High-Resolution Chemical Depth Profiling of Solid Material Using a Miniature Laser Ablation/Ionization Mass Spectrometer

High-resolution chemical depth profiling measurements of copper films are presented. The 10 μm thick copper test samples were electrodeposited on a Si-supported Cu seed under galvanostatic conditions in the presence of particular plating additives (SPS, Imep, PEI, and PAG) used in the semiconductor industry for the on-chip metallization of interconnects. To probe the trend of these plating additives toward inclusion into the deposit upon growth, quantitative elemental mass spectrometric measurements at trace level concentration were conducted by using a sensitive miniature laser ablation ionization mass spectrometer (LIMS), originally designed and developed for in situ space exploration. An ultrashort pulsed laser system (τ ∼ 190 fs, λ = 775 nm) was used for ablation and ionization of sample material. We show that with our LIMS system, quantitative chemical mass spectrometric analysis with an ablation rate at the subnanometer level per single laser shot can be conducted. The measurement capabilities of our instrument, including the high vertical depth resolution coupled with high detection sensitivity of ∼10 ppb, high dynamic range ≥10(8), measurement accuracy and precision, is of considerable interest in various fields of application, where investigations with high lateral and vertical resolution of the chemical composition of solid materials are required, these include, e.g., wafers from semiconductor industry or studies on space weathered samples in space research.

Isotopic-geochemical features of spontaneous gases from mud volcanoes in Eastern Georgia

Isotopic-geochemical study revealed presence of mantle He (3He/4He up to 223x10**-8) in gases from mud volcanoes of Eastern Georgia. This fact confirms that the Middle Kura basin fill encloses an intrusive body previously distinguished from geophysical data. Wide variations of carbon isotopic composition d13C in CH4 and CO2 and chemical composition of gas and water at temporally constant 3He/4He ratio indicate their relation with crustal processes. Unusual direct correlations of 3He/4He ratio with concentrations of He and CH4 and 40Ar/36Ar ratio can be explained by generation of gas in the Cenozoic sequence of the Middle Kura basin.

An initial study on atmospheric pressure ion transport by laser ionization and electrostatic fields.

Laser ionization of mixtures of gases at atmospheric pressure and the subsequent transport through electrostatic field is studied. A prototype is designed to perform the transport and detection of the ions. Relevance of the composition of the mixture of gases and ionization parameters is shown

Nueva tecnología para la separación de gases atmosféricos y captura de dióxido de carbono por aplicación de campos electromagnéticos y fotoionización

