I'll give you a couple examples. Google stores a huge amount of data in BigTable [1] which is fundamental for the operation of Gmail at scale. Another, Facebook initially used Cassandra [2] for it's Inbox search, then migrated to HBase when their needs changed for their new messaging feature.
Do we know if the the underlying data is stored in RDBMS? I'm guessing not at Google, but yes for Facebook/Inbox search. But my point is I'm not ruling it out, I'm open to different options.
[1] http://en.wikipedia.org/wiki/BigTable [2] http://en.wikipedia.org/wiki/Apache_Cassandra#History