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Advancing Trace Element Analysis with Atomic and Plasma Spectroscopy: Molecules and Nanoparticles
Ryszard Lobinski
National Center for Scientific Research (CNRS), Institute of Analytical and Physical Chemistry for the Environment and Materials (IPREM), France
The role and toxicity of trace metals in both environmental and biological systems are critically dependent not only on their total concentration, but on the specific chemical (species) and physicochemical (nanoparticles) forms, in which they occur.
Historically, atomic spectroscopic techniques, such as atomic absorption spectrometry (AAS), inductively coupled plasma optical emission spectrometry (ICP-OES), and, lateron, ICP mass spectrometry (ICP-MS), were used primarily, if not uniquely, for bulk elemental analysis. Their coupling with chromatographic or electrophoretic separations, so-called "hyphenated techniques", enabled the resolution of individual metal-containing species with sub-picogram sensitivity. These advances underpinned much of the progress in environmental and bioinorganic trace element speciation analysis, particularly in quantifying individual metal pollutants, explaining the metabolism of metal probes, and tracing the metal circulation routes in the environment. The emergence of single particle ICP-MS allowing the determination of particle size (based on signal intensity) and particle number concentration (based on spike frequency) made possible the analysis of insoluble metal species, thus extending the scope of speciation analysis beyond the molecular properties.
However, the atomic spectroscopic approaches often fall short when faced with the complexity and diversity of naturally occurring metal species, especially in biological systems and omics-level studies. The emergence of electrospray ionization and high-resolution accurate-mass (HRAM) mass spectrometry, including Fourier-transform ion cyclotron resonance (FT-ICR) and Orbitrap platforms, opened new avenues for the detection and identification of intact metal-containing molecules with resolutions by far exceeding those offered by chromatography or electrophoresis. By recognizing isotope patterns and using accurate mass profiling, HRAM-MS facilitates the direct molecular-level identification of metal complexes within complex biological or environmental matrices. It enables the mapping of dozens of trace metal species simultaneously across biological tissues, environmental compartments, or food chains—capturing a more realistic and functional picture of metal distribution and activity.
The lecture will discuss the evolution of atomic and plasma spectrometry to become essential complements to molecular mass spectrometry, providing critical isotopic, quantitative, and structural information. It will highlight the convergence of atomic spectrometric traditions with molecular innovations, illustrating how trace element analysis is being transformed by hybrid approaches. Recent examples of multimethod characterization of environmental and biological systems will be showcased, combining chemical and physico-chemical speciation analysis.
