Search

In 2011, the European Commission introduced new regulations on how nanomaterials are defined. Since then, researchers have emphasized that more complete characterization of nanoparticles (NPs) includes not just mass and size determinations, but also the determination of the particle number concentrations. In this study, two different sample introduction approaches for the analysis of NP suspensions with inductively coupled plasma mass spectrometry (ICP-MS) were investigated: pneumatic nebulization (sp-ICP-MS) and microdroplet generation (MDG-ICP-MS). These approaches were compared for the determination of particle number concentrations (PNCs) of gold and silver NP suspensions diluted in either ultra-pure water or citrate solution. For accurate sp-ICP-MS analysis, it is crucial to know the transport efficiency of nebulized sample into the plasma. Here, transport efficiencies, measured by the waste collection method, were 11-14% for Ag suspensions and 9-11% for Au. In contrast, the droplet transport efficiency of MDG-ICP-MS was 100%.Analysis by sp-ICP-MS yielded a lower particle number concentration than expected (only 20-40% of the expected value), whereas MDG-ICP-MS had NP recoveries up to 80%. This study indicates that NP reference materials are of major importance for particle number determination and detailed results on particle number concentrations for different suspensions with respect to storage time are discussed.

High‐resolution palaeorecords of climate are critical to improving current understanding of climate variability, its sensitivity and impact on the environment in the past and in the future. Sediments from the Cariaco Basin off the coast of Venezuela have proven to be sensitive recorders of tropical palaeoclimate variability down to an annual scale. However, the fingerprint of climate and sea level in the sediments of the last glacial period is still not completely understood. In this study, lamination analysis of sediments from the Cariaco Basin is extended to the last glacial period. Detailed sedimentological and geochemical analysis (laser ablation–inductively coupled plasma–mass spectrometry) reveals couplets of light‐coloured, terrigenous‐rich and dark‐coloured, biogenic opal‐rich laminae, which are interpreted to reflect the seasonal migration of the Intertropical Convergence Zone. In addition, a previously undescribed, nearly pure terrigenous lamina type is observed, which is referred to hereafter as a ‘C‐layer’. The C‐layers in the sedimentary sequence are interpreted as flood layers that originate from local rivers. The occurrence of these C‐layers is investigated for two core locations in the Cariaco Basin over the last 110 kyr by continuous X‐ray fluorescence scanning. Dansgaard–Oeschger oscillations are most clearly traced by proxies reflecting productivity and marine organic matter content of the sediment. In contrast, the abundance of terrigenous material differs at times between the two sites. On an interglacial to glacial timescale, the ability to record events causing C‐layers is likely to be influenced by changes in sea level and source proximity. On a millennial scale, both sediment cores contain more C‐layers during warmer interstadials compared to colder stadials during Marine Isotope Stage 3. This finding implies that interstadials were not only wetter than stadials, but probably also characterized by increased rainfall variability, leading to a

High‐resolution palaeorecords of climate are critical to improving current understanding of climate variability, its sensitivity and impact on the environment in the past and in the future. Sediments from the Cariaco Basin off the coast of Venezuela have proven to be sensitive recorders of tropical palaeoclimate variability down to an annual scale. However, the fingerprint of climate and sea level in the sediments of the last glacial period is still not completely understood. In this study, lamination analysis of sediments from the Cariaco Basin is extended to the last glacial period. Detailed sedimentological and geochemical analysis (laser ablation–inductively coupled plasma–mass spectrometry) reveals couplets of light‐coloured, terrigenous‐rich and dark‐coloured, biogenic opal‐rich laminae, which are interpreted to reflect the seasonal migration of the Intertropical Convergence Zone. In addition, a previously undescribed, nearly pure terrigenous lamina type is observed, which is referred to hereafter as a ‘C‐layer’. The C‐layers in the sedimentary sequence are interpreted as flood layers that originate from local rivers. The occurrence of these C‐layers is investigated for two core locations in the Cariaco Basin over the last 110 kyr by continuous X‐ray fluorescence scanning. Dansgaard–Oeschger oscillations are most clearly traced by proxies reflecting productivity and marine organic matter content of the sediment. In contrast, the abundance of terrigenous material differs at times between the two sites. On an interglacial to glacial timescale, the ability to record events causing C‐layers is likely to be influenced by changes in sea level and source proximity. On a millennial scale, both sediment cores contain more C‐layers during warmer interstadials compared to colder stadials during Marine Isotope Stage 3. This finding implies that interstadials were not only wetter than stadials, but probably also characterized by increased rainfall variability, leading to a

High‐resolution palaeorecords of climate are critical to improving current understanding of climate variability, its sensitivity and impact on the environment in the past and in the future. Sediments from the Cariaco Basin off the coast of Venezuela have proven to be sensitive recorders of tropical palaeoclimate variability down to an annual scale. However, the fingerprint of climate and sea level in the sediments of the last glacial period is still not completely understood. In this study, lamination analysis of sediments from the Cariaco Basin is extended to the last glacial period. Detailed sedimentological and geochemical analysis (laser ablation–inductively coupled plasma–mass spectrometry) reveals couplets of light‐coloured, terrigenous‐rich and dark‐coloured, biogenic opal‐rich laminae, which are interpreted to reflect the seasonal migration of the Intertropical Convergence Zone. In addition, a previously undescribed, nearly pure terrigenous lamina type is observed, which is referred to hereafter as a ‘C‐layer’. The C‐layers in the sedimentary sequence are interpreted as flood layers that originate from local rivers. The occurrence of these C‐layers is investigated for two core locations in the Cariaco Basin over the last 110 kyr by continuous X‐ray fluorescence scanning. Dansgaard–Oeschger oscillations are most clearly traced by proxies reflecting productivity and marine organic matter content of the sediment. In contrast, the abundance of terrigenous material differs at times between the two sites. On an interglacial to glacial timescale, the ability to record events causing C‐layers is likely to be influenced by changes in sea level and source proximity. On a millennial scale, both sediment cores contain more C‐layers during warmer interstadials compared to colder stadials during Marine Isotope Stage 3. This finding implies that interstadials were not only wetter than stadials, but probably also characterized by increased rainfall variability, leading to a

