scholarly journals Observation of charged droplets from electrospray ionization (ESI) plumes in API mass spectrometers

Author(s):  
Clara Markert ◽  
Marco Thinius ◽  
Laura Lehmann ◽  
Chris Heintz ◽  
Florian Stappert ◽  
...  

AbstractElectrospray ionization (ESI) generates bare analyte ions from charged droplets, which result from spraying a liquid in a strong electric field. Experimental observations available in the literature suggest that at least a significant fraction of the initially generated droplets remain large, have long lifetimes, and can thus aspirate into the inlet system of an atmospheric pressure ionization mass spectrometer (API-MS). We report on the observation of fragment signatures from charged droplets penetrating deeply the vacuum stages of three commercial mass spectrometer systems with largely different ion source and spray configurations. Charged droplets can pass through the ion source and pressure reduction stages and even into the mass analyzer region. Since droplet signatures were found in all investigated instruments, the incorporation of charged droplets is considered a general phenomenon occurring with common spray conditions in ESI sources.

2020 ◽  
Author(s):  
Rustam Lukmanov ◽  
Marek Tulej ◽  
Valentine Riedo ◽  
Niels Ligterink ◽  
Coenraad De Koning ◽  
...  

<p>In-situ Mars exploration requires new promising instrumentation that will be capable of delivering highly accurate chemical information about soils and rocks present at the Martian surface. Specific attention is drawn to the instruments that are capable of identifying extinct or extant microbes within the bulk of various solid samples (Tulej et al., 2015; Westall et al., 2015; Wiesendanger et al., 2018). A miniature Laser Ablation/Ionization Mass Spectrometer (LIMS) developed at the University of Bern is among the valid candidates (Wurz et al., 2012). The size of the mass analyzer is only Ø 60 mm × 160 mm and thus capable of being deployed on a rover or lander platform. In this contribution, we will present data collected from a 1.88 Ga Gunflint sample using a deep UV fs laser system as ablation ion source. The gunflint chert sample contains a population of microfossils entombed in the silica matrix and was chosen as a Martian analogue. Using the high stability of the UV laser and consequent uniform ablation, we performed large-scale spectra collection (90’000) in two modes - chemical imaging and depth profiling. With the current setup, we achieved a diameter of the analytical spot of ~10 µm for the depth profiling and ~5 µm for the imaging. Our results reveal that our LIMS instrument can identify the location of the microfossil lamination area as well as single microfossils by chemical means. We show how single mass unit spectral decomposition and subsequent kernel clustering reveal masses and intensity regions unique to the microfossils and inorganic host, thus providing the opportunity for automated identification of the spectra that are collected from the microfossils. We also show how transforming spectral intensities into spectral proximities can help to navigate the rich multidimensional datasets. We also address common interpretation problems in LIMS, when multiple mineralogical inclusions contribute to the output spectra acquired within the single analytical spot using ρ-networks and Principal Component Analysis (PCA). In combination with analysis of spectral proximities, this approach is particularly useful in attempts to assess the biogenicity of the putative terrestrial microfossils as well as potential Martian microfossils. Additionally, we discuss the data analysis pipeline and chemical composition of the microfossils and surrounding inorganic host in detail. </p> <p>Tulej M., Neubeck A., Ivarsson M., Riedo A., Neuland M. B., Meyer S., and Wurz P. (2015) Chemical Composition of Micrometer-Sized Filaments in an Aragonite Host by a Miniature Laser Ablation/Ionization Mass Spectrometer. Astrobiology, 15: 669-682.</p> <p>Westall F., Foucher F., Bost N., Bertrand M., Loizeau D., Vago J. L., Kminek G., Gaboyer F., Campbell K. A., Bréhéret J.-G. and others. (2015) Biosignatures on Mars: What, Where, and How? Implications for the Search for Martian Life. Astrobiology, 15: 998-1029.</p> <p>Wiesendanger R., Wacey D., Tulej M., Neubeck A., Ivarsson M., Grimaudo V., Moreno-García P., Cedeño-López A., Riedo A., Wurz P. and others. (2018) Chemical and Optical Identification of Micrometer-Sized 1.9 Billion-Year-Old Fossils by Combining a Miniature Laser Ablation Ionization Mass Spectrometry System with an Optical Microscope. Astrobiology, 18: 1071-1080.</p> <p>Wurz P., Abplanalp D., Tulej M., Iakovleva M., Fernandes V. A., Chumikov A., and Managadze G. G. (2012) Mass spectrometric analysis in planetary science: Investigation of the surface and the atmosphere. Solar System Research, 46: 408-422.</p> <p> </p>


