Microfishd: he might enjoy Civ 1, 2, or 3. He also might enjoy Railroad Tycoon 2
zeogold: I think I may just break down and cry.
I hear you - and I
am a strategy and RPG gamer. ;) What I mean by that is that while the wife and I are strategy and RPG gamers who have only recently gotten into the puzzle/adventure games, if your brother LOVED Myst, then you'll want to stick with zeogold and the others' advice on this. (And don't fault Microfishd too much, strats can be a different type of long-planning puzzle if done well.)
Quern - definitely this, if your brother's rig can handle the requirements. See HunchBluntley's post above.
Obduction - another very good one I would highly recommend here.
No on Firewatch - it has a bit of mystery and exploration but lacks that feel and sense of wonder and the see it from another way and think outside the box puzzles of Myst.
I would personally start with those.
IF your brother likes thinking and puzzles - then he might want to try a turn-based strategy game like
Sid Meier's Civilization III. It does not have the first person exploration and put-it-together puzzles of Myst, but is more a strategic long-term planning "stay up all night just one more turn" addictive bit-of-a-jigsaw empire building type of puzzle. Or he could look into a city-builder, which is more jigsaw planner and usually a bit less long term. However those would be something to see if he wanted to look into later. For now, I would stick with the majority's suggestions.
Also, definitely use the "Offline Backup Installers" as others have said. That way the games will not require internet connections and can be played offline at any time. :)
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zeogold: ... Schizm: Mysterious Journey is a decent Myst clone.
If you're willing to go outside of GOG, look into the Rhem and Aura: Fate of the Ages series.
X-com: I also recommend Ether One, which is a story driven environmental puzzler + one of those games I always fondly remember for good story, setting, sound and graphics/environment.
Hm, I'll have to go look these up myself. Thanks! :)