In dieser Doktorarbeit wurde eine analytische Methode zur Charakterisierung metallischer Nanopartikel (NPs) entwickelt und die Methode bei der Untersuchung natürlicher Proben angewendet. Mit einem analytisches System bestehend aus einem Mikrotropfengenerator (microdroplet generator, MDG) zusammen mit einem pneumatischen Zerstäuber und einem induktiv gekoppeltem Plasma-Massenspektrometer (ICP-MS) konnte eine quantitative und qualitative Charakterisierung von NPs durchgeführt werden. Der MDG wurde verwendet um die Kalibrierungsfunktion für die massenspektrometrische Quantifizierung der Metalle in den Nanopartikelproben, die über den pneumatischen Zerstäuber eingeführt wurden, einzurichten. Der Hauptvorteil dieser Anordnung besteht darin, dass mit dem MDG für jedes Metall Tropfen einer gewünschten Größe hergestellt werden können und eine 100 %-ige Transporteffizienz gegeben ist. Die eingeführte Masse korrelierte mit der Signalintensität von Nanopartikeln, so dass die mit dem MDG generierten Tropfen für die Kalibrierung verwendet werden konnten ohne dass Referenzmaterial erforderlich war. Die aufwändige und fehleranfällige Bestimmung der Effizienz eines Zerstäubers, die für die Bestimmung des Metallgehaltes von NPs mittels eines Einzelpartikel-ICP-MS (spICP-MS) erforderlich ist, konnte dadurch vermieden werden. Unter Anwendung dieser dualen Einführungsmethode wurden Größen und Konzentrationen einer Reihe von Standard Silber (Ag) NPs und Referenz Gold (Au) NPs mit hoher Genauigkeit bestimmt. Zusätzlich wurde mit einem neuen kommerziell verfügbaren ICP-Flugzeitmassenspektrometer (ICP-TOF-MS) Ag und Au NPs in unterschiedlichen Matrices charakterisiert: in verschiedenen Salzsäure (HCl)- und Salpetersäure (HNO3)- Konzentrationen und in Gegenwart verschiedener Elemente. Bei den unterschiedlichen Matrices war die Größenbestimmung innerhalb der gegebenen Standardabweichungen korrekt., In this doctoral thesis an analytical method for characterising metal nanoparticles (NPs) was developed and its application for investigating natural samples verified. An analytical system consisting of a microdroplet generator (MDG) used in combination with a pneumatic nebuliser (PN) and an inductively coupled plasma mass spectrometer (ICP-MS) proved capable of quantitatively and qualitatively identifying NPs. The MDG was used to establish the calibration function for mass quantification of the metal present in the sample NPs introduced via the PN. The major advantage of this configuration is that the MDG generated droplets of tailored size for any given metal while offering a 100 % transport efficiency. The introduced mass correlated with signal intensities of NPs and thus the microdroplet generated droplets could be used for calibration purposes without the need for any reference material. Thus, the tedious and error-prone nebuliser efficiency determination step that is required when determining the NP metal content using the single particle mode ICP-MS (spICP-MS) approach, could be avoided. With this dual sample introduction method, the sizes and concentrations of a range of standard silver (Ag) NPs and gold (Au) reference NPs were determined with high accuracy. Additionally, together with a new commercially available ICP-time of flight-MS (ICP-TOF-MS) the characterisation of Ag- and Au-NPs was carried out in various matrices: In hydrochloric (HCl) and nitric acid (HNO3) at a range of concentration and in different elemental environments. In the presence of matrices, it was found that the size characterisation of the NPs is correct within the standard deviation.

High‐resolution palaeorecords of climate are critical to improving current understanding of climate variability, its sensitivity and impact on the environment in the past and in the future. Sediments from the Cariaco Basin off the coast of Venezuela have proven to be sensitive recorders of tropical palaeoclimate variability down to an annual scale. However, the fingerprint of climate and sea level in the sediments of the last glacial period is still not completely understood. In this study, lamination analysis of sediments from the Cariaco Basin is extended to the last glacial period. Detailed sedimentological and geochemical analysis (laser ablation–inductively coupled plasma–mass spectrometry) reveals couplets of light‐coloured, terrigenous‐rich and dark‐coloured, biogenic opal‐rich laminae, which are interpreted to reflect the seasonal migration of the Intertropical Convergence Zone. In addition, a previously undescribed, nearly pure terrigenous lamina type is observed, which is referred to hereafter as a ‘C‐layer’. The C‐layers in the sedimentary sequence are interpreted as flood layers that originate from local rivers. The occurrence of these C‐layers is investigated for two core locations in the Cariaco Basin over the last 110 kyr by continuous X‐ray fluorescence scanning. Dansgaard–Oeschger oscillations are most clearly traced by proxies reflecting productivity and marine organic matter content of the sediment. In contrast, the abundance of terrigenous material differs at times between the two sites. On an interglacial to glacial timescale, the ability to record events causing C‐layers is likely to be influenced by changes in sea level and source proximity. On a millennial scale, both sediment cores contain more C‐layers during warmer interstadials compared to colder stadials during Marine Isotope Stage 3. This finding implies that interstadials were not only wetter than stadials, but probably also characterized by increased rainfall variability, leading to a

Manganese geochemistry in deep-sea sediments is known to vary greatly over the first few centimeters, which overlaps the in-sediment depth habitats of several benthic foraminiferal species. Here we investigated manganese incorporation in benthic foraminiferal shell carbonate across a six-station depth transect in the Gulf of Lions, NW Mediterranean, to unravel the impacts of foraminiferal ecology and Mn pore water geochemistry. Over this transect water depth increases from 350 to 1987m, while temperature (∼ 13°C) and salinity (∼ 38.5) remained relatively constant. Manganese concentrations in the tests of living (rose bengal stained) benthic foraminiferal specimens of Hoeglundina elegans, Melonis barleeanus, Uvigerina mediterranea, and Uvigerina peregrina were measured using laser ablation inductively coupled mass spectrometry (laser ablation ICP-MS). Pore water manganese concentrations show a decrease from shallow to deeper waters, which corresponds to a generally decreasing organic-matter flux with water depth. Differences in organic-matter loading at the sediment-water interface affects oxygen penetration depth into the sediment and hence Mn pore water profiles. Mn/Ca values for the investigated foraminiferal species reflect pore water geochemistry and species-specific microhabitat in the sediment. The observed degree of variability within a single species is in line with known ranges in depth habitat and gradients in redox conditions. Both the Mn/Ca ratio and interspecific variability hence reflect past Mn cycling and related early diagenetic processes within the sediment, making this a potential tool for bottom-water oxygenation and organic-matter fluxes. Dynamics of both in-sediment foraminiferal depth habitats and Mn cycling, however, limit the application of such a proxy to settings with relatively stable environmental conditions.

