In the case of DDG, that would be difficult. DDG uses SSL. If you make a mistake and type "duckduckgo.com" instead of "https://duckduckgo.com", it will automatically redirect you to the secure page. Unfortunately, that redirect gives a man-in-the-middle and opportunity to hijack your connection, even with SSL; however, that's tricky enough that its hard to imagine anyone pulling it off without ever being noticed.
HSTS allows a site to indicate that in the future it should always be loaded over a secure connection, so you only have an interceptable connection the very first time you visit that site. Both Firefox and Chrome allow sites to add themselves to a list to "preload" HSTS enforcement, so even that initial connection which is man-in-the-middle-able doesn't happen.
I don't see them in the current lists, so DDG should contact Mozilla and Google to get added to their preloaded HSTS lists[1][2] so all connections will automatically happen only over HTTPS.
The initial request/redirect response is insecure. So a MITM can intercept the redirect response and replace it with his own content. That content could be, for example, a 200 response status and HTML pulled from the attacker's HTTPS connection to the target site.
So rather than being redirected to a secure connection, I happily communicate with the attacker instead.
They don't need the existing SSL cert. The "beauty" of SSL is that they can use a cert generated by any CA trusted by your browser - or even a second one from the same CA -, even if there's already a cert issued by one.
It could also be named PRISM as a form of misdirection, to make people think that the codename referred to upstream-collection operations. (It's beyond doubt that upstream collection is still ongoing too, though.) Or it could be that spy organisations just like optical metaphors. FWIW the You Should Use Both slide seems to use PRISM to refer specifically to the "direct collection" and not the upstream collection capability.
Why do you think it is called PRISM? It's probably named for the way they are splitting the fiber and recording everything.