The Ontario Provincial Police said David James Leblanc was arrested Sunday evening on a road in Greenstone, about 250 kilometres northeast of Thunder Bay, Ont., after a nearly weeklong search.
Staff Sgt. Carl Pettigrew said officers received a report at around 6 p.m. of a suspicious man in distress on Lukinto Lake Road.
Pettigrew said someone saw a man wandering along the road with no shoes and in light clothing as temperatures hovered around the freezing mark.
"He appeared to be having the effects of being in the elements, not dressed for the conditions, suffering somewhat from exposure," Pettigrew said.
A spokesman for Ontario's attorney general said Leblanc appeared in court in Thunder Bay via video from the Greenstone detachment. Brendan Crawley said Leblanc was remanded into custody for six days and would be returned to Nova Scotia.
Nova Scotia RCMP Sgt. Alain LeBlanc said the Mounties hope to have Leblanc back in the province this week.
Police are also looking for 31-year-old Wayne Alan Cunningham, who they said could be headed to Calgary in a grey 2003 Hyundai Elantra with Nova Scotia license plate FBP 233.
Both men face charges of forcible confinement and sexual assault.
The RCMP in Nova Scotia began an investigation last week after a woman reported that a teenager arrived at her doorstep in the Lunenburg County community of Upper Chelsea, about 130 kilometres southwest of Halifax. The woman said the boy was in his bare feet and chained at his wrists and ankles.
In documents filed last week with the provincial court in Bridgewater, N.S., RCMP Const. Timothy Cole said a 16-year-old boy told them he was sleeping on the streets of Halifax last month when he woke up in a van and was taken to a home.
Cole said two men held the boy against his will, sexually assaulted him over several days and talked about trying to sell him.
The RCMP said the boy was taken to hospital with non-life threatening injuries.
Upper Chelsea resident Edwina Faulkner, 77, said she was shaken once she heard about the case.
"At first, it shocked me. And then it made me scared, because it is next door," said Faulkner, a widower who lives with her grandson and his wife.
"It's very unsettling. You don't expect that in a small country community."
The case has also raised the concerns of Nova Scotia's opposition parties. The Liberals and Progressive Conservatives said last week that more restrictive conditions should have been imposed on Leblanc when he was released in 2010 pending a hearing on unrelated charges of sexual assault and possessing child pornography.
Leblanc is due in court in Halifax in November to answer to charges related to possessing digital images of child pornography, sexual assault and touching a person under the age of 16.
At the time, Leblanc was released on conditions that he keep the peace and stay away from places where children may congregate, like schools and playgrounds.
Court documents show that he was charged with failing to comply with some of those conditions in 2011 and was sentenced to 18 days in a provincial facility.