Fundamental understanding of aerosol formation and particle transport are important aspects of understanding and improving laser-ablation ICP-MS. To obtain more information about particles entering the ICP, laser aerosols generated under different ablation conditions were collected on membrane filters. The particles and agglomerates were then visualised using scanning electron microscope (SEM) imaging. To determine variations between different sample matrices, opaque (USGS BCR-2G) and transparent (NIST SRM 610) glass, CaF2, and brass (MBH B26) samples were ablated using two different laser wavelengths, 193 and 266nm. This study showed that the condensed nano-particles (∼10nm in diameter) formed by laser ablation reach the ICP as micron-sized agglomerates; this is apparent from filters which contain only a few well-separated particles and particle agglomerates. Ablation experiments on different metals and non-metals show that the structure of the agglomerates is matrix-dependent. Laser aerosols generated from silicates and metals form linear agglomerates whereas particle-agglomerates of ablated CaF2 have cotton-like structures. Amongst other conditions, this study shows that the absorption characteristics of the sample and the laser wavelength determine the production of micron-sized spherical particles formed by liquid droplet ejection

Whereas colored andesine/labradorite had been thought unique to the North American continent, red andesine supposedly coming from the Democratic Republic of the Congo (DR Congo), Mongolia, and Tibet has been on the market for the last 10years. After red Mongolian andesine was proven to be Cu-diffused by heat treatment from colorless andesine starting material, efforts were taken to distinguish minerals sold as Tibetan and Mongolian andesine. Using nanosecond laser ablation-inductively coupled plasma mass spectrometry (ICPMS), the main and trace element composition of andesines from different origins was determined. Mexican, Oregon, and Asian samples were clearly distinguishable by their main element content (CaO, SiO2 Na2O, and K2O), whereas the composition of Mongolian, Tibetan, and DR Congo material was within the same range. Since the Li concentration was shown to be correlated with the Cu concentration, the formerly proposed differentiation by the Ba/Sr vs. Ba/Li ratio does not distinguish between samples from Tibet and Mongolia, but only between red and colorless material. Using femtosecond laser ablation multi-collector ICPMS in high-resolution mode, laboratory diffused samples showed variations up to 3‰ for 65Cu/63Cu within one mineral due to the diffusion process. Ar isotope ratio measurements proved that heat treatment will reduce the amount of radiogenic 40Ar in the samples significantly. Only low levels of radiogenic Ar were found in samples collected on-site in both mine locations in Tibet. Together with a high intra-sample variability of the Cu isotope ratio, andesine samples labeled as coming from Tibet are most probably Cu-diffused, using initially colorless Mongolian andesines as starting material. Therefore, at the moment, the only reliable source of colored andesine/labradorite remains the state of Oregon. Figure Cu diffusion can be used to turn a plain, colorless andesine into a red gemstone. Cu and Ar isotope ratios in combination with main and t

The dependence of analyte sensitivity and vaporization efficiency on the operating parameters of an inductively coupled plasma mass spectrometer (ICPMS) was investigated for a wide range of elements in aerosols, produced by laser ablation of silicate glass. The ion signals were recorded for different carrier gas flow rates at different plasma power for two different laser ablation systems and carrier gases. Differences in atomization efficiency and analyte sensitivity are significant for the two gases and the particle size distribution of the aerosol. Vaporization of the aerosol is enhanced when helium is used, which is attributed to a better energy-transfer from the plasma to the central channel of the ICP and a higher diffusion rate of the vaporized material. This minimizes elemental fractionation caused by sequential evaporation and reduces diffusion losses in the ICP. The sensitivity change with carrier gas flow variation is dependent on m/z of the analyte ion and the chemical properties of the element. Elements with high vaporization temperatures reach a maximum at lower gas flow rates than easily vaporized elements. The sensitivity change is furthermore dependent on m/z of the analyte ion, due to the mass dependence of the ion kinetic energies. The mass response curve of the ICPMS is thus not only a result of space charge effects in the ion optics but is also affected by radial diffusion of analyte ions and the mismatch between their kinetic energy after expansion in the vacuum interface and the ion optic settings

The figures of merit of a pulsed glow discharge time-of-flight mass spectrometer (GD-TOFMS) as a detector for gas chromatography (GC) analysis were evaluated. The mass resolution for the GD-TOFMS was determined on FWHM in the high mass range (208Pb+) as high as 5,500. Precision of 400 subsequent analyses was calculated on 63Cu+ to be better than 1% RSD with no significant drift over the time of the analysis. Isotope precision based on the 63Cu+/65Cu+ ratio over 400 analyses was 1.5% RSD. The limits of detection for gaseous analytes (toluene in methanol as solvent) were determined to be as low as several hundred ppb or several hundred pg absolute without using any pre-concentration technique. Furthermore, the different GD source parameters like capillary distance, cathode-anode spacing, and GD source pressure with regards to the accessible elemental, structural, and molecular information were evaluated. It was demonstrated that each of these parameters has severe influence on the ratio of elemental, structural, and parent molecular information in chemical speciation analysis

A method was developed for the precise and accurate determination of ovalbumin labelled with p-hydroxy-mercuribenzoic acid (pHMB) using polyacrylamide gel electrophoresis with ns-laser ablation-inductively coupled plasma mass spectrometry. Following systematic optimisation of the ablation process in terms of detection sensitivity, two different quantification strategies were applied: external calibration using standards of the derivatized protein after 13C+ normalization and, as a proof of concept, label-specific isotope dilution analysis (IDA) using pHMB enriched in the isotope 199Hg. Due to the inhomogeneous distribution of the protein within the gel bands, it could be demonstrated that the IDA approach was superior in terms of precision and accuracy. Furthermore, it permits a reliable quantification, if more complex separation protocols are applied, as typically occurring analyte loss and degradation can be compensated for as soon as complete mixture of spike and sample is achieved. The estimated limit of detection was 160fmol in the case of ovalbumin. In contrast to earlier studies using metals naturally present in proteins, no loss of mercury was observed during separation under denaturing conditions and other sample preparation steps. Using label-specific IDA, the measured isotope ratios in the gel corresponded to recoveries between 95% and 103%

