scholarly journals OLYMPIA - a compact laboratory Orbitrap-based high-resolution mass spectrometer laboratory set-up: Performance studies for gas composition measurement in analogues of planetary environments

Author(s):  
Illia Zymak ◽  
Arnaud Sanderink ◽  
Bertrand Gaubicher ◽  
Jan Žabka ◽  
Jean-Pierre Lebreton ◽  
...  

<p>In situ composition measurements at Saturn and its moons (Cassini-Huygens<sup>1,2</sup>) and at comet 67P/Churyumov-Gerasimenko (Rosetta<sup>3,4</sup>) unveiled the complexity of the atmospheric chemical composition and high abundance of organic compounds in the environments of Solar System bodies. The deciphering of the measurements, obtained by current state-of-the-art instruments, to obtain the composition of complex gas mixtures that include polyatomic molecules and volatile organic compounds (VOCs) often requires having recourse to instrument response modeling supplemented by theoretical chemical models.</p><p>One of the limitations in currently flown mass spectrometers is their limited mass resolving power. High mass-resolving power offers the capability to identify unambiguously almost all complex organic compounds. Such technique offers identification of almost all complex organic compounds without application of complementary separation techniques, e.g. chromatography, spectroscopy or collision induced dissociation. A new generation of space mass spectrometers under development (MASPEX<sup>5</sup>, MULTUM<sup>6</sup>, CORALS<sup>7</sup>, CRATER<sup>7</sup>, among others), aims at reaching mass resolution of > 50 000. CORALS and CRATER are Orbitrap-based instruments using CosmOrbitrap elements.</p><p>In collaboration with J. Herovsky institute, the Laboratoire de Physique et de Chimie de l'Environnement et de l'Espace (LPC2E) has developed a new laboratory test-bench based on the Orbitrap™ technology OLYMPIA (Orbitrap anaLYseur MultiPle IonisAtion) to evaluate several space applications of an Orbitrap-based space instrument using different ionization techniques. OLYMPIA is a compact, transportable set-up and is intended to be used as a stand-alone device (currently with an EI ionization source), but later intended to be coupled to different sources of ions. The next step in the next few months is to couple it with the LLILBID set-up in Berlin<sup>8</sup>.</p><p>OLYMPIA is currently directly coupled with a first prototype of a compact electron impact ionization source. A single shot provides a useful signal duration of 200-250ms second before it decays to the noise level, and provide mass resolution for Kr ion isotopes of the order of 30 000 and on C<sub>2</sub>H<sub>4</sub> on fragments of the order of 40 000. Kr is mostly being used to characterize the isotopic measurement capability of OLYMPIA and mixtures of C<sub>2</sub>H<sub>4</sub>, CO and N<sub>2</sub>gases in different proportions.  In this presentation we concentrate on the capability to detect low ethylene lighter VOC concentration in different mixtures of CO and N<sub>2</sub>. Sensitivity of the instrument is sufficient to detect traces of the carbon dioxide gas in mixture with molecular nitrogen abundant in less than 1% volume ratio.</p><p><strong>1</strong> Waite, J. H. et al. Space Sci. Rev. 114, 113–231 (2004)</p><p><strong>2</strong> Coates, A. J. et al. Geophys. Res. Lett. 34, (2007)</p><p><strong>3</strong> Balsiger, H. et al. Space Sci. Rev. 128, 745–801 (2007)</p><p><strong>4</strong> Le Roy, L. et al. A&A 583, (2015)</p><p><strong>5</strong> Brockwell, T. G. et al. in 2016 IEEE Aerospace Conference 1–17 (2016)</p><p><strong>6</strong> Shimma, S. et al. Anal. Chem. 82, 8456–8463 (2010)</p><p><strong>7</strong> Arevalo Jr, R. et al. Rapid Commun. Mass Spectrom. 32, 1875–1886 (2018)</p><p><strong>8</strong> Klenner, F. et al. Astrobiology 20, 179–189 (2019)</p>

2014 ◽  
Vol 20 (2) ◽  
pp. 577-581 ◽  
Author(s):  
Georges Slodzian ◽  
Ting-Di Wu ◽  
Noémie Bardin ◽  
Jean Duprat ◽  
Cécile Engrand ◽  
...  

