5

Take, for sake of concreteness, the preposition entlang (see also this related question).

At least, two uses are possible:

Genitive preposition: Entlang des Flusses gibt es …
Accusative postposition: Den Fluss entlang gibt es …

(I ignored the dative-variant since it is rare and it's something don't feel confortable with. But the answer explains it all.)

As for a relative clause, is genitive the only option?

der Fluss, entlang dessen es … gibt, …

or is it also possible with the accusative variant? like:

der Fluss, den entlang es … gibt, … (which somehow sounds awkward).

I guess the same rule would hold for other postpositions, like wegen.

5

Entlang takes either genitive, accusative or dative. It's accusative or rarely dative if following the substantive:

Es gibt Bäume den Fluss entlang.
Es gibt Bäume dem Fluss entlang.

And genitive or dative if preceding the substantive:

Es gibt Bäume entlang des Flusses.
Es gibt Bäume entlang dem Fluss.

Another variation is:

Es gibt Bäume am Fluss entlang.

In a relative clause it looks like this

Der Fluss, entlang dessen es Bäume gibt. (genitive)
Der Fluss, entlang dem es Bäume gibt. (dative)
Der Fluss, an dem entlang es Bäume gibt.

Using accusative sounds indeed odd in your example. I believe reason is the "es gibt"-structure. From a grammatical point of view, I don't see any reason why it should be wrong. Here's a different example, which is absolutely fine:

Man fährt im Schiff den Fluss entlang.
Der Fluss, den man im Schiff entlang fährt.

So, nothing wrong with:

Der Fluss, den entlang es Bäume gibt. (accusative)
Der Fluss, dem entlang es Bäume gibt. (dative)

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