Super Tier Spells start at Level 70

From the perspective of the tiers of magic, spells of this level could be considered spells, and not spells at the same time. To begin with, they did not consume MP, but instead could only be used a limited number of times per day. When one first learned them, they could only be used once daily. Every ten levels after level seventy, however, one could use them an additional time per day.
One could learn a single Super-Tier spell per level.
Rather than call them magic, they might be better described as skills.
In other words, the average Player could only use four Super-Tier spells per day at level one hundred. One might ask at this point — why not consecutively cast Super-Tier spells to defeat Shalltear? Indeed, the destructive power of Super-Tier magic was unrivaled, dwarfing even that of tenth-tier spells.

- Overlord; Vol 3; Chapter 4