhos, conferem alguma alteração na sua composição mineral e se os valores encontrados estão dentro dos valores de referência, nomeadamente no que diz respeito a questões de segurança alimentar, com particular atenção para alguns metais pesados como o Manganês, Níquel, Cobre, Zinco, Cádmio e Chumbo. Para tal, usámos 16 vinhos tintos, 16 vinhos brancos e 15 vinhos palhetes que foram gentilmente cedidos pela organização do concurso VITIFRADES do ano de 2014, e estudou-se a sua composição química elementar em 32 elementos (Na, Mg, Al, P, K, Ca, Sc, Mn, Fe, Co, Ni, Cu, Zn, Se, Sr, Cd, In, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Er, Tm, Yb, Pb e Bi) através de ICP-MS. Os resultados da análise multielementar permitiram concluir que os valores encontrados para estes vinhos estão dentro dos limites esperados, não se verificando nenhuma contaminação metálica, especialmente no que diz respeito a alguns elementos que podem levantar questões importantes de segurança alimentar devido à sua toxicidade

Development and application of a selenium speciation method in cattle feed and beef samples using HPLC-ICP-MS: evaluating the selenium metabolic process in cattle.

2016

Quantification of the uranium concentration in human urine by inductively coupled plasma-sector field mass spectrometry (ICP-SFMS)

In this study, the validation of a method for analyzing the uranium (U) concentration in human urine samples by inductively coupled plasma-sector field mass spectrometry (ICP-SFMS) was conducted. PROCORAD (the Association for the Promotion of Quality Control in Radiotoxicological Analysis) provided two urine samples spiked with unknown contents of U (Sample A = 33.6 ± 1.0 µg/L and Sample B = 3.3 ± 0.1 µg/L) and one unspiked sample as a blank. The analyses were directly performed on the diluted urine samples (dilution factor = 1:20) in 5% v/v HNO3. The results obtained by ICP-SFMS corresponded well with the reference values, and the limits of detection were 235U = 0.049 × 10-3 µg/L and 238U = 7.37 × 10-3 µg/L. The ICP-SFMS technique has been shown to be successful in the analysis of the U concentration in human urine samples and for the quantification of isotopic ratios.

Analytical methodologies based on X-Ray Fluorescence Spectrometry (XRF) and Inductively Couple Plasma Spectroscopy (ICP) for the assessment of metal dispersal around mining environments

La investigació que es presenta en aquesta tesi es centra en l'aplicació i millora de metodologies analítiques existents i el desenvolupament de nous procediments que poden ser utilitzats per a l'estudi dels efectes ambientals de la dispersió dels metalls entorn a les zones mineres abandonades. En primer lloc, es van aplicar diferents procediments d'extracció simple i seqüencial per a estudiar la mobilitat, perillositat i bio-disponibilitat dels metalls continguts en residus miners de característiques diferents. Per altra banda, per a estudiar les fonts potencials de Pb en la vegetació de les zones mineres d'estudi, una metodologia basada en la utilització de les relacions isotòpiques de Pb determinades mitjançant ICP-MS va ser avaluada. Finalment, tenint en compte l'elevat nombre de mostres analitzades per a avaluar l'impacte de les activitats mineres, es va considerar apropiat el desenvolupament de mètodes analítics d'elevada productivitat. En aquest sentit la implementació d'estratègies quantitatives així com l'aplicació de les millores instrumentals en els equips de XRF han estat avaluades per a aconseguir resultats analítics fiables en l'anàlisi de plantes. A més, alguns paràmetres de qualitat com la precisió, l'exactitud i els límits de detecció han estat curosament determinats en les diverses configuracions de espectròmetres de XRF utilitzats en el decurs d'aquest treball (EDXRF, WDXRF i EDPXRF) per a establir la capacitat de la tècnica de XRF com a tècnica alternativa a les clàssiques comunament aplicades en la determinació d'elements en mostres vegetals.

Evaluation of sample preparation procedures and krypton as an interference standard probe for arsenic speciation by HPLC-ICP-QMS

Different conditions of extraction using water, a methanol-water mixture and nitric acid solutions were evaluated for speciation of As(iii), As(v), DMA and MMA in plant samples that previously received As(v) after being sown and emergence was investigated. Microwave-assisted extraction (MAE) using diluted nitric acid solutions was also performed for arsenic extraction from chicken feed samples. The separation and determination of arsenic species were performed using HPLC-ICP-MS. The interference standard method (IFS) using 83Kr+ as the IFS probe was employed to minimize spectral interferences caused by polyatomic species, such as 40Ar 35Cl+. The extraction procedures tested presented adequate extraction efficiencies (90%), and the four arsenic species evaluated were found in plant samples. Extractions with diluted nitric acid solution at 90 °C were the most efficient strategy, with quantitative recoveries for all four As species in plant tissues. On the other hand, the methanol-water mixture was the solvent with the lowest extraction efficiency (50-60%). For chicken feed samples, MAE at 100 °C for 30 min resulted in an extraction efficiency of 97% and only As(v) was found, without any species interconversion. The IFS method contributed to improving precision and limits of detection and quantification for all tested extraction procedures. Significant improvements on accuracy were obtained by applying the IFS method and recoveries between 77 and 94%, and 82 and 93% were obtained for plant extracts and chicken feed samples, respectively. This journal is © 2013 The Royal Society of Chemistry.