Precise and accurate isotope ratio measurements are an important task in many applications such as isotope-dilution mass spectrometry, bioavailability studies, or the determination of isotope variations in geological or nuclear samples. The technique of MC-ICP-MS has attracted much attention because it permits the precise measurement of isotope compositions for a wide range of elements combined with excellent detection limits due to high ionisation efficiencies. However, the results are based mainly on measurements using continuous sample introduction. In the present study the determination of isotope ratios on various transient signals with a time duration of 30 to 60s has been achieved by coupling high-performance liquid chromatography to a multicollector inductively coupled plasma mass spectrometer. In order to investigate the origin of ratio drifts across the transient signals for this hyphenated technique, measurements with the same standard solutions were also carried out using a flow-injection device for sample introduction. As a result of this application it could be concluded that the main source of the bias in the measured isotope ratios is within the ICP-MS instead of fractionation effects on the chromatographic column material. Preliminary studies on short transient signals of gaseous samples (dry plasma) showed a reverse fractionation effect compared with wet plasma conditions (flow injection and HPLC)

To achieve separation of isobaric interferences and minimization of matrix related interferences for laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) electrothermal heating of laser generated aerosols was investigated by analyzing a range of solid samples: NIST SRM 610, MBH B26, BAM M381, BAM M601 and Tantalum. ICPMS measurements showed that individual elements can be removed from the laser-generated aerosol at characteristic temperatures for different solid materials. Signal reduction as high as 3 orders of magnitude were achieved for volatile elements, such as Ag and Cd when heating laser-generated aerosol of NIST SRM 610 silicate glass. A signal reduction of more than 99% was obtained for Rb while Sr remained practically unaffected. A temperature- and matrix-dependent change of particle size distribution after aerosol heating was observed by means of laser light scattering (direct aerosol visualization) and scanning electron microscopy. In the temperature range between 900 and 1,200°C, element unspecific signal suppression was observed, which could be related to a change of the particle size distributions

Ongoing discussions about the origin of elemental fractionation occurring during LA-ICP-MS analysis show that this problem is still far from being well understood. It is becoming accepted that all three possible sources (ablation, transport, excitation) contribute to elemental fractionation. However, experimental data about the vaporisation size limit of different particles in the ICP, as produced in laser ablation, have not been available until now. This information should allow one to determine the signal contributing mass within the ICP and would further clarify demands on suitable laser ablation systems and gas atmospheres in terms of their particle size distribution. The results presented here show a vaporisation size limit of laser induced particles, which was found at particle sizes between 90nm and 150nm using an Elan6000 ICP-MS. Due to the fact that the ICP-MS response was used as evaluation parameter, vaporisation and ionisation limits are not distinguishable. The upper limit was determined by successively removing the larger particles from the aerosol, which was created by ablation of a NIST610 glass standard at a wavelength of 266nm, using a recently developed particle separation device. Various particle fractions were separated from the aerosol entering the ICP. The decrease in signal intensity is not proportional to the decrease in volume, indicating that particles above 150nm in diameter are not completely ionised in the ICP. Due to the limited removal range of the particle separation device, which cannot remove particles smaller than 150nm, single hole ablations were used to determine the lower vaporisation limit. This is based on measurements showing that larger particles occur dominantly during the first 100laser pulses only. After this period, the ratio of ICP-MS counts and total particle volume was found to be constant while most of the particles are smaller than 90nm, indicating complete vaporisation and ionisation of these particles. To describ

Solution-doped metal powder pellets as well as aspirated liquids were used as calibration samples to analyze pure copper and zinc certified reference materials (CRMs) by femtosecond laser ablation ICP-MS. It was demonstrated that calibration by copper pellets resulted in relative deviations up to 20%, whereas fs-LA-ICP-MS among copper-based CRMs led to inaccuracies in the same range unless nominal mass fractions were chosen to be <3mg/kg. Calibration by zinc pellets generally provided better accuracy. Depending on the analyte considered, deviations below 10% were obtained even for mass fractions close to the limit of quantification. Our data, therefore, indicate solution-doped metal powder pellets to be suitable as calibration samples for fs-LA-ICP-MS of metals. Furthermore, the utilization of liquid standards for calibration was found to result in stronger deviations of up to 50% for both copper and zinc samples which, in addition, turned out to be dependent on the plasma conditions. Figure Different calibration strategies for fs-LA-ICP-MS

Regionally metamorphosed pelitic rocks at Campolungo, Central Alps, contain biotite, muscovite, garnet, staurolite, kyanite, and quartz, and the minor minerals tourmaline, plagioclase, chlorite, rutile, and ilmenite. Accessory allanite, apatite, monazite, potassium feldspar, xenotime, and zircon have also been identified. The bulk-rock chemical composition is similar to that of shales, and indicates that the protolith was deposited in an active continental margin setting. Element distribution maps, electron microprobe analyses and in situ UV-laser ablation inductively coupled plasma mass spectrometry data document a pronounced zoning in garnet and tourmaline porphyroblasts. Garnet displays a typical bell-shaped MnO zoning profile, with a maximum (∼3 wt %) in the euhedral core. Cores are also rich in Y and heavy rare earth elements (HREE; e.g. 2150 ppm Y). In their broad rim, all garnet crystals display a subhedral annulus (10-15 µm wide), which is distinctly enriched in Ca, Sr, Y, and HREE, and which probably resulted from the breakdown of allanite (at ∼550°C, ∼6·4 kbar). Another characteristic feature of garnet rims is their sinusoidal chondrite-normalized REE pattern, which may represent partial equilibration with a light REE-enriched medium, probably generated through the breakdown of metamorphic allanite. Similar REE patterns are exhibited by a Ca-poor internal zone (inside the annulus), which may represent an earlier partial equilibration following the breakdown of detrital monazite. The large tourmaline crystals exhibit an optically visible three-stage zoning, which comprises: a euhedral core; a continuously zoned inner rim with a prominent euhedral Ca-rich annulus; and an outer rim, which also displays a distinct Ca-rich annulus and is separated from the inner rim by a sutured boundary. This boundary represents a marked chemical discontinuity, characterized for example by a decrease in the Zn concentration from 250 ppm (inner rim) to 20 ppm (outer rim). This

The Braccia gabbro complex (Eastern Central Alps, Northern Italy) intruded the boundary between the Adriatic lowermost continental crust and the subcontinental upper mantle in Permian times. The gabbro complex consists mainly of gabbro-norites with minor dykes of quartz diorite and Fe-Ti-P-rich diorite. The gabbro-norites contain abundant cumulus clino- and orthopyroxene and only small amounts of olivine, indicating crystallization at high pressure (∼1·0 GPa). Slow, near-isobaric cooling of the gabbro erased compositional zoning of major and trace elements in magmatic minerals. Bulk-rock composition and the combination of mg-number in pyroxenes and modelling of mineral trace element data permit us to track the trace element enrichment in minerals and whole rocks. Some trace element rich gabbros represent frozen liquids, whereas others are cumulates formed from highly differentiated residual liquids. Differentiation of the gabbro complex is mainly driven by fractional crystallization of pyroxenes and plagioclase, resulting in a tholeiitic differentiation trend. The trace element composition of the parental melt was calculated from the most primitive pure cumulate found in the Braccia gabbro complex. This parental melt is similar to transitional mid-ocean ridge basalts, although the Braccia gabbro crystallized at the base of the continental crust. It is suggested that the parental melt originated from decompression melting of upwelling mantle within the spinel peridotite field. Thus, a thinned lithosphere with a high geothermal gradient existed at the northern part of the African plate in Permian times

