Creative Director
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If anyone in the party has Knowledge (nature), I'd have them make the roll. No matter what the result is, go ahead and give them a clue or two on how to kill it. If a wizard in the party has ray of frost, that's probably the easiest method to kill it. If there's a druid in the group, chill metal cast on the tip of a reach weapon should allow you to scrape the stuff off. If you have a character in the party that's got more than 18 hit points and is tough... he can have the other PCs tie a rope to him and he can make a charge at the door to try to break it down, and if the nonlethal damage puts him out, they can drag him back to safety. Summoned monsters are another good way to try to break down the door.
And if they seem about to abandon the door, you might want to have Shensen stir and call out for help.
Knowledge (dungeoneering) would also seem to be appropriate, but that's probably not as common as Knowledge (nature).
My party had interrogated one of the bad guys who had been on duty in the basement, so they knew Shensen was there. When they called out, she answered. But she didn't know how to help them get through the door. The party sorcerer ended up using a few lesser acid orbs on the door until it was sufficiently destroyed, then the party tank barrelled through what was left of the brown mold (just how much acid damage do you need to do to kill brown mold?) and rescued Shensen.
I went with Knowledge (Alchemy,) myself. I figured that if an inn is going to use as dangerous a substance as brown mold to keep their goods chilled, they're likely to have something on hand to deal with it in the event of a spill ("Cleanup on winerack nine!") I figured that it would be an alchemical substance of some sort that Shensen was probably counting on the thugs not recognizing.
When the party rogue and swashbuckler started nosing around the kitchen looking for something they could use to "burn" off the mold, I noted the Gnome swashbuckler has knowledge (Alchemy), and so I asked him to roll me a check. It was a good roll, and between him and the rogue, they were able to find enough of the alchemical "fungus-stunner" to make it work. Improvising it into a grenade-like weapon, they tossed it at the door, and it burst, causing most of the brown mold to go temporarily inert, so they could bust down the door without harm.
One could say I went easy on them, but it seemed a logical idea to me... and it was a good op to let the gnome swashbuckler player use his character's alchemy skill.
In my game they waited until the inn was safe, after that they heard Shensen when they went down, she told them about the mold and after the night, healed, she went through the door after casting another warp wood and resist element to free herself.
my group burned the lucky monkey down... it was a fun night. of course now there is a big giant patch of brown mold where the lucky monkey used to be... poor shensen...