Son numerosos los expertos que predicen que hasta pasado 2050 no se utilizarán masivamente las energías de origen renovable, y que por tanto se mantendrá la emisión de dióxido de carbono de forma incontrolada. Entre tanto, y previendo que este tipo de uso se mantenga hasta un horizonte temporal aún más lejano, la captura, concentración y secuestro o reutilización de dióxido de carbono es y será una de las principales soluciones a implantar para paliar el problema medioambiental causado. Sin embargo, las tecnologías existentes y en desarrollo de captura y concentración de este tipo de gas, presentan dos limitaciones: las grandes cantidades de energía que consumen y los grandes volúmenes de sustancias potencialmente dañinas para el medioambiente que producen durante su funcionamiento. Ambas razones hacen que no sean atractivas para su implantación y uso de forma extensiva. La solución planteada en la presente tesis doctoral se caracteriza por la ausencia de residuos producidos en la operación de captura y concentración del dióxido de carbono, por no utilizar substancias químicas y físicas habituales en las técnicas actuales, por disminuir los consumos energéticos al carecer de sistemas móviles y por evitar la regeneración química y física de los materiales utilizados en la actualidad. Así mismo, plantea grandes retos a futuras innovaciones sobre la idea propuesta que busquen fundamentalmente la disminución de la energía utilizada durante su funcionamiento y la optimización de sus componentes principales. Para conseguir el objetivo antes citado, la presente tesis doctoral, una vez establecido el planteamiento del problema al que se busca solución (capítulo 1), del estudio de las técnicas de separación de gases atmosféricos utilizadas en la actualidad, así como del de los sistemas fundamentales de las instalaciones de captura y concentración del dióxido de carbono (capítulo 2) y tras una definición del marco conceptual y teórico (capítulo 3), aborda el diseño de un prototipo de ionización fotónica de los gases atmosféricos para su posterior separación electrostática, a partir del estudio, adaptación y mejora del funcionamiento de los sistemas de espectrometría de masas. Se diseñarán y desarrollarán los sistemas básicos de fotoionización, mediante el uso de fuentes de fotones coherentes, y los de separación electrostática (capítulo 4), en que se basa el funcionamiento de este sistema de separación de gases atmosféricos y de captura y concentración de dióxido de carbono para construir un prototipo a nivel laboratorio. Posteriormente, en el capítulo 5, serán probados utilizando una matriz experimental que cubra los rangos de funcionamiento previstos y aporte suficientes datos experimentales para corregir y desarrollar el marco teórico real, y con los que se pueda establecer y corregir un modelo físico– matemático de simulación (capítulo 6) aplicable a la unidad en su conjunto. Finalmente, debido a la utilización de unidades de ionización fotónica, sistemas láseres intensos y sistemas eléctricos de gran potencia, es preciso analizar el riesgo biológico a las personas y al medioambiente debido al impacto de la radiación electromagnética producida (capítulo 7), minimizando su impacto y cumpliendo con la legislación vigente. En el capítulo 8 se planteará un diseño escalable a tamaño piloto de la nueva tecnología propuesta y sus principales modos de funcionamiento, así como un análisis de viabilidad económica. Como consecuencia de la tesis doctoral propuesta y del desarrollo de la unidad de separación atmosférica y de captura y concentración de dióxido de carbono, surgen diversas posibilidades de estudio que pueden ser objeto de nuevas tesis doctorales y de futuros desarrollos de ingeniería. El capítulo 9 tratará de incidir en estos aspectos indicando líneas de investigación para futuras tesis y desarrollos industriales. ABSTRACT A large number of experts predict that until at least 2050 renewable energy sources will not be massively used, and for that reason, current Primary Energy sources based on extensive use of fossil fuel will be used maintaining out of control emissions, Carbon Dioxide above all. Meanwhile, under this scenario and considering its extension until at least 2050, Carbon Capture, Concentration, Storage and/or Reuse is and will be one of the main solutions to minimise Greenhouse Gasses environmental effect. But, current Carbon Capture and Storage technology state of development has two main problems: it is a too large energy consuming technology and during normal use it produces a large volume of environmentally dangerous substances. Both reasons are limiting its development and its extensive use. This Ph Degree Thesis document proposes a solution to get the expected effect using a new atmospheric gasses separation system with the following characteristics: absence of wastes produced, it needs no chemical and/or physical substances during its operation, it reduces to minimum the internal energy consumptions due to absence of mobile equipment and it does not need any chemical and/or physical regeneration of substances. This system is beyond the State of the Art of current technology development. Additionally, the proposed solution raises huge challenges for future innovations of the proposed idea finding radical reduction of internal energy consumption during functioning, as well as regarding optimisation of main components, systems and modes of operation. To achieve this target, once established the main problem, main challenge and potential solving solutions (Chapter 1), it is established an initial starting point fixing the Atmospheric Gasses Separation and Carbon Capture and Storage developments (Chapter 2), as well as it will be defined the theoretical and basic model, including existing and potential new governing laws and mathematical formulas to control its system functioning (Chapter 3), this document will deal with the design of an installation of an operating system based on photonic ionization of atmospheric gasses to be separated in a later separation system based on the application of electrostatic fields. It will be developed a basic atmospheric gasses ionization prototype based on intense radioactive sources capable to ionize gasses by coherent photonic radiation, and a basic design of electrostatic separation system (Chapter 4). Both basic designs are the core of the proposed technology that separates Atmospheric Gasses and captures and concentrates Carbon Dioxide. Chapter 5 will includes experimental results obtained from an experimental testing matrix covering expected prototype functioning regimes. With the obtained experimental data, theoretical model will be corrected and improved to act as the real physical and mathematical model capable to simulate real system function (Chapter 6). Finally, it is necessary to assess potential biological risk to public and environment due to the proposed use of units of intense energy photonic ionization, by laser beams or by non–coherent sources and large electromagnetic systems with high energy consumption. It is necessary to know the impact in terms of and electromagnetic radiation taking into account National Legislation (Chapter 7). On Chapter 8, an up scaled pilot plant will be established covering main functioning modes and an economic feasibility assessment. As a consequence of this PhD Thesis, a new field of potential researches and new PhD Thesis are opened, as well as future engineering and industrial developments (Chapter 9).

