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Vollering traded blows with Annemiek van Vleuten (Movistar) on the steepest part of the climb but proved too strong in the final few hundred metres, finishing three seconds ahead of her compatriot and nine ahead of third-placed Ricarda Bauernfeind (Canyon-SRAM).
The SD Worx rider overtook previous GC leader Marianne Vos (Jumbo-Visma) as a result of her victory and now holds a five-second advantage over van Vleuten with two stages remaining.
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Full replay: Stage 5 - La Vuelta Femenina 2023
It only took the first category climb for the peloton to split on the fifth stage, with the Puerto de Navafria leaving 25 riders in front and Vos among those dropped during its 11.5-kilometre ascent.
At the top of the climb, Elise Chabbey (Canyon-SRAM) extended her lead in the mountains classification, but a crash with 35 kilometres remaining saw Niamh Fisher-Black (SD Worx) and Ane Santesteban (Team Jayco-AlUla) go down in the front peloton.
Movistar, SD Worx and EF Education-TIBCO-SVB worked with Jumbo-Visma to close the gap between the two groups, and the margin was down to 30 seconds by the time of the Mirador de Penas Llanas.
Gaia Realini (Trek-Segafredo) led the way on the five-kilometre climb before Vollering took control two kilometres from the finish line.
Only van Vleuten and Bauernfeind could keep pace with the 26-year-old, and while the Movistar rider launched an attack in the final 300 metres, it wasn’t enough to deny Vollering from victory.
“Today was a hard day,” Vollering said after the race. “It looked really good for us (after the Puerto de Navafria), we were still with three in the group, but then Niamh crashed, unfortunately.
“She was super strong, and we really hoped that she could come back. I was just really keen to win this one for Niamh.”
“I thought I would just go my own pace because I know I can keep a hard pace for a long time, and I hoped to drop as many as possible, as soon as possible,” she added.
“In the end, we were still three. Annemiek tried to go over me, and I was like, ‘OK, now is the time to give it my all’. At first, I thought, ‘Oh, this is maybe a bit too early, it’s still a long way’, but in the end, it was enough.”
Watch Stage 6 of La Vuelta Femenina tonight via SBS On Demand, with LIVE coverage commencing from 10pm (AEST).
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