Drop some vinegar on the rock. If it fizzes, then it's unsafe. Another way to do it, is put the rock in a bucket of water. Check the pH before adding the rock. A few days later, check the pH of the bucket water. If it's higher or lower, then it's unsafe.
A good scrubbing and soaking before adding (should it be safe) should also ensure saftey
As you already know, obsidian is a volcanic glass and unreactive. The white inclusions of snowflake obsidian are cristobalite, which is a form of quartz (SiO[sub]2[/sub], the same as sand). I think it should be OK in a fishtank.
Information from http/www.mindat.org/mineralindex.php