As mentioned by @inteq you can set on-up script on ppp profile. But no need to create each profile for each user just to create new change mss script.
Just copy the script below and paste on the ppp profile default / default-encryption script if currently you only use default / default-encryption profile.
The script above will create a new firewall on new ppp interface and use the username as comment when the ppp user logged in. When the user logged out, the mangle rule will be deleted.