Notifications seem to primarily depend on which Topics you watch:
You can watch a topic to be notified when a new question is added. This is a great way to keep informed about what is going on in your site.
To watch a topic:
- Go to Questions > Topics
- Choose Watch next to any topics you wish to be notified about.
If you are an administrator you can also add and remove people from the watchers list for a topic. Navigate to the topic then choose Edit beside the Watchers list.
You can see/test this on the Topics tab on this very site for example.
Strangely it isn't possible to watch all topics at once, however, you can watch all questions with the resp. Watch all button on the Questions tab of your instance (understandably not available on this site) - according to @Bill Arconati's response in the comments section, this is essentially the same as watching all current and future topic.
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