Hi, ashes in themselves are not definite evidence of fire-setting in a mine - as you mention in your wiki article, fires can be used underground as a means of ventilation control. There is a characteristic "doming" to a rock surface which has been fireset, so I'd be interested to see if that was identified in the Welsh gold mines.
There are a number of articles on firesetting in the online archives of the Peak District Mines Historical Society at
http://www.pdmhs.com/BackIssues.asp Vol 12 no3 was specifically looking at pre-powder mining and there are a number of other articles looking at prehistoric UK and overseas firesetting. The recent work by John Barnatt and Terry Worthington isn't online at the moment (you'll have to buy a copy if you want to read it). This found that most Peak District firesetting was done in the 16th and 17th centuries, generally using coal rather than wood (although use of horse bones is mentioned in documentary records), and the fireset surfaces weren't quenched but allowed to cool, the ore picked off and brushed away from the working face.
Follow the horses, Johnny my laddie, follow the horses canny lad-oh!