You should have posted this in the DIY section but to answer your question styrofoam itself is inert and harmless in the water column. I use it under big rocks in my tank to prevent scratches and damage to the tank. Hope that helps.
The concrete if you use it will need to be soaked. Just plain styrofoam itself is inert. If you cover the styrofaom with concrete you will have to soak and drain the background several times until the ph is stabilized.
I would use drylok instead of concrete much easier doesn't need weeks or months to cure and won't mess with ph. This is the method I plan on using. Do a quick google search on it will tell you everything you need to know