I would estimate the skill of the creators spellcraft and make a roll each time the item is used underwater. This would make it unreliable, sometime it would work and sometime it would not. This would be more fun and in the spirit of the rule.
The ring of mystic fire only affects the upcoming spell once
The ring of mystic fire (Magic Item Compendium 125) (7,500 gp; 0 lbs.) does, indeed, grant "a bonus to the amount of damage you deal with the next fire spell you cast before the end of your turn," but the ring only grants that bonus once. Each ray of a scorching ray spell isn't the spell; instead, the whole spell creates multiple rays. The ring improves the spell's damage only once by a maximum of +4d6 no matter how many effects result from the ring-modified spell.
(Ruling that each ray of the scorching ray spell benefits from the ring multiplies the power of the ring by the number of rays—with rather extreme consequences at low levels, especially given that the ring increases also the wearer's caster level for fire spells!)
Although the DM has several options available to adjudicate the ring's effect—allowing the player to distribute the total number of extra dice damage the ring grants among the rays before (or even after) the rays're launched, for instance—, this DM would keep things simple and have the player add the extra damage to his PC's first ray in a volley from the spell scorching ray, in much the same way that precision damage applies to the first attack in a similar volley (Rules Compendium 42). (In fact, I have a fire wizard in a current campaign who's eyeing this very item, and that's how I'm ruling it works.)
Hence, for example, under such a ruling, a level 6 caster wearing a ring of mystic fire can take a swift action to spend 3 of the ring's charges. Then the caster can cast scorching ray, creating 2 rays (because of the increase in caster level granted by the ring) and making 2 ranged touch attacks. If the first ray hits, it deals 8d6 points of fire damage. If the second ray hits, it deals 4d6 points of fire damage.
Sounds like fire damage to me, but you're burning them with superheated steam instead of flame.