2009 ◽  
Vol 6 (1) ◽  
pp. 39-46
Author(s):  
Francis Beaudry ◽  
Robert B. Moore

An intermediate electrode was developed to improve the transfer of ions in atmospheric pressure from a first location, the ion source, to a second location, the mass spectrometer. The new apparatus increase the efficiency of mass analysis of molecular constituents of liquids, including trace analysis of chemical entities, in which an electrospray (ES) or IonSpray™ (IS) technique is used to produce electrically charged droplets which divide and evaporate to form gaseous ions of the molecular constituents. The gas phase ions are transported to the mass spectrometer by an electric field generated by a new electrode design that separates the two fundamental functions of an electrospray or an IonSpray™, which are the nebulization of charged droplets and the transport of ions into the mass analyzer. The results suggest that the new apparatus provide a gain in signal intensity up to 10 compared with the commercial product. A significant improvement in ion transport results in higher precision and accuracy and/or reduction of the amount of material needed for analysis.


2021 ◽  
Vol 217 (1) ◽  
Author(s):  
J. Simcic ◽  
D. Nikolić ◽  
A. Belousov ◽  
D. Atkinson ◽  
C. Lee ◽  
...  

AbstractTo date, a variety of different types of mass spectrometers have been utilized on missions to study the composition of atmospheres of solar system bodies, including Venus, Mars, Jupiter, Titan, the moon, and several comets. With the increasing interest in future small probe missions, mass spectrometers need to become even more versatile, lightweight, compact, and sensitive.For in situ exploration of ice giant atmospheres, the highest priority composition measurements are helium and the other noble gases, noble gas isotopes, including 3He/4He, and other key isotopes like D/H. Other important but lower priority composition measurements include abundances of volatiles C, N, S, and P; isotopes 13C/12C, 15N/14N, 18O/17O/16O; and disequilibrium species PH3, CO, AsH3, GeH4, and SiH4. Required measurement accuracies are largely defined by the accuracies achieved by the Galileo (Jupiter) probe Neutral Mass Spectrometer and Helium Abundance Detectors, and current measurement accuracies of solar abundances.An inherent challenge of planetary entry probe mass spectrometers is the introduction of material to be sampled (gas, solid, or liquid) into the instrument interior, which operates at a vacuum level. Atmospheric entry probe mass spectrometers typically require a specially designed sample inlet system, which ideally provides highly choked, nearly constant mass-flow intake over a large range of ambient pressures. An ice giant descent probe would have to operate for 1-2 hours over a range of atmospheric pressures, possibly covering 2 or more orders of magnitude, from the tropopause near 100 mbar to at least 10 bars, in an atmospheric layer of depth beneath the tropopause of about 120 km at Neptune and about 150 km at Uranus.The Jet Propulsion Laboratory’s Quadrupole Ion Trap Mass Spectrometer (QITMS) is being developed to achieve all of these requirements. A compact, wireless instrument with a mass of only 7.5 kg, and a volume of 7 liters (7U), the JPL QITMS is currently the smallest flight mass spectrometer available for possible use on planetary descent probes as well as small bodies, including comet landers and surface sample return missions. The QITMS is capable of making measurements of all required constituents in the mass range of 1–600 atomic mass units (u) at a typical speed of 50 mass spectra per second, with a sensitivity of up to $10^{13}$ 10 13  counts/mbar/sec and mass resolution of $m/\Delta m=18000$ m / Δ m = 18000 at m/q = 40. (Throughout this paper we use the unit of m/q = u/e for the mass-to-charge ratio, where atomic mass unit and elementary charge are $1~\text{u} = 1.66\times 10^{-27}~\text{kg}$ 1 u = 1.66 × 10 − 27 kg and $1\text{e} = 1.6\times 10^{-19}$ 1 e = 1.6 × 10 − 19 C, respectively.) The QITMS features a novel MEMS-based inlet system driven by a piezoelectric actuator that continuously regulates gas flow at inlet pressures of up to 100 bar.In this paper, we present an overview of the QITMS capabilities, including instrument design and characteristics of the inlet system, as well as the most recent results from laboratory measurements in different modes of operation, especially suitable for ice giant atmospheres exploration.