The most voluminous silicic volcanic eruptions in the geological past were associated with caldera collapses above giant silicic magma reservoirs. The thermal evolution of these sub-caldera magma reservoirs controls the volume of eruptible magma and eruptive style. Here we combine high-precision zircon U-Pb geochronology, trace element analyses of the same mineral grains, and mass balance modeling of zircon trace element compositions allowing us to track the thermal and chemical evolution of the Oligocene Fish Canyon Tuff magma reservoir (Colorado, United States) as a function of absolute time. Systematic compositional variations in U-Pb dated zircons record ∼440 k.y. of magma evolution. An early phase of volumetric growth was followed by a period of cooling and crystallization, during which the Fish Canyon magma approached complete solidification. Subsequent remelting, due to underplated andesitic recharge magmas, began 219 ± 45 k.y. prior to eruption, and led to the generation of ∼5000 km3 of eruptible crystal-rich (∼45 vol%) dacite. Age-equivalent, but compositionally different, zircons in an andesite enclave from late-erupted Fish Canyon Tuff tie the growth and thermal evolution of the upper-crustal reservoir to a lower-crustal magma processing zone. Our results demonstrate that the combination of high-precision dating and trace element analyses of accessory zircons can reveal invaluable information about the chemical and thermal histories of silicic magmatic systems and provides critical input parameters for fluid dynamic modeling.

The most voluminous silicic volcanic eruptions in the geological past were associated with caldera collapses above giant silicic magma reservoirs. The thermal evolution of these sub-caldera magma reservoirs controls the volume of eruptible magma and eruptive style. Here we combine high-precision zircon U-Pb geochronology, trace element analyses of the same mineral grains, and mass balance modeling of zircon trace element compositions allowing us to track the thermal and chemical evolution of the Oligocene Fish Canyon Tuff magma reservoir (Colorado, United States) as a function of absolute time. Systematic compositional variations in U-Pb dated zircons record ∼440 k.y. of magma evolution. An early phase of volumetric growth was followed by a period of cooling and crystallization, during which the Fish Canyon magma approached complete solidification. Subsequent remelting, due to underplated andesitic recharge magmas, began 219 ± 45 k.y. prior to eruption, and led to the generation of ∼5000 km3 of eruptible crystal-rich (∼45 vol%) dacite. Age-equivalent, but compositionally different, zircons in an andesite enclave from late-erupted Fish Canyon Tuff tie the growth and thermal evolution of the upper-crustal reservoir to a lower-crustal magma processing zone. Our results demonstrate that the combination of high-precision dating and trace element analyses of accessory zircons can reveal invaluable information about the chemical and thermal histories of silicic magmatic systems and provides critical input parameters for fluid dynamic modeling.

The most voluminous silicic volcanic eruptions in the geological past were associated with caldera collapses above giant silicic magma reservoirs. The thermal evolution of these sub-caldera magma reservoirs controls the volume of eruptible magma and eruptive style. Here we combine high-precision zircon U-Pb geochronology, trace element analyses of the same mineral grains, and mass balance modeling of zircon trace element compositions allowing us to track the thermal and chemical evolution of the Oligocene Fish Canyon Tuff magma reservoir (Colorado, United States) as a function of absolute time. Systematic compositional variations in U-Pb dated zircons record ∼440 k.y. of magma evolution. An early phase of volumetric growth was followed by a period of cooling and crystallization, during which the Fish Canyon magma approached complete solidification. Subsequent remelting, due to underplated andesitic recharge magmas, began 219 ± 45 k.y. prior to eruption, and led to the generation of ∼5000 km3 of eruptible crystal-rich (∼45 vol%) dacite. Age-equivalent, but compositionally different, zircons in an andesite enclave from late-erupted Fish Canyon Tuff tie the growth and thermal evolution of the upper-crustal reservoir to a lower-crustal magma processing zone. Our results demonstrate that the combination of high-precision dating and trace element analyses of accessory zircons can reveal invaluable information about the chemical and thermal histories of silicic magmatic systems and provides critical input parameters for fluid dynamic modeling.

The most voluminous silicic volcanic eruptions in the geological past were associated with caldera collapses above giant silicic magma reservoirs. The thermal evolution of these sub-caldera magma reservoirs controls the volume of eruptible magma and eruptive style. Here we combine high-precision zircon U-Pb geochronology, trace element analyses of the same mineral grains, and mass balance modeling of zircon trace element compositions allowing us to track the thermal and chemical evolution of the Oligocene Fish Canyon Tuff magma reservoir (Colorado, United States) as a function of absolute time. Systematic compositional variations in U-Pb dated zircons record ∼440 k.y. of magma evolution. An early phase of volumetric growth was followed by a period of cooling and crystallization, during which the Fish Canyon magma approached complete solidification. Subsequent remelting, due to underplated andesitic recharge magmas, began 219 ± 45 k.y. prior to eruption, and led to the generation of ∼5000 km3 of eruptible crystal-rich (∼45 vol%) dacite. Age-equivalent, but compositionally different, zircons in an andesite enclave from late-erupted Fish Canyon Tuff tie the growth and thermal evolution of the upper-crustal reservoir to a lower-crustal magma processing zone. Our results demonstrate that the combination of high-precision dating and trace element analyses of accessory zircons can reveal invaluable information about the chemical and thermal histories of silicic magmatic systems and provides critical input parameters for fluid dynamic modeling.

Ten Early Bronze Age (BzA1, 2200-2000 BC) copper artefacts from the central Valais region from Switzerland were studied for their elemental composition and lead isotope ratios. In order to answer the archaeological question of a local copper supply, a database for copper minerals across the Valais (Switzerland) has been established. This database contains 69 data on lead isotope ratios as well as additional information on the minerals and geochemical associations for copper minerals from 38 locations in the Valais. Comparisons of the artefacts were also made with data pertaining to minerals from various deposits from Europe and Anatolia taken from the literature. The provenance of the materials is very diverse. Some of the data are compatible with the data from the copper mineral deposits of the Valais region. Moreover, three copper lunulae were identified as possibly Tuscan, which demonstrates contacts between Italy and the Valais region. This pattern also establishes a multiplicity of provenances for the metal and cultural influences in the Alpine environment of the Rhone Valley of Switzerland at the beginning of the Early Bronze Age.

