Resurgent Spaniard Alberto Contador (Tinkoff-Saxo) replaced Movistar's Quintana at the top of the overall standings after out-performing his main rivals in a highly technical race against the clock from the Monastery of Santa Maria de Veruela to Borja.
Britain's Chris Froome (Team Sky) struggled on the narrow, undulating and often coarse roads of the northern province of Aragon, the 2013 Tour de France winner setting only the tenth best time to stay in fifth place overall, 1:18 down on Contador.
Omega Pharma-Quick Step's Martin - the triple world time trial champion - completed the demanding course in a time of 47:02 to beat Switzerland's Fabian Cancellara (Trek Factory Racing) by 11 seconds and Colombian team-mate Rigoberto Uran by 15 seconds.
Contador came home 39 seconds down on Martin to confirm that he is back to his best following a broken leg sustained in July's Tour de France.
But the image of the day will be that of Quintana being thrown over his handlebars on a tight bend before landing in a heap as his bike smashed to pieces against the guardrail.
Quintana - wearing a full red skin suit as the race leader - had set the fifth-best time at the first intermediate check, trailing pace-setter Contador by just 20 seconds after the summit of the Cat.3 Alto de Moncayo after 11.2km.
What happened next turned the race - and Quintana - on its head. Adjusting his boot straps at the start of the descent, the 24-year-old overshot the right-hand bend before struggling to readjust his line. Having run into the gravel on the side of the road, Quintana's bike clipped the barrier and sent the race leader flying.
Quintana acrobatically flipped over and met the tarmac with an expert tuck and roll onto his back. But the Giro d'Italia champion was clearly dazed by the incident, lying motionless on the road for over a minute before remounting on a new bike (the frame of his original steed had smashed to smithereens sending a wheel over the barrier and a saddle spinning across the road).
His skin suit torn to shreds but his shaken body displaying no visible cuts or bruises, Quintana completed the fast downhill and flat section of the course rather gingerly, crossing the finish line 4:07 down on Martin. He dropped to 11th place on GC, 3:25 down on Contador.
Besides the new race leader and the stage victor Martin, the big winner of the day was Uran who rose to third place on GC, 59 seconds behind Contador. Uran held the joint-best time with Martin at the second intermediate check after 30km before fading slightly in the closing moments to secure his third place on the stage.
Even before the race favourites had rolled down the start ramp, Swiss specialist Cancellara had issued a warning about the state of the roads, which he succinctly described as "bad, bad".
"There's not just hill, downhill, false flat and straight roads. The asphalt was really bad. It has nothing to do with a time trial in my opinion," Cancellara said.
"Can you imagine for Alberto [Contador], [Chris] Froome, Purito [Rodriguez], Alejandro [Valverde] and [Nairo] Quintana? It will be even worse for them on those roads after the climb. This is how it is but I hope they look for better roads than this [in the future]."
Alberto Contador (Tinkoff-Saxo) sur le chrono de la Vuelta 2014
Viewing the riders grapple with the cobbled roads leading out of the monastery before a series of concrete slabs, it was easy to appreciate Cancellara's concerns. The subsequent series of climb were played out on a patchwork quilt of coarse, uneven asphalt - the steepest gradient of which Froome clearly underestimated.
The Sky rider looked to have got his gear ratios all wrong as he was forced out of the saddle of his time trial bike on the Cat.3 ascent - something many riders avoided by opting for road bikes ahead of a bike swap at the summit.
Froome was outside the top ten at the second check after looking cagey and concerned on the descent, before coming home 1:32 down on Martin for tenth place - more than 30 seconds slower than his Sky team-mate Vasil Kiryienka.
BMC pair Samuel Sanchez and Cadel Evans finished fourth and fifth ahead of the Belorussian, while Quintana's Movistar team-mate Alejandro Valverde settled for eighth place at 1:01.
Valverde stays in second place on GC but now trails Contador by 27 seconds. Colombia's Winner Anacona (Lampre-Merida) put in a surprisingly solid effort to retain his fourth place in the standings, 1:12 off the summit. Rodriguez, too, preserved his sixth place and is now 1:37 behind the Spanish race leader.
Besides Quintana, the only other rider to drop out of the top ten was French youngster Warren Barguil of Giant-Shimano, who is now 15th. Italy's Fabio Aru (Astana) and Dutchman Robert Gesink (Belkin) dropped one place each to eighth and ninth, now sandwiched by seventh-place Sanchez tenth-place Italian Damiano Caruso (Cannondale).
RIDE OF THE DAY: The world of cycling is running out of superlatives for Tony Martin when it comes to describing his efforts against the clock. Put simply, Martin's ITT victories are often so much of a given that they overlooked or seen as a mere subplot to the battle for GC taking place later in the day.
DAY TO FORGET: While Chris Froome's performance confirms that the British rider has not recovered from his Tour injuries to the extent that Contador has, even the Team Sky rider will count his lucky stars he was not victim to the kind of crash that derailed Nairo Quintana. One upshot for the viewers is that Quintana will now - injuries permitting - be forced to go on the offensive in the mountains, provided that he is not reduced to a support role alongside team-mate Valverde.
COMING UP: An instant shot at redemption for Quintana with a short but sharp 153.4km stage 11 from Pamplona that concludes with with a Cat.1 ascent of the Alto de San Miguel. It's a 10km climb with an average gradient of 10% and steeper ramps towards the top - ideal terrain for the Colombian to reduce the deficit a little.
- Sports & Recreation
- Alberto Contador
- Chris Froome
- Fabian Cancellara
- Rigoberto Uran
- Tony Martin