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

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.