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I have many users using a Debian system through thin clients and I'm looking for a way to setup file associations globally for all the XFCE4 desktop environments.

Is there a way to setup the associations for Thunar or another file manager and the xfce desktop icons so that they are all the same accross all users?

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To do that system-wide you need to create /usr/share/applications/mimeapps.list as follows

[Default Applications]
application/pdf=evince.desktop
image/png=eog.desktop

Use xdg-mime to find out the mime-type of your files:

xdg-mime query filetype /etc/passwd

You can find available applications with ls /usr/share/applications/*.desktop

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