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Five men were killed when one besieged district was hit by mortar fire as Sunday's evacuation operation got under way.
Aid teams evacuated hundreds of exhausted civilians from besieged districts of the city of Homs on Sunday, as Syria's regime and rebels again accused each other of violating a truce.
The evacuation of some of 3,000 trapped people who had little more than olives and herbs to eat for more than 600 days came ahead of a new round of peace talks.
The Damascus delegation and members of the opposition began arriving in Switzerland for a new round of the so-called Geneva II peace talks scheduled to begin on Monday.
Sunday's evacuation from Homs was the second in three days after a UN-brokered truce for besieged districts of Syria's third city began on Friday.
Five men were killed when one besieged district was hit by mortar fire as Sunday's evacuation operation got under way, the Syrian Observatory for Human Rights said.
They were the latest deaths in a nearly three-year conflict that has killed 136,000 people and displaced millions.
"Four hundred and twenty besieged people came out today from the Old City districts of Homs, and the operation is still under way," Homs governor Talal al-Barazi said.
Television footage showed women, children and elderly men getting off the buses that brought them out of the besieged areas.
They appeared visibly exhausted and frail, in video broadcast by Beirut-based channel Al-Mayadeen. Children, carried by their parents, looked pale.
The civilians were aided by UN staff wearing helmets and blue vests, and by Syrian Red Crescent volunteers. There was also a strong Syrian army presence at the evacuation site.
"We had nothing. All the children were sick, we even had nothing to drink," said one exhausted woman, her three children standing round her.
State television said the operation took place under fire from "armed terrorist groups", using regime terminology for the rebels.
But the Britain-based Observatory echoed claims by activists in the besieged areas that at least five people were killed in shelling that targeted the besieged district of Qarabis.
Activists accused pro-regime militiamen positioned in neighborhoods bordering the besieged districts, who opposed the truce, of firing the mortar rounds.
Shelling also targeted an aid convoy entering the besieged districts on Saturday in an attack that killed five residents and wounded 20, the Observatory said.
Sunday's evacuation was the second after 83 people were brought out on Friday's first day of the truce.
In other areas of strife-torn Syria, another 300 people were killed on Saturday, according to the Observatory.
Regime, opposition in Geneva
Homs, much of which has been reduced to rubble, was dubbed "the capital of the revolution" by activists before a bloody 2012 offensive by regime forces recaptured much of the city.
The 600-day siege was a key point of discussion during a first round of peace talks in Switzerland last month, but which yielded few concrete results.
On Sunday, the regime delegation and members of the opposition National Coalition arrived for the second round of Geneva II, sources close to the delegations told AFP.
The government delegation is headed by Foreign Minister Walid Muallem, as was the case for the first round of talks 10 days ago.
Of the opposition delegates, one source said: "Some of them have arrived, each one arriving separately. Each member is travelling in from a different country."
It was not yet clear if Coalition chief Ahmad Jarba was among them.
Muallem is set to meet UN-Arab League envoy Lakhdar Brahimi at 7:00 pm in Geneva, a source close to his delegation told AFP.
But the two warring sides appear far from being able to reach any compromise.
While the regime insists that the talks focus on fighting "terrorism," the opposition is demanding that the priority in Geneva be agreement on a transition that excludes President Bashar al-Assad.
Meanwhile, the extreme violence in Syria raged on.
Saturday's death toll of around 300 included some 20 men executed by loyalists in the central province of Hama, the Observatory said.
In the besieged Palestinian camp of Yarmuk, south of Damascus, a man and a woman died of malnutrition, it said.
Since the army began blockading Yarmuk in June last year, some 80 people have died as a result of food and medical shortages, the Observatory says.
Agence France-Presse contributed to this report.