During carbon steel manufacture, slag residues are generated to remove material impurities from liquid metal and thus control the quality of carbon steel. As the utilization of secondary metallurgical slags is not as efficient as those of primary slags, a comprehensive characterization of steel ladle slag was performed. Pseudo-total concentrations of a wide range of elements were determined during a 6-week sampling period with relevant physical and chemical properties, sequential extraction of trace elements, and parallel mineralogical characterization of extraction residues from a representative combined sample. According to the results, only Cr and V occurred in elevated concentrations with respective 6-week mean values of 198 and 310 mg kg−1 (d.w.). The residual standard deviation of the weekly pseudo-total concentration values of the aforementioned elements (24 and 31 %, respectively) indicated that significant variation in the concentration of trace elements can occur due to fluctuation in process conditions and/or slag characteristics. The sequential extraction procedure suggested potential phytoavailability of V (123 mg kg−1, d.w., amounting to 41 % of the respective pseudo-total concentration) through, e.g., changes in prevailing redox conditions. Although the analytical approach was validated by the analysis of a certified reference material and the calculation of extraction recoveries, the mineralogical characterization of parallel extraction residues indicated non-selectivity of the procedure coupled with potential redistribution phenomena during extraction with hydrogen peroxide and ammonium acetate.