Helium isotope ratios and pore gases in deep-sea sediments of the Japan Sea

We have measured the 3He/4He and 4He/20Ne ratios and chemical compositions of gases exsolved from deep-sea sediments at two sites (798 and 799) in the Japan Sea. The 3He/4He and 4He/20Ne ratios vary from 0.642 Ratm (where Ratm is the atmospheric 3He/4He ratio of 1.393*10**-6) to 0.840 Ratm, and from 0.41 to 4.5, respectively. Helium in the samples can be explained by the mixing between atmospheric helium dissolved in bottom water of the Japan Sea and crustal helium in the sediment. The sedimentary helium is enriched in mantle-derived 3He compared with those from the Japan Trench and the Nankai Trough. This suggests that the basement of the Japan Sea has relatively large remnants of mantle-derived helium compared with that of the Pacific. Major chemical compositions of the samples are methane and nitrogen. There is a positive correlation between methane content and helium content corrected for air component. Based on the 3He/4He-Sum C/3He diagram, the major part of methane can be attributed to crustal and/or organic origin.

3He/4He ratios of pore gases in pore water and chemical composition of sediments at DSDP Sites 87-583 and 87-584

We have measured the 3He/4He and 20Ne/4He ratios of gases dissolved in the pore water in sediments at two sites in the Nankai Trough (Site 583) and the Japan Trench (Site 584). The 3He/4He and 20Ne/4He ratios vary from 0.215 * 10**-6 to 1.23 * 10**-6 and from 50 * 10**-3 to 2700 * 10**-3, respectively. These values can be explained by mixing two components, one from the atmosphere and one with a 3He/4He ratio of (0.2 to 0.3) * 10**-6. The latter component may be derived from the ocean crust near the subduction zone.

Molecular and isotopic compositions of hydrocarbons at DSDP Site 76-533

In an investigation of gas hydrates in deep ocean sediments, gas samples from Deep Sea Drilling Project Site 533 on the Blake Outer Ridge in the northwest Atlantic were obtained for molecular and isotopic analyses. Gas samples were collected from the first successful deployment of a pressure core barrel (PCB) in a hydrate region. The pressure decline curves from two of the four PCB retrievals at in situ pressures suggested the presence of small amounts of gas hydrates. Compositional and isotopic measurements of gases from several points along the pressure decline curve indicated that (1) biogenic methane (d13C = -68 per mil; C1/C2 = 5000) was the dominant gas (>90%); (2) little fractionation in the C1/C2 ratio or the C carbon isotopic composition occurred as gas hydrates decomposed during pressure decline experiments; (3) the percent of C3, i-C4, and CO2 degassed increased as the pressure declined, indicating that these molecules may help stabilize the hydrate structure; (4) excess nitrogen was present during initial degassing; and (5) C1/C2 ratios and isotopic ratios of C gases were similar to those obtained from conventional core sampling. The PCB gas also contained trace amounts of saturated, acyclic, cyclic, and aromatic C5-C14 hydrocarbons, as well as alkenes and tetrahydrothiophenes. Gas from a decomposed specimen of gas hydrate had similar molecular and isotopic ratios to the PCB gas (d13C of -68 per mil for methane and a C1/C2 ratio of about 6000). Regular trends in the d13C of methane (about -95 to -60 per mil) and C1/C2 ratios (about 25000 to 2000) were observed with depth. Capillary gas chromatography (GC) and total scanning fluorescence measurements of extracted organic material were characteristic of hydrocarbons dominated by a marine source, though significant amounts of perylene were also present.

Ionization in atmospheres of brown dwarfs and extrasolar planets. V. Alfvén Ionization

