The victims were Regina Michelle Crowder, 48, of Fountain Valley, Jon Michael Schwarz, 50, of Tustin, David Mark Terman, 59, of Santa Ana and Edith Mae, 62, of Elko, Nevada.
The crash was reported around 4:30 p.m. on E. Santiago Canyon Road at Hicks Haul Road in Silverado, officials said.
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Investigators said the two motorcycles were heading in opposite directions when the one heading northbound tried to pass a Scion TC and slammed into the other motorcycle heading southbound.
Two men motorcyclists and their two female passengers died at the scene. All of the motorcycle riders were wearing helmets.
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Officials said that section of Santiago Canyon Road has a double yellow line, meaning it is illegal to pass traffic. It is hard to see oncoming traffic in the area because of curves in the road, they said.
The driver of the Scion that the motorcyclist tried to pass was not directly involved in the collision, but remained at the scene, officials said.
The canyon is a popular route for motorcyclists, especially in the summer, and signs warn motorists to watch out for bikes on the road. The California Highway Patrol said it often gets calls for excessive motorcycle noise and speeding in the area.