Nicolas Roche finished fifth in today's fourth stage of the Vuelta a Espana.
Roche was placed well throughout the race and is 24 seconds behind the leader Joaquim Rodriguez.
Tour de France runner-up Chris Froome moved to within a second of the lead after the fourth stage of the Vuelta a Espana.
Australia's Simon Clarke claimed the stage win but Team Sky's Froome moved up the rankings after Valverde lost significant ground on the 161-kilometre stage.
Valverde had led the chasing pack by 19 seconds, but was down in ninth tonight, to allow Joaquim Rodriguez to take over the leader's red jersey.
Froome crossed over in the main pack along with Rodriguez, who himself finished second at the Giro d'Italia earlier this summer, to remain a second behind the Spaniard.
Clarke outsprinted Germany's Tony Martin to the ski-resort finish at Valdezcaray with Assan Bazayev in third.
Tomorrow's 168km fifth stage will see the riders start and finish in Logrono.