It's most likely to avoid having the same two callsigns in the air at the same time.
Say there's a flight #123 from Nashville to Las Vegas with a stop in Dallas. If the BNA-DFW leg is 3 hours late, but the company wants to get the DFW-LAS flight out on time, they may add a letter to the callsign to avoid having the same callsign arriving and departing at the same time. Delta uses 9000 series flight numbers when that happens.
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