Formation of iron oxides clusters induced by resonant laser ablation/ionization

Abstract The present work has been conducted by Time-of-Flight Laser Microprobe Mass Spectrometry (TOF-LMMS) in resonant or non-resonant ionization modes. The targets (micrometric particles of powdered iron oxides Fe 1− x O, Fe 3 O 4 and Fe 2 O 3 ) were synthesized, on the one hand, from iron 54 isotopes and, on the other hand, from natural iron 56 isotopes. The positive-ion cluster distributions showed a strong correlation with the stoichiometry of iron in oxides. This correlation is even more striking when the resonant ionization process of iron at 278.8 nm is used. The dissociation energy of the Fe-O bond in the Fe 1− x O bulk also affects the distribution of the intensity of clusters. A better understanding of the way cluster ions (Fe 2 + and Fe 2 O + ) are formed will improve our ability to interpret the mass spectra of iron oxides. Indeed, results show that the way Fe 2 + dimer and Fe 2 O + ions are formed is closely associated with the presence of the neutral species FeO and singlet oxygen 1 O 2 ( 1 Δ g ). Fourier-transform ion cyclotron resonance mass spectrometry (FT/ICR/MS) has been used to detect the presence of oxygen in the singlet 1 O 2 ( 1 Δ g ) state in the plume generated by laser ablation. The in situ identification of iron oxides in biological samples is very important for studying their role as carriers of certain toxic molecules (e.g. PAH).