1969 ◽  
Vol 24 (9) ◽  
pp. 1147-1152 ◽  
Author(s):  
H. Budzikiewicz, ◽  
H. H. Inhoffen

1. A method is described for the simultaneous monitoring of H2O, O2, CO2 and their 18O-labelled analogs in experiments on the photosynthesis both of aquatic and terrestrial plants. The apparatus consists of a Varian-MAT mass spectrometer with a modified inlet system equipped at the entrance of the ion source with a polyethylene membrane permeable for H2O, O2 and CO2.2. Experiments have been performed with Chlorella pyrenoidosa Chick. using H218O and K2C18O3 as substrates while H2O and O2 and CO2 in solution as well as their 18O-labelled analogs were monitored during dark and light periods.3. It has been observed that the isotopic composition of the photosynthetic oxygen corresponds to that of the surrounding water and differs grossly from that of the dissolved CO2 and K2CO3. It is concluded that either H2O is the precursor of the photosynthetic oxygen or that in case CO2 is involved a very fast and complete equilibration between the latter and H2O has to occur after CO2 enters the cell.


Author(s):  
Jurij Simcic ◽  
Dragan Nikolic ◽  
Anton Belousov ◽  
David Atkinson ◽  
Stojan Madzunkov

<p>To date a variety of different types of Mass Spectrometers has been utilized on missions to study the composition of atmospheres of many solar system bodies including Venus, Mars, Jupiter, Titan, the moon and several comets. For in-situ exploration of ice giant atmospheres, the highest priority composition measurements are helium and the other noble gases, noble gas isotopes, and other key isotopes including <sup>3</sup>He/<sup>4</sup>He and D/H. Other important but lower priority composition measurements include abundances of volatiles C, N, S, and P, isotopes <sup>13</sup>C/<sup>12</sup>C, <sup>15</sup>N/<sup>14</sup>N, <sup>18</sup>O/<sup>17</sup>O/<sup>16</sup>O and disequilibrium species PH<sub>3</sub>, CO, AsH<sub>3</sub>, GeH<sub>4</sub>, and SiH<sub>4</sub>. Required measurement accuracies are largely defined by the accuracies achieved by the Galileo (Jupiter) probe Neutral Mass Spectrometer and Helium Abundance Detectors, and current measurement accuracies of solar abundances<sup>[1]</sup>.</p><p>The Jet Propulsion Laboratory’s Quadrupole Ion Trap Mass Spectrometer (QITMS)<sup>[2] </sup>is a compact, wireless instrument with a mass of only 7.5 kg, designed to meet these requirements and challenges specific to the planetary probe missions. It is currently the smallest flight MS available, capable of making measurements of all required constituents in the mass range 1-600Da, with a sensitivity of up to 10<sup>13</sup> counts/mbar/sec and resolution of m/∆m=12000 at 40Da.</p><p>During a fly-by or a descent mission, the time available to perform an in-situ measurement is usually short. This makes it challenging to measure the abundances of minor constituents for which long integration times are needed. Mass spectrometers largely employ a non-discriminatory electron impact ionization of sampled gas mixtures for creating ions, which means the probability to create and trap ion fragments of trace species is very low and further destabilized by space charge effects due to an excessive number of ions from dominant species. A selective resonant ejection technique was employed to lower the amount of major constituent species, while keeping the minor constituents intact, which resulted in higher accuracy measurements of minor species.</p><p>Another inherent challenge of planetary entry probe mass spectrometers is the introduction of material to be sampled into the instrument interior, which operates at vacuum. Atmospheric entry probe mass spectrometers typically require a specially designed sample inlet system, which ideally provides highly choked, nearly constant mass-flow intake over a large range of ambient pressures. An ice giant descent probe would have to operate over a range of atmospheric pressures covering 2 or more orders of magnitude, 100 mb to 10+ bars, in an atmospheric layer of ~120 km at Neptune to ~150 km at Uranus. The QITMS features a novel MEMS based inlet system driven by a piezo-electric actuator that continuously regulates gas flow at inlet pressures of up to 100 bar.</p><p>In this paper, we present an overview of the QITMS capabilities including instrument design and characteristics of the inlet system, as well as the most recent results from laboratory measurements in different modes of operation.</p><p>[1] Mousis, O., et al., Pl. Sp. Sci., 155 12–40, 2018.</p><p>[2] Madzunkov, S.M., Nikolic, D., J. Am. Soc. Mass Spectrom. 25(11), 2014.</p>


Sign in / Sign up

Export Citation Format

Share Document