AbstractIn situ microanalysis of solid samples is often performed using secondary ion mass spectrometry (SIMS) with a submicron ion probe. The destructive nature of the method makes it mandatory to prevent information loss by using instruments combining efficient collection of secondary ions and a mass spectrometer with parallel detection capabilities. The NanoSIMS meets those requirements with a magnetic spectrometer but its mass selectivity has to be improved for accessing opportunities expected from polyatomic secondary ions. We show here that it is possible to perform D/H ratio measurement images using 12CD−/12CH−, 16OD−/16OH−, or 12C2D−/12C2H− ratios. These polyatomic species allow simultaneous recording of D/H ratios and isotopic compositions of heavier elements like 15N/14N (via 12C15N−/12C14N−) and they provide a powerful tool to select the phase of interest (e.g., mineral versus organics). We present high mass resolution spectra and an example of isotopic imaging where D/H ratios were obtained via the 12C2D−/12C2H− ratio with 12C2D− free from neighboring mass interferences. Using an advanced mass resolution protocol, a “conventional” mass resolving power of 25,000 can be achieved. Those results open many perspectives for isotopic imaging at a fine scale in biology, material science, geochemistry, and cosmochemistry.


2005 ◽  
Vol 11 (3) ◽  
pp. 261-266 ◽  
Author(s):  
Daisuke Okumura ◽  
Michisato Toyoda ◽  
Morio Ishihara ◽  
Itsuo Katakuse

This paper describes experiments demonstrating the high mass-resolving power of the MULTUM II multi-turn type time-of-flight (ToF) mass spectrometer with a 1.308-meter circuit controlled by four toroidal electric sector fields1 and an electron ionization (EI) ion source. A mass resolution of 250,000 [full-width at half maximum: (FWHM)] was obtained for N2+ after a flight time of 9.0 ms (flight cycles: 1200, flight length: 1500 m). A doublet of 12C5H514N and 13C12C5H6 ( m/Δ m = 9746; Δ m: mass difference of doublet, m: mass of lighter ion of doublet) was separated and a mass resolution of 91,000 (FWHM) was obtained. A doublet of CDCl2 and CH2Cl2 ( m/Δ m = 54,162) was also separated. A mass resolution of 115,000 (FWHM) was then achieved. When one peak of these doublets was used as a calibrant, the mass of the other peak was determined within a few ppm by mass difference. The ToF depending on the square of m/z was significantly larger than the systematic errors in the ToF, so that good mass accuracy was obtained by one-point mass determination.


1959 ◽  
Vol 14 (9) ◽  
pp. 822-827 ◽  
Author(s):  
H. A. Tasman ◽  
A. J. H. Boerboom ◽  
H. Wachsmuth

In previous papers 1.2we presented the radial second order imaging properties of inhomogeneous magnetic sector fields with normal incidence and exit at plane boundaries. These fields may provide very high mass resolving power and mass dispersion without increase in radius or decrease of slit widths. In the present paper the calculations are extended to include the effect of oblique incidence and exit at curved boundaries. The influence of the fringing fields on axial focusing when the boundaries are oblique, is accounted for. It is shown that the second order angular aberration may Le eliminated by appropriate curvature of the boundaries.


2018 ◽  
Author(s):  
Christian D. Kelstrup ◽  
Konstantin Aizikov ◽  
Tanveer S. Batth ◽  
Arne Kreutzman ◽  
Dmitry Grinfeld ◽  
...  

ABSTRACTA popular method for peptide quantification relies on isobaric labeling such as tandem mass tags (TMT) which enables multiplexed proteome analyses. Quantification is achieved by reporter ions generated by fragmentation in a tandem mass spectrometer. However, with higher degrees of multiplexing, the smaller mass differences between the reporter ions increase the mass resolving power requirements. This contrasts with faster peptide sequencing capabilities enabled by lowered mass resolution on Orbitrap instruments. It is therefore important to determine the mass resolution limits for highly multiplexed quantification when maximizing proteome depth. Here we defined the lower boundaries for resolving TMT reporter ions with 0.0063 Da mass differences using an ultra-high-field Orbitrap mass spectrometer. We found the optimal method depends on the relative ratio between closely spaced reporter ions and that 64 ms transient acquisition time provided sufficient resolving power for separating TMT reporter ions with absolute ratio changes up to 16-fold. Furthermore, a 32 ms transient processed with phase-constrained spectrum deconvolution provides >50% more identifications with >99% quantified, but with a slight loss in quantification precision and accuracy. These findings should guide decisions on what Orbitrap resolution settings to use in future proteomics experiments relying on TMT reporter ion quantification with identical integer masses.


