Breaking the boundaries in spectrometry. Molecular analysis with atomic spectrometric techniques

Since the development of atomic spectrometry, trace element and isotopic analysis has been mainly based on the monitoring of atomic spectra and monoionic species. However, according to the literature and considering the current instrumental developments, it seems that some of the remaining challenges in this field can be mitigated via the measurement of molecular spectra or of polyatomic ions. This review discusses recent advances in three of the most important atomic techniques (laser-induced breakdown spectrometry, high-resolution continuum source atomic absorption spectrometry and inductively coupled plasma mass spectrometry) and how the monitoring of such molecules or polyatomic ions containing the target analyte enables attaining better selectivity and opens new ways to determine non-metals and to obtain isotopic information. •Elemental analysis benefits from monitoring highly resolved molecular spectra.•New possibilities for isotopic analysis using optical methods are discussed.•Producing and measuring polyatomic species in ICP-MS/MS improves selectivity.•Applications of the most representative atomic techniques are highlighted.