Analytical spectrometry methods based on plasma source (ICP-AES, ICP-MS) enable multi-elemental quantitative characterization of various materials. Reliability of measured elemental concentrations strongly depends on spectral and/or non-spectral matrix interferences. Iron-based materials that contain numerous analites at trace concentration level are representatives of extremely demanding analytical samples. The estimation of magnitude of interferences and sensitivity of determination are prerequisites in elemental profiling of such kind of material. In this work, the elemental profiles of archaeological samples from an early-iron production along with samples of iron nanoparticles were analysed by ICP-AES method. The selection of emission lines that are free from interferences was performed after testing of matrix effects. For this purpose the model solutions and real sample matrix, which consists of solution of iron meteorites, were used. By background emission correction, the sensitive emission lines of transition metals, lanthanides and selected semi-metals were selected for the purpose of elemental profiling of samples. Archaeometallurgical samples from bloom iron production were characterized by XRF and SEM-EDS methods, additionally. The extended range of obtained elemental concentrations was subdued to chemometric processing. Multivariate statistical analysis (PCA, HCA) has showed clear discernment between samples of inhomogeneous material. It provided classification of examined samples on groups, such as bloom iron, ceramic rich slag and ore material. DrThe purity of synthesized iron nanoparticles was determined by ICP-AES method using the adjusted operational parameters. The prepared zero-valent iron nanoparticles (nZVI) were also characterised using SEM-EDS, XRD, TGA and IR methods. The capability of ICP-AES method in tracking of metal sorption on prepared nanoparticles was examined. In particular, the removal of chromium (VI) at low levels from aqueous solutions was emphasized. The results show that high content iron samples were successfully analysed by ICP-AES method after proper line selection and applied background corrections. In addition, the elemental profiles of samples were complemented by information that were gained through combination of spectroscopy and chemometric methods.