2013 ◽  
Vol 405 (18) ◽  
pp. 6069-6076 ◽  
Author(s):  
Donald F. Smith ◽  
Andras Kiss ◽  
Franklin E. Leach ◽  
Errol W. Robinson ◽  
Ljiljana Paša-Tolić ◽  
...  

1993 ◽  
Vol 316 ◽  
Author(s):  
Craig Jasper ◽  
Scott Klingbeil ◽  
K.S. Jones ◽  
H.G. Robinson

ABSTRACTControl of threshold voltage during gallium arsenide (GaAs) Metal Semiconductor Field Effect Transistor (MESFET) processing is critical. Channel formation typically is done using ion implantation of 29Si+ from a SiF4 source. The use of Si+ presents a variety of potential cross-contamination problems. 28Si+ and 30Si+ beams can become contaminated with 28N2+, 28CO+, and 30NO+. While 29Si+ is relatively pure, the abundance of 29Si+ in the mass spectrum is 4.67%, thus reducing the potential beam current. This study investigates the effects of varying the mass resolving power of an Eaton 6200AV implanter on the electrical parameters and defect formation. The mass resolving power was adjusted by changing the mean path size through the slit of the aperture opening and magnetic separator current. Electrical device characterization measured a small shift in saturated source-drain current (Idss) and break down voltage, while threshold voltage shifts of approximately 80 mV were observed, with the various mass resolution powers. Transmission Electron Microscopy (TEM) showed that there is minimal change in the extended defect density with changes in isotope and aperture opening. Secondary Ion Mass Spectrometry (SIMS) measured the amount of cross contamination and these results correlated well with the observed changes in device electrical properties.


2017 ◽  
Vol 17 (9) ◽  
pp. 5583-5599 ◽  
Author(s):  
Aleksandra Marsh ◽  
Rachael E. H. Miles ◽  
Grazia Rovelli ◽  
Alexander G. Cowling ◽  
Lucy Nandy ◽  
...  

Abstract. Hygroscopicity data for 36 organic compounds, including amino acids, organic acids, alcohols and sugars, are determined using a comparative kinetics electrodynamic balance (CK-EDB). The CK-EDB applies an electric field to trap-charged aqueous droplets in a chamber with controlled temperature and relative humidity (RH). The dual micro dispenser set-up allows for sequential trapping of probe and sample droplets for accurate determination of droplet water activities from 0.45 to > 0.99. Here, we validate and benchmark the CK-EDB for the homologous series of straight-chain dicarboxylic acids (oxalic–pimelic) with measurements in better agreement with Universal Quasichemical Functional Group Activity Coefficients (UNIFAC) predictions than the original data used to parametrise UNIFAC. Furthermore, a series of increasingly complex organic compounds, with subtle changes to molecular structure and branching, are used to rigorously assess the accuracy of predictions by UNIFAC, which does not explicitly account for molecular structure. We show that the changes in hygroscopicity that result from increased branching and chain length are poorly represented by UNIFAC, with UNIFAC under-predicting hygroscopicity. Similarly, amino acid hygroscopicity is under-predicted by UNIFAC predictions, a consequence of the original data used in the parametrisation of the molecular subgroups. New hygroscopicity data are also reported for a selection of alcohols and sugars and they show variable levels of agreement with predictions.


2013 ◽  
Vol 66 (12) ◽  
pp. 713-717 ◽  
Author(s):  
Kanae Teramoto ◽  
Tomohiko Tamura ◽  
Satoshi Hanada ◽  
Takafumi Sato ◽  
Hiroko Kawasaki ◽  
...  

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