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Herein, we investigate silicate-phosphate glasses from the SiO 2 –P 2 O 5 –K 2 O–MgO–SO 3 system enriched with various amounts of sulfur, as a nutrient indispensable for the proper development of plants, in order to gain a profound understanding of the structure of such materials. An inherent capability of glasses from the studied system to incorporate sulfate groups into the vitreous matrix was discussed on the basics of the results from XRF, XRD and internal Al 2 O 3 standard techniques. It has been found, that as much as 3 mol.% of SO 3 can be loaded into the glass batches to obtain fully amorphous material, while beyond this limit K 2 SO 4 crystallizes within the matrix. Comprehensive spectroscopic investigation, comprising Raman, Middle Infrared (MIR), 29Si and 31P MAS-NMR, X-ray absorption spectroscopy (XANES and XAS) techniques, has been implemented in order to determine an impact of sulfur on silicate-phosphate glass framework. On this basics, it has been concluded, that sulfur exists in the vitreous matrix in the form of specific domains, in which [SO 4 ]2- anions are surrounded by the shell of charge-compensating K+ cations. Such sulfate groupings maintain their individuality without direct bonding to silico-oxygen or phospho-oxygen subnetwork. Spectroscopic results revealed also, that the presence of sulfur affects silico-oxygen subnetwork to a significantly greater extent than the phospho-oxygen one. It has been demonstrated, that along with SO 3 addition, the more polymerized Q S i 3 units increase in abundance at the expense of less polymerized Q S i 2 groups. Results of the present study are believed to contribute to a greater understanding of the nature of sulfur-bearing oxide glasses. [ABSTRACT FROM AUTHOR]