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The paper presents the results of studies carried out using differential thermal analysis (DTA) and differential scanning calorimetry (DSC), conjugated with thermogravimetry (TG). Measurements were made for samples with differentiated compositions, mainly consisting of ammonium nitrate with fertilizer purity and compounds that may be present in nitrogen fertilizers as potential additives or contaminants. The possibilities of applied techniques and recommendations concerning proper selection of measurement conditions are described. Furthermore, the method of interpretation of the obtained results is presented, which allows evaluating the thermal stability of the tested mixtures for the safety and quality of nitrogen fertilizers.