It's looking for the main texture file for some reason...
Obviously, this is an Xfire problem, BUT I'm going to see if I can help

Hokay (now that Xfire has finished hammering my drive looking for games)...
Open up the main Xfire window, click on Tools, then Options. Click on the Games tab, then look under Not Installed (or maybe in Installed, if there's an error with the command line), and find Natural Selection. Make sure the Game Path box reads "C:\Program Files\Steam" (without quotation marks), or "C:\Program Files (x86)\Steam" (for all you 64-bit people

). Click Apply, and see if it finds the game then.
For some reason at some point, you (or an update) has told Xfire to look for the ns.wad file, when it actually needs an executable file to find the game. NS is launched as "C:\Program Files\Steam\steam.exe" -applaunch 70 -game ns. So looking for a wad file (which is the master texture file iirc) is pointless.
Hope that helps