Derivatization of polar organic compounds - performed directly in the inlet system of a mass spectrometer

Author(s):  
I. Fogy ◽  
H. Stipsits ◽  
E.R. Schmid ◽  
W. Kubelka
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.


2018 ◽  
Vol 18 (13) ◽  
pp. 9527-9545 ◽  
Author(s):  
Qian Xiao ◽  
Mei Li ◽  
Huan Liu ◽  
Mingliang Fu ◽  
Fanyuan Deng ◽  
...  

Abstract. Emissions from ships at berth play an important role regarding the exposure of high density human populations to atmospheric pollutants in port areas; however, these emissions are not well understood. In this study, volatile organic compounds (VOCs) and particle emissions from 20 container ships at berth were sampled and analyzed during the “fuel switch” period at Jingtang Port in Hebei Province, China. VOCs and particles were analyzed using a gas chromatography-mass spectrometer (GC-MS) and a single particle aerosol mass spectrometer (SPAMS), respectively. VOC analysis showed that alkanes and aromatics, especially benzene, toluene and heavier compounds e.g., n-heptane, n-octane and n-nonane, dominated the total identified species. Secondary organic aerosol (SOA) yields and ozone (O3) forming potential were 0.017 ± 0.007 g SOA g−1 VOCs and 2.63 ± 0.37 g O3 g−1 VOCs, respectively. Both positive and negative ion mass spectra from individual ships were derived and the intensity of specific ions were quantified. Results showed that elemental carbon (35.74 %), elemental carbon–organic carbon mixtures (33.95 %) and Na-rich particles (21.12 %) were major classes, comprising 90.7 % of the particles observed. Particles from ship auxiliary engines were in the 0.2 to 2.5 µm size range, with a peak occurring at around 0.4 µm. The issue of using vanadium (V) as tracer element was examined, and it was found that V was not a proper tracer of ship emissions when using low sulfur content diesel oil. The average percentage of sulfate particles observed in shipping emissions before and after switching to marine diesel oil remained unchanged at 24 %. Under certain wind conditions, when berths were upwind of emission sources, the ratios before and after 1 January were 35 and 27 % respectively. The impact of atmospheric stability was discussed based on PM2.5 and primary pollutant (carbon monoxide) concentration. With a background of frequent haze episodes and complex mechanisms of particulate accumulation and secondary formation, the impact of atmospheric stability is believed to have been weak on the sulfate contribution from shipping emissions. The results from this study provide robust support for port area air quality assessment and source apportionment.


Ocean Science ◽  
2019 ◽  
Vol 15 (4) ◽  
pp. 925-940 ◽  
Author(s):  
Charel Wohl ◽  
David Capelle ◽  
Anna Jones ◽  
William T. Sturges ◽  
Philip D. Nightingale ◽  
...  

Abstract. We present a technique that utilises a segmented flow coil equilibrator coupled to a proton-transfer-reaction mass spectrometer to measure a broad range of dissolved volatile organic compounds. Thanks to its relatively large surface area for gas exchange, small internal volume, and smooth headspace–water separation, the equilibrator is highly efficient for gas exchange and has a fast response time (under 1 min). The system allows for both continuous and discrete measurements of volatile organic compounds in seawater due to its low sample water flow (100 cm3 min−1) and the ease of changing sample intake. The equilibrator setup is both relatively inexpensive and compact. Hence, it can be easily reproduced and installed on a variety of oceanic platforms, particularly where space is limited. The internal area of the equilibrator is smooth and unreactive. Thus, the segmented flow coil equilibrator is expected to be less sensitive to biofouling and easier to clean than membrane-based equilibration systems. The equilibrator described here fully equilibrates for gases that are similarly soluble or more soluble than toluene and can easily be modified to fully equilibrate for even less soluble gases. The method has been successfully deployed in the Canadian Arctic. Some example data from underway surface water and Niskin bottle measurements in the sea ice zone are presented to illustrate the efficacy of this measurement system.


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