I've been playing with an implementation on top of lightning mdb[1]. Your profile doesn't have an email but feel free to email me if you're interested.
100GB isn't that big a deal. If you have at least 16GB of RAM it should be a breeze. There are much larger data sets in OpenLDAP in production around the world.
But I wouldn't choose python for large scale data processing work. The python CPU/memory overhead is like 100:1, compared to C. (This is why I worked on rtorrent and ditched the original bittorrent client ASAP, and why I hate bitbake....)
The biggest problem currently is actually degrading performance, although I'm almost 100% sure that this isn't caused by lmdb itself, but rather by the bindings I've tried.
In the end, doing it directly in C is probably the only thing that will actually work.