I've just found a John Penaluna on a list of people who were at Burra between 1845 - 1851, on the Burra History website, although there are no details of how long he was actually there for. Mary Jane Penaluna's birth there in 1850 does seem to indicate he's "my" John, so it's looking more and more likely that he isn't the convict John Penaluna, after all. Finding him on a ship destined for Adelaide around 1847, along with Ann, would be a huge help.
Fourteen Dunstans/Dunstones were also named, and of those, three may possibly be siblings of John's wife Ann: Richard, Sarah Jane and Thomas, but this is only guesswork at this stage. Thomas Dunstan came out to South Australia on the Cressy in 1847, with his parents Benjamin and Jane, some of his siblings, and his first wife Ann nee Caddy. He returned to Cornwall in 1854, to marry his wife's younger sister Grace after Ann's death and then popped up in Creswick and Ballarat shortly after. I have no proof of where he was prior to 1854, but interestingly, the Burra website mentions that many of the Burra miners left "practically en masse" for the goldfields of Creswick and Ballarat in 1852, so Thomas could have well been at Burra between 1847 and 1852 at least. Frustratingly, there's no mention of a Benjamin, Jane or Nicholas Dunstan being at Burra, so I can only assume that the date they left England, and their destination, meant that they were probably headed for the copperfields of either Kapunda or the Burra.