Observations of continuous radio and sporadic X-ray emission from low-mass objects suggest they harbor localized plasmas in their atmospheric environments. For low-mass objects, the degree of thermal ionization is insufficient to qualify the ionized component as a plasma, posing the question: what ionization processes can efficiently produce the required plasma that is the source of the radiation? We propose Alfv´en ionization as a mechanism for producing localized pockets of ionized gas in the atmosphere, having sufficient degrees of ionization ( 10−7) that they constitute plasmas. We outline the criteria required for Alfv´en ionization and demonstrate its applicability in the atmospheres of low-mass objects such as giant gas planets, brown dwarfs, and M dwarfs with both solar and sub-solar metallicities. We find that Alfv´en ionization is most efficient at mid to low atmospheric pressures where a seed plasma is easier to magnetize and the pressure gradients needed to drive the required neutral flows are the smallest. For the model atmospheres considered, our results show that degrees of ionization of 10−6–1 can be obtained as a result of Alfv´en ionization. Observable consequences include continuum bremsstrahlung emission, superimposed with spectral lines from the plasma ion species (e.g., He, Mg, H2, or CO lines). Forbidden lines are also expected from the metastable population. The presence of an atmospheric plasma opens the door to a multitude of plasma and chemical processes not yet considered in current atmospheric models. The occurrence of Alfv´en ionization may also be applicable to other astrophysical environments such as protoplanetary disks.

Estandarización del método para alcoholemias por cromatografía de gases

La ingesta de etanol se ha relacionado a consecuencias lamentables a nivel social, familiar y jurídico; siendo importante el desarrollo de métodos de detección de etanol en sangre, prueba más confiable a nivel cuantitativo. En el presente trabajo se realizó la primera fase de la optimización de un método para el análisis de alcoholemia por cromatografía de gases con inyección directa y detección de ionización de llama (GC-FID). Se realizó la optimización de algunos parámetros cualitativos y cuantitativos, incluyendo tiempos de retención estables, selectividad del método demostrado por la ausencia de sustancias interferentes en el análisis; linealidad a bajos niveles con un coeficiente de determinación de R2 = 0.996. La aplicabilidad del método en un pool de 33 muestras con distintas concentraciones de etanol tomadas cómo puntos de referencia de baja, media y alta concentración. La cuantificación se realizó por estandarización interna mediante el uso de un estándar interno (n-butanol) y la estandarización externa mediante la curva de calibración a 4 niveles.

Preparation and characterization of tin oxide nanowires on SiC

Interest in nanowires of metal oxide oxides has been exponentially growing in the last years, due to the attracting potential of application in electronic, optical and sensor field. We have focused our attention on the sensing properties of semiconducting nanowires as conductometric and optical gas sensors. Single crystal tin dioxide nanostructures were synthesized to explore and study their capability in form of multi-nanowires sensors. The nanowires of SnO2 have been used to produce a novel gas sensor based on Pt/oxide/SiC structure and operating as Schottky diode. For the first time, a reactive oxide layer in this device has been replaced by SnO2 nanowires. Proposed sensor has maintained the advantageous properties of known SiC- based MOS devices, that can be employed for the monitoring of gases (hydrogen and hydrocarbons) emitted by industrial combustion processes.

Rapid differentiation of isomeric lipids by photodissociation mass spectrometry of fatty acid derivatives

RATIONALE Both traditional electron ionization and electrospray ionization tandem mass spectrometry have demonstrated limitations in the unambiguous identification of fatty acids. In the former case, high electron energies lead to extensive dissociation of the radical cations from which little specific structural information can be obtained. In the latter, conventional collision-induced dissociation (CID) of even-electron ions provides little intra-chain fragmentation and thus few structural diagnostics. New approaches that harness the desirable features of both methods, namely radical-driven dissociation with discrete energy deposition, are thus required. METHODS Herein we describe the derivatization of a structurally diverse suite of fatty acids as 4-iodobenzyl esters (FAIBE). Electrospray ionization of these derivatives in the presence of sodium acetate yields abundant [M+Na]+ ions that can be mass-selected and subjected to laser irradiation (=266nm) on a modified linear ion-trap mass spectrometer. RESULTS Photodissociation (PD) of the FAIBE derivatives yields abundant radical cations by loss of atomic iodine and in several cases selective dissociation of activated carboncarbon bonds (e.g., at allylic positions) are also observed. Subsequent CID of the [M+NaI]center dot+ radical cations yields radical-directed dissociation (RDD) mass spectra that reveal extensive carboncarbon bond dissociation without scrambling of molecular information. CONCLUSIONS Both PD and RDD spectra obtained from derivatized fatty acids provide a wealth of structural information including the position(s) of unsaturation, chain-branching and hydroxylation. The structural information obtained by this approach, in particular the ability to rapidly differentiate isomeric lipids, represents a useful addition to the lipidomics tool box. Copyright (c) 2013 John Wiley & Sons, Ltd.

