A web application (or SharePoint web part in my case) may throw System.UnauthorizedAccessException error below if the file you are trying to access is not available. The file may not exist or you may not have permissions to access it.
An exception of type “System.UnauthorizedAccessException” occurred in mscorlib.dll but was not handled in user code. Additional information: Access to the path ‘\networkshare\filename.ext’ is denied.”