Spanish rider had suffered two falls in the earlier stages
One of the pre-event favourites to win this year's Tour de France has pulled out during the ninth stage.
Two-time champion Alberto Contador has been struggling with injuries.
The Spaniard stopped before getting into the team car, between Vielha Val d'Aran in Spain and Andorra-Arcalis in the Pyrenees.
Contador had suffered two falls in the first two days of action. The first had left him with road rash from his knee to his shoulder on his right side, although he avoided any muscular injuries.
The 33-year-old previously won the tour in 2007 and 2009.
In 2014, he also abandoned the Tour due to injury.