Entwicklung eines Verfahrens zur Ultraspurenbestimmung der Platingruppenelemente in Umwelt- und geologischen Proben mit einem ICP-QMS unter Verwendung der Isotopenverdünnungsanalyse sowie geeigneter Separationstechniken

ZusammenfassungSchwerpunkt dieser Arbeit war die Verfahrensentwicklung zur Ultraspurenbestimmung der Platingruppenelemente (PGE) in Umwelt- und geologischen Proben unter Verwendung der massenspektrometrischen Isotopenverdünnungsanalyse mit anschließender Bestimmung an einem Quadrupol ICP-MS (ICP-QMSIVA). Geeignete Separationstechniken in der Probenaufbereitung, um die PGE von der Matrix der untersuchten Proben zu trennen, stellten eine richtige und präzise Bestimmung der Ultraspuren an einem Quadrupol ICP-MS sicher.Das Verfahren konnte anhand von geologischen Referenzmaterialien aus Kanada sichergestellt werden. Gerade die Wiederholungsbestimmungen der verschiedenen Referenzmaterialien unter Verwendung des ICP-QMSIVA Verfahrens sind beispiellos und in dieser Form noch nicht in der Literatur beschrieben. Durch systematische Messungen konnten Richtigkeit und Präzision des Verfahrens bestätigt werden und die Inhomogenität des Referenzmaterials UMT-1 bezüglich Pt bewiesen werden. Das in dieser Arbeit entwickelte Verfahren zur Ultraspurenbestimmung der PGE mit ICP-QMSIVA wurde im Rahmen des Projektes 'Production and certification of a road dust reference material for platinum, palladium and rhodium (PGEs) in automative catalytic converters (PACEPAC)' der Europäischen Union zur Zertifizierung von zwei Referenzmaterialien für Umweltproben eingesetzt. Hierbei wurde bei der Zertifizierung ('intercomparison round') eine sehr gute Übereinstimmung der Ergebnisse mit dem gewichteten Mittelwert der Ergebnisse für Pd und Pt mit den übrigen teilnehmenden Laboratorien festgestellt. Die mit der hier entwickelten Methode erhaltenen Ergebnisse wurden ohne Ausnahme für alle gemessenen Elemente zur Zertifizierung herangezogen. Damit leistete die vorliegende Arbeit einen erheblichen Beitrag zum erfolgreichen Abschluß dieses Projekts. Den Erwartungen hinsichtlich Richtigkeit und Reproduzierbarkeit des entwickelten Verfahrens wurde somit voll entsprochen. Erneut konnte die große Bedeutung der Isotopenverdünnungstechnik für die Zertifizierung von Referenzmaterialien aufgezeigt werden, da mit dieser Technik bei sachgerechtem Einsatz Ergebnisse hoher Richtigkeit erzielt werden. Durch vergleichende Messungen mit der NiS-Dokimasie und NAA, die in einer Kooperation mit dem Kernchemischen Institut der Universität Mainz durchgeführt wurden, und dem hier verwendeten Verfahren, konnten übereinstimmende Daten, hinsichtlich der Abnahme der Konzentrationen von Pd und Pt in Abhängigkeit von der Entfernung zu einer Autobahn, erzielt werden. Diese Arbeit und die Forschungsergebnisse, die mit der anerkannten NAA erzielt wurden, zeigen, daß die PGE durch Katalysatoren von Automobilen überwiegend metallisch emittiert werden. Der anthropogene Eintrag der PGE in die Umwelt kann mit dem ICP-QMSIVA Verfahren weiterhin sehr gut verfolgt werden.

Sample locations, CTD data, mean spring and annual temperatures and salinities from World Ocean Atlas (WOA, 2001), and ICP-OES Mg/Ca data

Due to its strong gradient in salinity and small temperature gradient the Mediterranean provides an ideal setting to study the impact of salinity on the incorporation of Mg into foraminiferal tests. We have investigated tests of Globorotalia inflata and Globigerina bulloides in plankton tow and core top samples from the Western Mediterranean using ICP-OES for bulk analyses and LA-ICP-MS for analyses of individual chambers in single specimens. Mg/Ca observed in G. inflata are consistent with existing calibrations, whereas G. bulloides had significantly higher Mg/Ca than predicted, particularly in core top samples from the easterly stations. Scanning Electron Microscopy and Laser Ablation ICP-MS revealed secondary overgrowths on some tests, which could explain the observed high core top Mg/Ca. We suggest that the Mediterranean intermediate and deep water supersaturated with respect to calcite cause these overgrowths and therefore increased bulk Mg/Ca. However, the different species are influenced by diagenesis to different degrees probably due to different test morphologies. Our results provide new perspectives on reported anomalously high Mg/Ca in sedimentary foraminifera and the applicability of the Mg/Ca paleothermometry in high salinity settings, by showing that (1) part of the signal is generated by precipitation of inorganic calcite on the foraminifer test due to increased calcite saturation state of the water and (2) species with high surface-to-volume shell surfaces are potentially more affected by secondary Mg-rich calcite encrustation.