create app launcher and change icon on xfce desktop
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Just do a right-click on the Desktop and click on Add Launcher in the menu. That will open a dialog, where you can choose the program to launch and the icon and text that will be displayed. If you want it to be persistent in your live-environment copy the ~/Desktop-folder to /etc/skel in your base-system, change the owner of the folder and all files in it to root and recreate your live-system.