Time-of-flight secondary ion mass spectrometry: new application for urinary stones analysis

Dissertação para obtenção do Grau de Doutor em Engenharia Física

Secondary Ion Mass Spectrometry (SIMS): principles and applications

This article outlines the basis of the technique and shows some examples of applications in order to exhibit the expectations of this technique invaried scientific fields.

Combined Secondary Ion Mass Spectrometry Depth Profiling and Focused Ion Beam Analysis of Cu Films Electrodeposited under Oscillatory Conditions

The recrystallization behavior of Cu films electrodeposited under oscillatory conditions in the presence of plating additives was studied by means of secondary ion mass spectrometry (SIMS) and focused ion beam analysis. When combined with bis-(sodium-sulfopropyl)-disulfide (SPS), Imep levelers (polymerizates of imidazole and epichlorohydrin) show characteristic oscillations in the galvanostatic potential/time transient measurements. These are related to the periodic degradation and restoration of the active leveler ensemble at the interface. The leveler action relies on adduct formation between the Imep and MPS (mercaptopropane sulfonic acid)-stabilized CuI complexes that appear as intermediates of the copper deposition when SPS is present in the electrolyte. SIMS depth profiling proves that additives are incorporated into the growing film preferentially under transient conditions during the structural breakdown of the leveler ensemble and its subsequent restoration. In contrast, Cu films electrodeposited in the presence of a structurally intact Imep–CuI–MPS ensemble remain largely contamination free.

Intra-ring variability of Cr, As, Cd, and Pb in red oak revealed by secondary ion mass spectrometry: Implications for environmental biomonitoring

Reconstructing the history of ambient levels of metals by using tree-ring chemistry is controversial. This controversy can be resolved in part through the use of selective microanalysis of individual wood cells. Using a combination of instrumental neutron activation analysis and secondary ion mass spectrometry, we have observed systematic inhomogeneity in the abundance of toxic metals (Cr, As, Cd, and Pb) within annual growth rings of Quercus rubra (red oak) and have characterized individual xylem members responsible for introducing micrometer-scale gradients in toxic metal abundances. These gradients are useful for placing constraints on both the magnitude and the mechanism of heavy metal translocation within growing wood. It should now be possible to test, on a metal-by-metal basis, the suitability of using tree-ring chemistries for deciphering long-term records of many environmental metals.

The geomagnetic mass spectrometer— mass and energy dispersions of ionospheric ion flows into the magnetosphere

NASA's Dynamics Explorer (DE) mission was designed to study the coupling between the Earth's magnetosphere, ionosphere and neutral thermosphere1. One area of major interest is the outflow of ionospheric plasma into the magnetosphere, the scale and significance of which is only now becoming apparent with the advent of mass-resolving, low-energy ion detectors. Here we compare observations of ion flows in the polar magnetosphere, made by the retarding ion mass spectrometer (RIMS)2 on DE1, with those made simultaneously in the topside ionosphere by the ion drift meter (IDM)3 on the lower-altitude DE2 spacecraft. The results show the dayside auroral ionosphere to be a significant and highly persistent source of plasma for the magnetosphere. The upwelling ionospheric ions are spatially dispersed, according to both their energy and mass, by the combined actions of the geomagnetic field and the dawn-to-dusk convection electric field, in an effect analogous to the operation of an ion mass spectrometer.

