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The Italian Cannondale rider broke away with four other riders after just 3km of a day marred by abysmal weather and later forged clear on his own for the biggest win of his career.
Race leader Vincenzo Nibali (Astana) and Chris Horner (RadioShack-Leopard) crossed the line in Andorra almost four minutes later in second and third respectively after dropping all of their rivals for overall victory on the climb to the summit finish on the category-one Collada de la Gallina.
Joaquim Rodriguez (Katusha) limited his losses to the pair to 16 seconds, but Alejandro Valverde (Movistar) shipped almost a minute after dropping behind earlier in the stage as he struggled in the treacherous conditions.
Nicolas Roche (Saxo-Tinkoff) fared even worse, losing more than seven minutes and, in the process, falling out of contention in the general classification after suffering badly from a combination of the cold and the difficult final climb.
The weather was so bad that Ivan Basso (Cannondale), who had been seventh in the general classification, and breakaway rider Luis Leon Sanchez (Belkin) were both forced to abandon the race through hypothermia, while Vacansoleil-DCM duo Lieuwe Westra and Wout Poels also failed finish.
The stage had promised to be one of the marquee days of the race, with an ascent of the especial-category Port de Envalira - the race's highest point at 2,410m - being followed by the Gallina, which was first of three consecutive Pyrenean summit finishes.
A high-pedigree, five-man breakaway containing Ratto, Sanchez and world champion Philippe Gilbert (BMC) moved clear just after the starting flag and built up a sizeable lead, but their numbers were reduced to three when two men fell away on the lower slopes of the 26.7km climb of the huge Envalira.
Ratto, Sanchez and Gilbert ploughed on as a trio and stretched their lead to over 12 and a half minutes as they crested the summit, but then Ratto moved into sole lead by descending down the other side at a breakneck speed, despite the rain-soaked road surface.
Sanchez took fewer risks but still could not avoid crashing in the treacherous conditions and later abandoned the race as his health became a genuine concern.
Result of stage 14:
1. Daniele Ratto (Italy / Cannondale) 4:24:00"
2. Vincenzo Nibali (Italy / Astana) +3:53"
3. Chris Horner (U.S. / RadioShack) +3:55"
4. Joaquim Rodriguez (Spain / Katusha) +4:11"
5. Samuel Sanchez (Spain / Euskaltel) +4:19"
6. Alejandro Valverde (Spain / Movistar) +4:43"
7. Thibaut Pinot (France / FDJ.fr) +4:46"
Overall standing after 14 stages:
1. Vincenzo Nibali (Italy / Astana) 53:56:49"
2. Chris Horner (U.S. / RadioShack) +50"
3. Alejandro Valverde (Spain / Movistar) +1:42"
4. Joaquim Rodriguez (Spain / Katusha) +2:57"
5. Domenico Pozzovivo (Italy / AG2R) +3:43"
6. Nicolas Roche (Ireland / Saxo-Tinkoff) +4:06"
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