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With the peloton still together and speeds high, the two team leaders came down on the descent of the Alto del Vivero with 23 kilometres to go, Mas immediately being examined by team doctors while Carapaz looked ginger with a pair of bloody knees.
The Ecuadorian managed after a while to slowly climb back on the bike and continue the stage, but the same couldn't be said for Mas as it was later confirmed the Spaniard had abandoned the race with a suspected shoulder injury.
Mas' exit marks a second consecutive Tour de France cut short after not starting last year's Stage 19 due to testing positive for COVID-19. Movistar will now need to look for another strategy as the race continues.
Carapaz managed to finish the stage but looked in serious pain from doing so as he crossed the line over 15 minutes behind winner Adam Yates (UAE Team Emirates) a deficit that effectively ends his contention for the general classification virtually before it began.
Expectations were high for the Olympic champion, heading into his first Tour de France as an EF Education-EasyPost rider following a move from INEOS Grenadiers before the start of the season, but the race looks to be a missed opportunity after scans revealed a small fracture to his left kneecap.
"He looked to be in quite a bit of pain when he came in there," EF Education-EasyPost directeur sportif Tom Southam said of Carapaz at the finish. "Which is to be expected because I think he came down pretty hard.
"It’s a blow. It can happen to anyone on any day of the race. There weren’t crashes today so I think it magnifies the impact of that one."
EF were luckier than Movistar in that their American rider Neilson Powless took the King of the Mountains jersey today, not leaving them completely back to square one with 20 stages to go.
"We need to work out what the next steps are," Southam continued. "But if you look at our team, there are plenty of guys who can step up to the plate and can do stuff.
"We’ve got plenty of other options. It’s not like we came here with Richard and seven other guys to ride for him."