Ozone-induced dissociation : Elucidation of double bond position within mass-selected lipid ions

Ions formed from lipids during electrospray ionization of crude lipid extracts have been mass-selected within a quadrupole linear ion trap mass spectrometer and allowed to react with ozone vapor. Gas-phase ion-molecule reactions between unsaturated lipid ions and ozone are found to yield two primary product ions for each carbon-carbon double bond within the molecule. The mass-to-charge ratios of these chemically induced fragments are diagnostic of the position of unsaturation within the precursor ion. This novel analytical technique, dubbed ozone-induced dissociation (OzID), can be applied both in series and in parallel with conventional collision-induced dissociation (CID) to provide near-complete structural assignment of unknown lipids within complex mixtures without prior fractionation or derivatization. In this study, OzID is applied to a suite of complex lipid extracts from sources including human lens, bovine kidney, and commercial olive oil, thus demonstrating the technique to be applicable to a broad range of lipid classes including both neutral and acidic glycerophospholipids, sphingomyelins, and triacylglycerols. Gas-phase ozonolysis reactions are also observed with different types of precursor ions including \[M + H](+), \[M + Li](+), \[M + Na](+), and \[M H](-): in each case yielding fragmentation data that allow double bond position to be unambiguously assigned. Within the human lens lipid extract, three sphingomyelin regioisomers, namely SM(d18:0/15Z-24:1), SM(d18:0/17Z-24:1), and SM(d18:0/19Z-24:1), and a novel phosphatidylethanolamine alkyl ether, GPEtn(11Z-18:1e/9Z18:1), are identified using a combination of CID and OzID. These discoveries demonstrate that lipid identification based on CID alone belies the natural structural diversity in lipid biochemistry and illustrate the potential of OzID as a complementary approach within automated, high-throughput lipid analysis protocols.

Stability of the bituminous coal microstructure upon exposure to high pressures of helium

Small-angle neutron scattering (SANS) and ultra-small-angle neutron scattering (USANS) measurements of the structure of two Australian bituminous coals (particle size of 1-0.5 mm) before, during, and after exposure to 155 bar of helium were made to identify any effects of pressure alone on the pore size distribution of coal and any irreversible effects upon exposure to high pressures of helium in the pore size range from 3 nm to 10 μm. No irreversible effects upon exposure were identified for any pore size. No effects of pressure on pore size distribution were observed, except for a small effect at a pore size of about 2 μm for one coal. This study provides a convenient baseline for SANS and USANS investigations on sorption of gases at elevated pressures on coals, by distinguishing between the effect of pressure alone on coal pore size distribution and against the effect of the gas to be investigated.

Mass spectrometric studies of the oxocarbons CnOn (n=3-6)

The anion radicals CnOn-. (n = 3-6) can be generated by ionization of cyclic carbonyl compounds in the negative ion mode. The ions as well as the corresponding neutral counterparts are probed by means of different mass spectrometric techniques. The results suggest that oxocarbons, i.e. cyclic polyketones, are formed under conservation of the skeletons of the precursor molecules. At least for n = 3, however, the experimental findings indicate partial rearrangement of the expected cyclopropanetrione structure to an oxycarboxylate for the anion, i.e. O-.-C=C-CO2-. For n = 4 and 6 almost complete dissociation of the neutral polyones into carbon monoxide is found, whereas for n = 5 a distinct recovery signal indicates the generation of genuine cyclopentanepentaone.

Plasma-controlled metal catalyst saturation and the initial stage of carbon nanostructure array growth

The kinetics of the nucleation and growth of carbon nanotube and nanocone arrays on Ni catalyst nanoparticles on a silicon surface exposed to a low-temperature plasma are investigated numerically, using a complex model that includes surface diffusion and ion motion equations. It is found that the degree of ionization of the carbon flux strongly affects the kinetics of nanotube and nanocone nucleation on partially saturated catalyst patterns. The use of highly ionized carbon flux allows formation of a nanotube array with a very narrow height distribution of half-width 7 nm. Similar results are obtained for carbon nanocone arrays, with an even narrower height distribution, using a highly ionized carbon flux. As the deposition time increases, nanostructure arrays develop without widening the height distribution when the flux ionization degree is high, in contrast to the fairly broad nanostructure height distributions obtained when the degree of ionization is low.