Orbitool: a software tool for analyzing online Orbitrap mass spectrometry data

The Orbitrap mass spectrometer has recently been proved to be a powerful instrument to accurately measure gas-phase and particle-phase organic compounds with a greater mass resolving power than other widely used online mass spectrometers in atmospheric sciences. We develop an open-source software tool (Orbitool, https://orbitrap.catalyse.cnrs.fr, last access: 4 February 2021) to facilitate the analysis of long-term online Orbitrap data. Orbitool can average long-term data while improving the mass accuracy by re-calibrating each mass spectrum, assign molecular formulae of compounds and their isotopes to measured signals, and export time series and mass defect plots. The noise reduction procedure in Orbitool can separate signal peaks from noise and reduce the computational and storage expenses. Chemical ionization Orbitrap data from laboratory experiments on ozonolysis of monoterpenes and ambient measurements in urban Shanghai were used to test Orbitool. For the test dataset, the average mass accuracy was improved from <2 to <0.5 ppm by mass calibrating each spectrum. The denoising procedure removed 97 % of the noise peaks from a spectrum averaged for 30 min while maintaining the signal peaks, substantially helping the automatic assignment of unknown species. To illustrate the capabilities of Orbitool, we used the most challenging and complex dataset we have collected so far, which consists of ambient gas-phase measurements in urban Shanghai. These tests showed that Orbitool was able to automatically assign hundreds of molecular formulae as well as their isotopes with high accuracy.

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

&lt;p&gt;In situ composition measurements at Saturn and its moons (Cassini-Huygens&lt;sup&gt;1,2&lt;/sup&gt;) and at comet 67P/Churyumov-Gerasimenko (Rosetta&lt;sup&gt;3,4&lt;/sup&gt;) 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.&lt;/p&gt;&lt;p&gt;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&lt;sup&gt;5&lt;/sup&gt;, MULTUM&lt;sup&gt;6&lt;/sup&gt;, CORALS&lt;sup&gt;7&lt;/sup&gt;, CRATER&lt;sup&gt;7&lt;/sup&gt;, among others), aims at reaching mass resolution of &gt; 50 000. CORALS and CRATER are Orbitrap-based instruments using CosmOrbitrap elements.&lt;/p&gt;&lt;p&gt;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&amp;#8482; 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&lt;sup&gt;8&lt;/sup&gt;.&lt;/p&gt;&lt;p&gt;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&lt;sub&gt;2&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt; 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&lt;sub&gt;2&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;, CO and N&lt;sub&gt;2&lt;/sub&gt;gases in different proportions.&amp;#160; In this presentation we concentrate on the capability to detect low ethylene lighter VOC concentration in different mixtures of CO and N&lt;sub&gt;2&lt;/sub&gt;. 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.&lt;/p&gt;&lt;p&gt;&lt;strong&gt;1&lt;/strong&gt; Waite, J. H. et al. Space Sci. Rev. 114, 113&amp;#8211;231 (2004)&lt;/p&gt;&lt;p&gt;&lt;strong&gt;2&lt;/strong&gt; Coates, A. J. et al. Geophys. Res. Lett. 34, (2007)&lt;/p&gt;&lt;p&gt;&lt;strong&gt;3&lt;/strong&gt; Balsiger, H. et al. Space Sci. Rev. 128, 745&amp;#8211;801 (2007)&lt;/p&gt;&lt;p&gt;&lt;strong&gt;4&lt;/strong&gt; Le Roy, L. et al. A&amp;A 583, (2015)&lt;/p&gt;&lt;p&gt;&lt;strong&gt;5&lt;/strong&gt; Brockwell, T. G. et al. in 2016 IEEE Aerospace Conference 1&amp;#8211;17 (2016)&lt;/p&gt;&lt;p&gt;&lt;strong&gt;6&lt;/strong&gt; Shimma, S. et al. Anal. Chem. 82, 8456&amp;#8211;8463 (2010)&lt;/p&gt;&lt;p&gt;&lt;strong&gt;7&lt;/strong&gt; Arevalo Jr, R. et al. Rapid Commun. Mass Spectrom. 32, 1875&amp;#8211;1886 (2018)&lt;/p&gt;&lt;p&gt;&lt;strong&gt;8&lt;/strong&gt; Klenner, F. et al. Astrobiology 20, 179&amp;#8211;189 (2019)&lt;/p&gt;