Metastable BrO(2+) and NBr(2+) molecules in the gas phase

The doubly positively charged gas-phase molecules BrO(2+) and NBr(2+) have been produced by prolonged high-current energetic oxygen (17 keV (16)O(-)) ion surface bombardment (ion beam sputtering) of rubidium bromide (RbBr) and of ammonium bromide (NH(4)Br) powdered ionic salt samples, respectively, pressed into indium foil. These novel species were observed at half-integer m/z values in positive ion mass spectra for ion flight times of roughly similar to 12 mu s through a magnetic-sector secondary ion mass spectrometer. Here we present these experimental results and combine them with a detailed theoretical investigation using high level ab initio calculations of the ground states of BrO(2+) and NBr(2+), and a manifold of excited electronic states. NBr(2+) and BrO(2+), in their ground states, are long-lived metastable gas-phase molecules with well depths of 2.73 x 10(4) cm(-1) (3.38 eV) and 1.62 x 10(4) cm(-1) (2.01 eV); their fragmentation channels into two monocations lie 2.31 x 10(3) cm(-1) (0.29 eV) and 2.14 x 10(4) cm(-1) (2.65 eV) below the ground state minimum. The calculated lifetimes for NBr(2+) (v '' < 35) and BrO(2+) (v '' < 18) are large enough to be considered stable against tunneling. For NBr(2+), we predicted R(e) = 3.051 a(0) and omega(e) = 984 cm(-1); for BrO(2+), we obtained 3.033 a(0) and 916 cm(-1), respectively. The adiabatic double ionization energies of BrO and NBr to form metastable BrO(2+) and NBr(2+) are calculated to be 30.73 and 29.08 eV, respectively. The effect of spin-orbit interactions on the low-lying (Lambda + S) states is also discussed. (C) 2011 American Institute of Physics. [doi:10.1063/1.3562121]

Chemical and isotopic compositions of Archean magmatic and metasedimentary rocks and minerals from the Podolia domain, Ukrainian Shield

Zircons from the oldest magmatic and metasedimentary rocks in the Podolia domain of the Ukrainian shield were studied and dated by the U-Pb method on a NORDSIM secondary-ion mass spectrometer. Age of zircon cores in enderbite gneisses sampled in the Kazachii Yar and Odessa quarries on the opposite banks of the Yuzhnyi Bug River reaches 3790 Ma. Cores of terrigenous zircons in quartzites from the Odessa quarry as well as in garnet gneisses from the Zaval'e graphite quarry have age within 3650-3750 Ma. Zircon rims record two metamorphic events around 2750-2850 Ma and 1900-2000 Ma. Extremely low U content in zircons of the second age group indicates conditions of the granulite facies metamorphism in Paleoproterozoic within the Podolia domain. Measured data on orthorocks (enderbite-gneiss) and metasedimentary rocks unambiguously suggest existence of the ancient Paleoarchean crust in the Podolia (Dniester-Bug) domain of the Ukrainian shield. They contribute in our knowledge of scales of formation and geochemical features of the primordial crust.

On the prospective detection of polyoxymethylene in comet 67P/Churyumov–Gerasimenko with the COSIMA instrument onboard Rosetta

The presence of polyoxymethylene (POM) in cometary grains has been debated years ago. Although never proven, its presence can not be excluded. Rosetta, the ESA mission to comet 67P/Churyumov–Gerasimenko, may answer this question. On board the spacecraft, COSIMA (COmetary Secondary Ion Mass Analyzer) will analyze the grains ejected from the nucleus using a Time Of Flight Secondary Ion Mass Spectrometer (TOF-SIMS). In this paper we report the extent to which COSIMA will be able to detect POM if this compound is present on cometary grains. We have analyzed two kinds of POM polymers with a laboratory model of COSIMA. Positive mass spectra display alternating sequence of peaks with a separation of 30.011 Da between 1 and 600 Da related to formaldehyde and its oligomers but also to the fragmentation of these oligomers. The separation of 30.011 Da of numbers peaks, corresponding to the fragmentation into H2CO is characteristic of POM and we show that it could be highlight by mathematical treatment. POM lifetime on COSIMA targets have also been studied as POM is thermally instable. It can be concluded that the cometary grains analysis have to be planned not too long after their collection in order to maximize the chances to detect POM. This work was supported by the Centre National d'Etudes Spatiales (CNES).

