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The goal settled a dour battle in which both teams struggled to play constructive football in the very blustery conditions.
Honours were even on an uneventful 1st half in which both teams battled for supremecy. Gary Montgomery made a full length save from Marc Richards and again from a shot on the turn from Paul Hayes.
At the othe end Martin Butler was inches away from converting a poor back pass and a 10 minute purple patch for Rotherham saw midfielder John Mullin have a 20 yarder blocked and leading scorer Deon Burton thrash a bicycle kick wide.
The best chance of the half though fell to the visitors when neat passing on the edge of the box put ayes clea but he could only screw wide from 6 yards.
Rotherham had the wind at their backs in the 2nd half but had a let off when good work by Jacob Burns put Chris Shuker in space 5 yards out but he strike wide of goal.
Rotherham captain Colin Murdock placed a header narrowly over from a Grant Leadbitter corner as the match opened up and play switched from end to end.
Another good effort by Andy Monkhouse had Nick Colgan in the Barnsley goal stretching but the Millers were rocked back on their heels when Devaney, on as a sub for only 10 minutes, pounced for the winner.
Rotherham launched a late rally but failed to threaten and are now without a win in 9 league games.