Numerical analysis of trajectories in a Cassinian ion trap of second order with trap door ion inlet

Ion traps like the Orbitrap are well known mass analyzers with very high resolving power. This resolving power is achieved with help of ions orbiting around an inner electrode for long time, in general up to a few seconds, since the mass signal is obtained by calculating the Fourier Transform of the induced signal caused by the ion motion. A similar principle is applied in the Cassinian Ion Trap of second order, where the ions move in a periodic pattern in-between two inner electrodes. The Cassinian ion trap has the potential to offer mass resolving power comparable to the Orbitrap with advantages regarding the experimental implementation. In this paper we have investigated the details of the ion motion analyzing experimental data and the results of different numerical methods, with focus on increasing the resolving power by increasing the oscillation frequency for ions in a high field ion trap. In this context the influence of the trap door, a tunnel through which the ions are injected into the trap, on the ion velocity becomes especially important.

Exploring the Efficiency of UHPLC-Orbitrap MS for the Determination of 20 Pharmaceuticals and Acesulfame K in Hospital and Urban Wastewaters with the Aid of FPSE

Aside from the classical residues of persistent organic pollutants (POPs), the occurrence of emerging contaminants (ECs) in the environment has become a subject of increasing concern due to their harmful impact on the aquatic environment. Wastewater treatment plant (WWTP) effluents are major sources of environmental pollution. Therefore, data concerning their existence is required. In this study, twenty compounds representative of different drug groups considered ECs and belonging to antibiotics, antipsychotics, anti-inflammatory drugs plus acesulfame K were selected to be accurately detected and quantified with UHPLC–LTQ-Orbitrap MS in hospital and urban WWTP effluents. Chromatographic parameters (column efficiency, mobile phase, etc.), as well as mass spectrometry conditions concerning ionization mode and Orbitrap analysis (ESI options, mass resolving power, AGC target, tube lens, injection time), were evaluated. Moreover, a novel fabric phase sorptive extraction (FPSE) method based on fiber glass coated with PEG300 was employed as sample preparation process. Experimental parameters affecting extraction and desorption steps such as sample pH, extraction time, ionic strength, elution time and solvent have been optimized. The optimized methodology was validated providing excellent linearity (R2 > 0.99), and low detection and quantification limits up to 3.1 and 9.3 ng/L, for carbamazepine, respectively. Relative recoveries ranged from 81.1% to 114.0%, while a medium matrix effect for most of the target compounds occurred. Applying the above analytical method in effluents of WWTPs from NW Greece, nine compounds were quantified with concentrations that varied from 55.4 to 728.4 ng/L.

Orbitool: A software tool for analyzing online Orbitrap mass spectrometry data

The Orbitrap mass spectrometer has recently been proved to be a powerful instrument to accurately measure gas-phase and particle-phase organic compounds with a greater mass resolving power than other widely-used online mass spectrometers in atmospheric sciences. We develop an open-source software tool (Orbitool, https://orbitrap.catalyse.cnrs.fr) to facilitate the analysis of long-term online Orbitrap data. Orbitool can average long-term data while maintaining the mass accuracy by re-calibrating each mass spectrum, identify chemical compositions and isotopes of measured signals, and export time series and mass defect plots. The noise reduction procedure in Orbitool can separate signal peaks from noise and greatly reduce the computational and storage expenses. Chemical-ionization Orbitrap data from laboratory experiments on ozonolysis of monoterpenes and ambient measurements in urban Shanghai were used to successfully test Orbitool. For the test dataset, the average mass accuracy was improved from