The laser ablation characteristics of yttria-stabilized zirconia (YSZ) have been investigated as a function of the target microstructure and dopant level for different nanosecond- [ArF, KrF, and XeCl excimers; Nd:YAG (yttrium aluminum garnet) (fourth harmonic)] and femtosecond-laser sources [Ti:sapphire (fundamental and third harmonic)]. Particle ejection, which compromises the quality of coatings prepared by pulsed laser deposition (PLD), was analyzed in detail. Nanosecond-laser pulses cause a severe thermomechanical surface cracking and exfoliation of micron-sized fragments on a microsecond to millisecond time scale in the case of 8–9.5 mol % Y2O3-doped, fully stabilized zirconia (8YSZ and 9.5YSZ) targets. As a consequence of the intrinsic material brittleness, fully stabilized YSZ coatings deposited by PLD contained particles for all tested conditions. Lower doped partially stabilized zirconia (3YSZ) exhibits a superior fracture toughness attributed to a laser-induced partial transition to the monoclinic phase, detected by Raman spectroscopy, which enables the deposition of particle-free dense thin films by conventional PLD using nanosecond-UV laser radiation at moderate fluences of 1.2–1.5 J/cm2. The ablation dynamics of ultrashort laser pulses differ fundamentally from the nanosecond regime as evidenced, e.g., by time-resolved shadowgraphy and light scattering experiments. Femtosecond pulses prevent the exfoliation of micron-sized fragments but result invariably in a pronounced ejection of submicron particles. The resulting PLD coatings are porous and reveal a large surface roughness as they consist of an agglomeration of nanoparticles. Femtosecond-NIR pulses provide a factor of 2.5–10 higher material removal rates compared to nanosecond- and femtoseco- nd-UV pulses. The ablation metrics, i.e., threshold fluence and effective absorptivity, mainly depend on the laser wavelength while the pulse duration, target microstructure, and dopant level are of minor import

Laser ablation of zirconia-based ceramics in the ns- and fs-regime: Origin and elimination of target fragmentation in PLD

Microbial mats collected at cold methane seeps in the Black Sea carry out anaerobic oxidation of methane (AOM) to carbon dioxide using sulfate as the electron acceptor. These mats, which predominantly consist of sulfate-reducing bacteria and archaea of the ANME-1 and ANME-2 type, contain large amounts of proteins very similar to methyl-coenzyme M reductase from methanogenic archaea. Mass spectrometry of mat samples revealed the presence of two nickel-containing cofactors in comparable amounts, one with the same mass as coenzyme F430 from methanogens (m/z = 905) and one with a mass that is 46 Da higher (m/z = 951). The two cofactors were isolated and purified, and their constitution and absolute configuration were determined. The cofactor with m/z = 905 was proven to be identical to coenzyme F430 from methanogens. For the m/z = 951 species, high resolution ICP-MS pointed to F430 + CH2S as the molecular formula, and LA-ICP-SF MS finally confirmed the presence of one sulfur atom per nickel. Esterification gave two stereoisomeric pentamethyl esters with m/z = 1021, which could be purified by reverse phase HPLC and were subjected to comprehensive NMR analysis, allowing determination of their constitution and configuration as (172S)−172-methylthio-F430 pentamethyl ester and (172R)−172-methylthio-F430 pentamethyl ester. The corresponding diastereoisomeric pentaacids could also be separated by HPLC and were correlated to the esters via mild hydrolysis of the latter. Equilibration of the pentaacids under acid catalysis showed that the (172S) isomer is the naturally occurring albeit thermodynamically less stable one. The more stable (172R) isomer (80% at equilibrium) is an isolation artifact generated under the acidic conditions necessary for the isolation of the cofactors from the calcium carbonate-encrusted mats.

Microbial mats collected at cold methane seeps in the Black Sea carry out anaerobic oxidation of methane (AOM) to carbon dioxide using sulfate as the electron acceptor. These mats, which predominantly consist of sulfate-reducing bacteria and archaea of the ANME-1 and ANME-2 type, contain large amounts of proteins very similar to methyl-coenzyme M reductase from methanogenic archaea. Mass spectrometry of mat samples revealed the presence of two nickel-containing cofactors in comparable amounts, one with the same mass as coenzyme F430 from methanogens (m/z = 905) and one with a mass that is 46 Da higher (m/z = 951). The two cofactors were isolated and purified, and their constitution and absolute configuration were determined. The cofactor with m/z = 905 was proven to be identical to coenzyme F430 from methanogens. For the m/z = 951 species, high resolution ICP-MS pointed to F430 + CH2S as the molecular formula, and LA-ICP-SF MS finally confirmed the presence of one sulfur atom per nickel. Esterification gave two stereoisomeric pentamethyl esters with m/z = 1021, which could be purified by reverse phase HPLC and were subjected to comprehensive NMR analysis, allowing determination of their constitution and configuration as (172S)−172-methylthio-F430 pentamethyl ester and (172R)−172-methylthio-F430 pentamethyl ester. The corresponding diastereoisomeric pentaacids could also be separated by HPLC and were correlated to the esters via mild hydrolysis of the latter. Equilibration of the pentaacids under acid catalysis showed that the (172S) isomer is the naturally occurring albeit thermodynamically less stable one. The more stable (172R) isomer (80% at equilibrium) is an isolation artifact generated under the acidic conditions necessary for the isolation of the cofactors from the calcium carbonate-encrusted mats.

