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Post‐blast fumes are hazardous and known to cause severe health related issues of workers. Further, these harmful gases have a significant impact on the surrounding environment. Thus, it is imperative to have an in‐depth understanding of the real time detonation fume generation in underground space to avoid hazardous health risk of the worker. In this context, the mapping of toxic fume concentrations generated by the detonation of ANFO explosives in the actual field is a fascinating area of research that has a great environmental impact. This article examined the real‐time analysis of toxic fumes generated by ammonium nitrate fuel oil (ANFO) explosives at various locations of a metalliferous underground mine. Furthermore, detonation parameters of various ANFO explosive compositions were also studied at the mining site. On‐site blasting studies were performed with ANFO explosives, and post‐detonation fume measurements enabled us to map the CO and NOx concentrations in underground spaces. Toxic fumes like CO and NOx were analyzed before and after each blasting operation at different intervals, and found within the allowed limit as per the Directorate General of Mines Safety guidelines. Additionally, an empirical correlation has been established to evaluate the maximum detonation velocity based on the alteration of ammonium nitrate and fuel oil composition. [ABSTRACT FROM AUTHOR]