PGP isn't user friendly, but from the Snowden leaks we learned it is one of the few encryption standards the NSA hasn't been able to break. TLS and most configs of VPN protocols were shown to be easily compromised. PGP was basically shown to be a show stopper.
Perhaps older versions of SSL, but there is no evidence that anyone has compromised TLS.
There is evidence that encrypted traffic was stored and research was done on the metadata of these connections but that is no surprise. That may be what they were referring to.
1. http://m.spiegel.de/international/germany/a-1010361.html