Assigning dates to thin gneissic veins in high-grade metamorphic terranes: A cautionary tale from Akilia, southwest Greenland

A granodiorite from Akilia, southwest Greenland, previously suggested to date putative life-bearing rocks to greater than or equal to3.84 Ga, is re-investigated using whole-rock major and trace-element geochemistry, and detailed cathodoluminescence image-guided secondary ion mass spectrometer analyses of zircon U-Th-Pb and rare earth elements. Complex zircon internal structure reveals three episodes of zircon growth and/or recrystallization dated to c. 3.84 Ga, 3.62 Ga and 2.71 Ga. Rare earth element abundances imply a significant role for garnet in zircon generation at 3.62 Ga and 2.71 Ga. The 3.62 Ga event is interpreted as partial melting of a c. 3.84 Ga grey gneiss precursor at granulite facies with residual garnet. Migration of this 3.62 Ga magma (or melt-crystal mush) away from the melt source places a maximum age limit on any intrusive relationship. These early Archaean relationships have been complicated further by isotopic reworking in the 2.71 Ga event, which could have included a further episode of partial melting. This study highlights a general problem associated with dating thin gneissic veins in polyphase metamorphic terranes, where field relationships may be ambiguous and zircon inheritance can be expected.

Integrated Pb- and S-isotope investigation of sulphide minerals from the early Archaean of southwest Greenland

We present high-spatial resolution secondary ion mass spectrometry (SIMS) measurements of Pb and S isotopes in sulphides from early Archaean samples at two localities in southwest Greenland. Secondary pyrite from a 3.71 Ga sample of magnetite-quartz banded iron formation in the Isua Greenstone Belt, which has previously yielded unradiogenic Pb consistent with its ancient origin, contains sulphur with a mass independently fractionated (MIF) isotope signature (Delta(33)S =+3.3 parts per thousand). This reflects the secondary mineralization of remobilized sedimentary S carrying a component modified by photochemical reactions in the early Archaean atmosphere. It further represents one of the most extreme positive excursions so far known from the early Archaean rock record. Sulphides from a quartz-pyroxene rock and an ultramafic boudin from the island of Akilia, in the Godth (a) over circle bsfjord, have heterogeneous and generally radiogenic Pb isotopic compositions that we interpret to represent partial re-equilibration of Pb between the sulphides and whole rocks during tectonothermal events at 3.6, 2.7 and 1.6 Ga. Both these samples have Delta(33)S=0 (within analytical error) and therefore show no evidence for MIF sulphur. These data are consistent with previous interpretations that the rock cannot be proven to have a sedimentary origin. Our study illustrates that SIMS S-isotope measurements in ancient rocks can be used to elucidate early atmospheric parameters because of the ability to obtain combined S and Pb-isotope data, but caution must be applied when using such data to infer protolith. When information from geological context, petrography and chronology (i.e. by Pb isotopes) is combined and fully evaluated, Delta(33)S signatures from sulphides and their geological significance can be interpreted with a higher degree of confidence. (c) 2005 Elsevier B.V All rights reserved.

Evaluation of multiple reaction monitoring cubed for the analysis of tachykinin related peptides in rat spinal cord using a hybrid triple quadrupole–linear ion trap mass spectrometer

Targeted peptide methods generally use HPLC-MS/MRM approaches. Although dependent on the instrumental resolution, interferences may occur while performing analysis of complex biological matrices. HPLC-MS/MRM3 is a technique, which provides a significantly better selectivity, compared with HPLC-MS/MRM assay. HPLC-MS/MRM3 allows the detection and quantitation by enriching standard MRM with secondary product ions that are generated within the linear ion trap. Substance P (SP) and neurokinin A (NKA) are tachykinin peptides playing a central role in pain transmission. The objective of this study was to verify whether HPLC-HPLCMS/ MRM3 could provide significant advantages over a more traditional HPLC-MS/MRM assay for the quantification of SP and NKA in rat spinal cord. The results suggest that reconstructed MRM3 chromatograms display significant improvements with the nearly complete elimination of interfering peaks but the sensitivity (i.e. signal-to-noise ratio) was severely reduced. The precision (%CV) observed was between 3.5% - 24.1% using HPLC-MS/MRM and in the range of 4.3% - 13.1% with HPLC-MS/MRM3, for SP and NKA. The observed accuracy was within 10% of the theoretical concentrations tested. HPLC-MS/MRM3 may improve the assay sensitivity to detect difference between samples by reducing significantly the potential of interferences and therefore reduce instrumental errors.