Chemical Ionization Mass Spectrometry: Applications for the In Situ Measurement of Nonvolatile Organics at Ocean Worlds.

A new technique that has applications for the detection of nonvolatile organics on Ocean Worlds has been developed. Here, liquid mixtures of fatty acids (FAs) and/or amino acids (AAs) are introduced directly into a miniature quadrupole ion trap mass spectrometer (QITMS) developed at Jet Propulsion Laboratory and analyzed. Two ionization methods, electron impact and chemical ionization (EI and CI, respectively), are compared and contrasted. Further, multiple CI reagents are tested to explore their potential to "soften" ionization of FAs and AAs. Both EI and CI yield mass spectra that bear signatures of FAs or AAs; however, soft CI yields significantly cleaner mass spectra that are easier to interpret. The combination of soft CI with tandem mass spectrometry (MS/MS) has also been demonstrated for AAs, generating "fingerprint" mass spectra of fragments from protonated parent ions. To mimic potential Ocean World conditions, water is used as the primary collision gas in MS/MS experiments. This technique has the potential for the in situ analysis of molecules in the cryogenic plumes of Ocean Worlds (e.g., Enceladus) and comets with the ultimate goal of detecting potential biosignatures.

Computer Modeling of an Ion Trap Mass Analyzer, Part I: Low Pressure Regime.

We present the multi-particle simulation program suite Computational Ion Trap Analyzer (CITA) designed to calculate the ion trajectories within a Paul quadrupole ion trap developed by the Jet Propulsion Laboratory (JPL). CITA uses an analytical expression of the electrodynamic field, employing up to six terms in multipole expansion and a modified velocity-Verlet method to numerically calculate ion trajectories. The computer code is multithreaded and designed to run on shared-memory architectures. CITA yields near real-time simulations with full propagation of 26 particles per second per core. As a consequence, a realistic numbers of trapped ions (100+ million) can be used and their trajectories modeled, yielding a representative prediction of mass spectrometer analysis of trace gas species. When the model is compared with experimental results conducted at low pressures using the conventional quadrupole and dipole excitation modes, there is an excellent agreement with the observed peak shapes. Owing to the program's efficiency, CITA has been used to explore regions of trapping stability that are of interest to experimental research. These results are expected to facilitate a fast and reliable modeling of ion dynamics in miniature quadrupole ion trap and improve the interpretation of observed mass spectra. Graphical Abstract ᅟ.