Die Strukturen der Erdalkalimetall-Subnitride (EA2N) von Calcium, Strontium und Barium ermöglichen mit ihrem schichtartigen Aufbau aus EA6N-Oktaedern Intercalationsreaktionen. Die Redox-Intercalation von Stickstoff in Sr2N wurde an Einkristallen untersucht. Nur durch eine drastische Erhöhung des Reaktionsgasdruckes im Vergleich zu den Reaktionen an mikrokristallinen Proben wurde die Intercalation der Diazenidionen in die Kristalle zu Sr4N3 und SrN möglich. Für eine analoge Intercalation von Wasserstoff in Sr2N konnten die Reaktionsbedingungen dahingehend optimiert werden, dass erstmals phasenreines Strontiumnitridhydrid (Sr2N)H bzw. deuterid (Sr2N)D erhalten wurde. Anhand von Intercalationsreaktionen mit Sr2N Kristallen konnte gezeigt werden, dass der Intercalationsprozess, erkennbar an der deutlichen Farbänderung von schwarz nach bersteinfarben, von außen nach innen fortschreitet. Als Methode zur räumlich aufgelösten Analyse wurde die Laserablation, in Kombination mit einem ICP - Massenspektrometer (LA-ICP-MS) verwendet. In der Literatur beschriebene Quantifizierungsstrategien wurden auf die Anwendbarkeit für die gegebene Fragestellung untersucht. Mit der ortsaufgelösten Analyse von Einkristallen konnte gezeigt werden, dass die Intercalation von Stickstoff in die Kristalle kontinuierlich von den Kanten zur Kristallmitte fortschreitet.

Die Strukturen der Erdalkalimetall-Subnitride (EA2N) von Calcium, Strontium und Barium ermöglichen mit ihrem schichtartigen Aufbau aus EA6N-Oktaedern Intercalationsreaktionen. Die Redox-Intercalation von Stickstoff in Sr2N wurde an Einkristallen untersucht. Nur durch eine drastische Erhöhung des Reaktionsgasdruckes im Vergleich zu den Reaktionen an mikrokristallinen Proben wurde die Intercalation der Diazenidionen in die Kristalle zu Sr4N3 und SrN möglich. Für eine analoge Intercalation von Wasserstoff in Sr2N konnten die Reaktionsbedingungen dahingehend optimiert werden, dass erstmals phasenreines Strontiumnitridhydrid (Sr2N)H bzw. deuterid (Sr2N)D erhalten wurde. Anhand von Intercalationsreaktionen mit Sr2N Kristallen konnte gezeigt werden, dass der Intercalationsprozess, erkennbar an der deutlichen Farbänderung von schwarz nach bersteinfarben, von außen nach innen fortschreitet. Als Methode zur räumlich aufgelösten Analyse wurde die Laserablation, in Kombination mit einem ICP - Massenspektrometer (LA-ICP-MS) verwendet. In der Literatur beschriebene Quantifizierungsstrategien wurden auf die Anwendbarkeit für die gegebene Fragestellung untersucht. Mit der ortsaufgelösten Analyse von Einkristallen konnte gezeigt werden, dass die Intercalation von Stickstoff in die Kristalle kontinuierlich von den Kanten zur Kristallmitte fortschreitet.

Die Strukturen der Erdalkalimetall-Subnitride (EA2N) von Calcium, Strontium und Barium ermöglichen mit ihrem schichtartigen Aufbau aus EA6N-Oktaedern Intercalationsreaktionen. Die Redox-Intercalation von Stickstoff in Sr2N wurde an Einkristallen untersucht. Nur durch eine drastische Erhöhung des Reaktionsgasdruckes im Vergleich zu den Reaktionen an mikrokristallinen Proben wurde die Intercalation der Diazenidionen in die Kristalle zu Sr4N3 und SrN möglich. Für eine analoge Intercalation von Wasserstoff in Sr2N konnten die Reaktionsbedingungen dahingehend optimiert werden, dass erstmals phasenreines Strontiumnitridhydrid (Sr2N)H bzw. deuterid (Sr2N)D erhalten wurde. Anhand von Intercalationsreaktionen mit Sr2N Kristallen konnte gezeigt werden, dass der Intercalationsprozess, erkennbar an der deutlichen Farbänderung von schwarz nach bersteinfarben, von außen nach innen fortschreitet. Als Methode zur räumlich aufgelösten Analyse wurde die Laserablation, in Kombination mit einem ICP - Massenspektrometer (LA-ICP-MS) verwendet. In der Literatur beschriebene Quantifizierungsstrategien wurden auf die Anwendbarkeit für die gegebene Fragestellung untersucht. Mit der ortsaufgelösten Analyse von Einkristallen konnte gezeigt werden, dass die Intercalation von Stickstoff in die Kristalle kontinuierlich von den Kanten zur Kristallmitte fortschreitet.

Die Strukturen der Erdalkalimetall-Subnitride (EA2N) von Calcium, Strontium und Barium ermöglichen mit ihrem schichtartigen Aufbau aus EA6N-Oktaedern Intercalationsreaktionen. Die Redox-Intercalation von Stickstoff in Sr2N wurde an Einkristallen untersucht. Nur durch eine drastische Erhöhung des Reaktionsgasdruckes im Vergleich zu den Reaktionen an mikrokristallinen Proben wurde die Intercalation der Diazenidionen in die Kristalle zu Sr4N3 und SrN möglich. Für eine analoge Intercalation von Wasserstoff in Sr2N konnten die Reaktionsbedingungen dahingehend optimiert werden, dass erstmals phasenreines Strontiumnitridhydrid (Sr2N)H bzw. deuterid (Sr2N)D erhalten wurde. Anhand von Intercalationsreaktionen mit Sr2N Kristallen konnte gezeigt werden, dass der Intercalationsprozess, erkennbar an der deutlichen Farbänderung von schwarz nach bersteinfarben, von außen nach innen fortschreitet. Als Methode zur räumlich aufgelösten Analyse wurde die Laserablation, in Kombination mit einem ICP - Massenspektrometer (LA-ICP-MS) verwendet. In der Literatur beschriebene Quantifizierungsstrategien wurden auf die Anwendbarkeit für die gegebene Fragestellung untersucht. Mit der ortsaufgelösten Analyse von Einkristallen konnte gezeigt werden, dass die Intercalation von Stickstoff in die Kristalle kontinuierlich von den Kanten zur Kristallmitte fortschreitet.