UHPLC/ESI Q-Orbitrap Quantitation of 655 Pesticide Residues in Fruits and Vegetables—A Companion to an nDATA Working Flow

Background Effective and expansive methods for multiresidue pesticide analysis are desired for routine monitoring programs. These methods are complex, especially when several hundred pesticides are involved. Objective Two approaches to sort data and identify isomers and isobaric ions in pesticide mixtures were evaluated to determine whether they could be differentiated by mass resolving power and/or chromatographic resolution. Method This study presents an application of ultra-high performance liquid chromatography electrospray Q-Orbitrap mass spectrometry (UHPLC/ESI Q-Orbitrap) along with QuEChERS for the quantitation of 655 pesticide residues in fruits and vegetables. Results From the developed method, 94.7% of the 655 pesticides in fruits and 93.9% of those in vegetables had recoveries between 81% and 110%; 98.3% in both fruits and vegetables had an intermediate precision of ≤20%; and 97.7% in fruits or 97.4% in vegetables showed measurement uncertainty of ≤50%. When the retention time difference (ΔtR) of two isomers was ≥0.12 min, they were chromatographically resolved. Twenty five out of 35 pairs or groups of isomers were chromatographically separated (ΔtR ≥ 0.12 min), but 14 pairs were not resolved (ΔtR &lt; 0.12 min). There were 493 pairs of pesticides with a mass-to-charge difference of &lt;1 Da. Only one pair of isobaric ions could not be separated by mass and chromatographic resolution. Highlights UHPLC/ESI Q-Orbitrap along with QuEChERS sample preparation offers a practical quantitative companion method to a non-target data acquisition for target analysis workflow for pesticide residue analysis in routine monitoring programs for food safety.

A high resolution multi-turn TOF mass analyzer

An ion optical design of a high resolution multi-turn time-of-flight mass analyzer (MT-TOF MA) is presented. The analyzer has rotationally symmetric main electrodes with additional mirror symmetry about a mid-plane orthogonal to the axis of symmetry. Rotational symmetry allows a higher density of turns in the azimuthal (drift) direction compared to MT-TOF MAs that are linearly extended in the drift direction. Mirror symmetry about a mid-plane helps to achieve a high spatial isochronicity of the ions’ motion. The analyzer comprises a pair of polar-toroidal sectors S1 and S3, a pair of polar (trans-axial) lenses, and a pair of conical lenses for longitudinal and lateral focusing. A toroidal sector S2 located at the mid-plane of the analyzer has a set of embedded drift focusing segments providing focusing and spatial isochronicity in the drift direction. The ions’ drift in the azimuthal direction can be reversed by using dedicated reversing deflectors. This gives the possibility of several operational modes with different numbers of turns and passes in the drift direction. According to numerical simulations, the mass resolving power of the analyzer ranges from [Formula: see text]40 k (fwhm) at small (typically below ten) numbers of turns to [Formula: see text]450 k (fwhm) at 96 turns.

Time-of-flight mass spectrographs of high mass resolving power

The masses of charged atoms and molecules were first investigated by laterally dispersive sector field mass analyzers, which early on already achieved high mass resolving powers. Equally, high mass resolving powers were achieved by time-of-flight mass analyzers during the last decades. These measurements became possible when fast and precise electronic circuitries became available. Such techniques have been developed and used extensively for the mass analysis of short-lived nuclei, whose mass values reveal insight in processes that describe the formation of elements in star explosions. Precise mass determinations of short-lived ions have been performed for energetic ions in large accelerator storage rings as well as for low-energy ions in time-of-flight mass spectrographs with long flight paths. Similarly, precise mass measurements can also be performed for molecular ions that help to reveal the structure of molecules. In case of very high mass resolving powers, the mass determination of molecular ions can be so high that the measured ion mass directly reveals the molecule’s sum formula.