I tried:
process.MainModule.FileName.Contains(\"x86\")
But it threw an exception for a x64 process:
Win32Exception:
Neither WMI's Win32_Process or System.Diagnostics.Process offer any explicit property.
How about iterating through the loaded modules (Process.Modules), a 32bit process will have loaded %WinDir%\syswow64\kernel32.dll while a 64bit process will have loaded it from %WinDir%\system32\kernel32.dll (this is the one dll that every Windows process loads).
NB. This test will, of course, fail on a x86 OS instance.