Die vorliegende Arbeit stellt die Ergebnisse der methodologischen Entwicklung räumlich aufgelöster Analyse mittels Scanning Laserablation-ICP-Massenspektrometrie dar. Eine neue Behandlung zur Quantifizierung transienter analytischer Signale wurde für die Wiederherstellung von Konzentrationsprofilen vorgeschlagen. Die Anwendung der entwickelten Modelle auf die räumlich aufgelöste Analyse mittels LA-ICP-MS ermöglicht verbesserten Informationsgewinn und lässt dadurch eine höhere räumliche Auflösung erreichen. Die Anwendbarkeit der LA-ICP-MS für die räumlich aufgelöste Bestimmung der Stöchiometrie in supraleitenden Borokarbiden wurde untersucht. Der Einfluss apparativer Größen auf das analytische Signal wurde aufgeklärt, um die Messbedingungen zu optimieren. Zusätzlich wurden Fraktionierungseffekte untersucht, um die Ursache und deren Auswirkung auf die Analyse supraleitender Borokarbiden zu erklären., This work represents the results of the methodological development of spatially resolved analysis by scanning laser ablation ICP mass spectrometry. A new approach to the quantification of transient analytical signals was proposed to reveal the concentration profile. An application of the developed models on spatially resolved analysis by LA-ICP-MS allows to gain more information from experimental data and hence to achieve better spatial resolution. The applicability of LA-ICP-MS to the spatially resolved determination of the stoichiometry of superconducting borocarbides was investigated. The effect of experimental parameters on analytical signals was elucidated in order to optimize the experimental conditions. In addition, fractionation effects were investigated to identify the causes for fractionation and their influence on the analysis of superconducting borocarbides.

Die vorliegende Arbeit stellt die Ergebnisse der methodologischen Entwicklung räumlich aufgelöster Analyse mittels Scanning Laserablation-ICP-Massenspektrometrie dar. Eine neue Behandlung zur Quantifizierung transienter analytischer Signale wurde für die Wiederherstellung von Konzentrationsprofilen vorgeschlagen. Die Anwendung der entwickelten Modelle auf die räumlich aufgelöste Analyse mittels LA-ICP-MS ermöglicht verbesserten Informationsgewinn und lässt dadurch eine höhere räumliche Auflösung erreichen. Die Anwendbarkeit der LA-ICP-MS für die räumlich aufgelöste Bestimmung der Stöchiometrie in supraleitenden Borokarbiden wurde untersucht. Der Einfluss apparativer Größen auf das analytische Signal wurde aufgeklärt, um die Messbedingungen zu optimieren. Zusätzlich wurden Fraktionierungseffekte untersucht, um die Ursache und deren Auswirkung auf die Analyse supraleitender Borokarbiden zu erklären., This work represents the results of the methodological development of spatially resolved analysis by scanning laser ablation ICP mass spectrometry. A new approach to the quantification of transient analytical signals was proposed to reveal the concentration profile. An application of the developed models on spatially resolved analysis by LA-ICP-MS allows to gain more information from experimental data and hence to achieve better spatial resolution. The applicability of LA-ICP-MS to the spatially resolved determination of the stoichiometry of superconducting borocarbides was investigated. The effect of experimental parameters on analytical signals was elucidated in order to optimize the experimental conditions. In addition, fractionation effects were investigated to identify the causes for fractionation and their influence on the analysis of superconducting borocarbides.

Die vorliegende Arbeit stellt die Ergebnisse der methodologischen Entwicklung räumlich aufgelöster Analyse mittels Scanning Laserablation-ICP-Massenspektrometrie dar. Eine neue Behandlung zur Quantifizierung transienter analytischer Signale wurde für die Wiederherstellung von Konzentrationsprofilen vorgeschlagen. Die Anwendung der entwickelten Modelle auf die räumlich aufgelöste Analyse mittels LA-ICP-MS ermöglicht verbesserten Informationsgewinn und lässt dadurch eine höhere räumliche Auflösung erreichen. Die Anwendbarkeit der LA-ICP-MS für die räumlich aufgelöste Bestimmung der Stöchiometrie in supraleitenden Borokarbiden wurde untersucht. Der Einfluss apparativer Größen auf das analytische Signal wurde aufgeklärt, um die Messbedingungen zu optimieren. Zusätzlich wurden Fraktionierungseffekte untersucht, um die Ursache und deren Auswirkung auf die Analyse supraleitender Borokarbiden zu erklären., This work represents the results of the methodological development of spatially resolved analysis by scanning laser ablation ICP mass spectrometry. A new approach to the quantification of transient analytical signals was proposed to reveal the concentration profile. An application of the developed models on spatially resolved analysis by LA-ICP-MS allows to gain more information from experimental data and hence to achieve better spatial resolution. The applicability of LA-ICP-MS to the spatially resolved determination of the stoichiometry of superconducting borocarbides was investigated. The effect of experimental parameters on analytical signals was elucidated in order to optimize the experimental conditions. In addition, fractionation effects were investigated to identify the causes for fractionation and their influence on the analysis of superconducting borocarbides.

Die vorliegende Arbeit stellt die Ergebnisse der methodologischen Entwicklung räumlich aufgelöster Analyse mittels Scanning Laserablation-ICP-Massenspektrometrie dar. Eine neue Behandlung zur Quantifizierung transienter analytischer Signale wurde für die Wiederherstellung von Konzentrationsprofilen vorgeschlagen. Die Anwendung der entwickelten Modelle auf die räumlich aufgelöste Analyse mittels LA-ICP-MS ermöglicht verbesserten Informationsgewinn und lässt dadurch eine höhere räumliche Auflösung erreichen. Die Anwendbarkeit der LA-ICP-MS für die räumlich aufgelöste Bestimmung der Stöchiometrie in supraleitenden Borokarbiden wurde untersucht. Der Einfluss apparativer Größen auf das analytische Signal wurde aufgeklärt, um die Messbedingungen zu optimieren. Zusätzlich wurden Fraktionierungseffekte untersucht, um die Ursache und deren Auswirkung auf die Analyse supraleitender Borokarbiden zu erklären., This work represents the results of the methodological development of spatially resolved analysis by scanning laser ablation ICP mass spectrometry. A new approach to the quantification of transient analytical signals was proposed to reveal the concentration profile. An application of the developed models on spatially resolved analysis by LA-ICP-MS allows to gain more information from experimental data and hence to achieve better spatial resolution. The applicability of LA-ICP-MS to the spatially resolved determination of the stoichiometry of superconducting borocarbides was investigated. The effect of experimental parameters on analytical signals was elucidated in order to optimize the experimental conditions. In addition, fractionation effects were investigated to identify the causes for fractionation and their influence on the analysis of superconducting borocarbides.

In-torch LA-ICP-MS was implemented into an in-house-built ICP-TOFMS system. The fast data acquisition capabilities of the new configuration allowed simultaneous multi-element measurement and readout of in-torch LA-ICP-MS signals with 30μs time resolution. The measurements confirmed previously observed fine structures of in-torch generated signals and provided new insights in the dynamic processes in the plasma on a microsecond time scale. The new setup is described in detail and first figures of merit are given. Figure Time dependent multi element signal after laser ablation in the torch of an ICP-TOFMS instrument