I found out myself which actual limit I am hitting here:
From http://www.datastax.com/documentation/cql/3.1/cql/cql_using/use_collections_c.html:
Cassandra includes collection types that provide an improved way of handling tasks, such as building multiple email address capability into tables. Observe the following limitations of collections:
The maximum size of an item in a collection is 64K.
The error message is not ideal, at least it was not clear what the actual problem is to me!