My take on using natural lava-based rock is that with the possible exception of good quality tuffa, most volcanic rock is really not suitable for reef aquariums because it is not porous enough. Although most lava/pumice rocks appear to be very porous, and the surface will provide area for aerobic bacteria for nitrification, they are usually a closed-cell interna structure which means water can not flow through the stone, only over and around the surface textures. This limits its usefulness for biofiltration as it can not host the anaerobic bactiera that performs denitrification, which means the lava rock will be a nitrate factory. Natural coral based rock, live or dry, has an open-cell construction of coral skeleton plus caveties and tubes from clams and worms that allows water to wick throughout the interior of the rock. This internal waterway is the perfect environment for denitrification to occur and is why live rock is so good as the main filtration system in reef tanks.
I won't go into the possible toxicity of the lava rock as I don't know of anything specific to be concerned with. I think the softness of tuffa may make it a concern for leaching if there is anything toxic in its makeup. In the past, I have used the soft porous tuffa rock in my reef tanks, but, only a few small (fist sized or smaller) pieces, so, I'm sure I didn't have enough to notice any bad effect of leaching if it did occur. These tuffa rocks encrusted nicely with coraline and ended up looking like any other liverock. The harder lava rocks are basically glass, so, if properly cleaned to remove dried on/embedded organic matter, should be safe enough to use.