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Fighting continued in the rebel-held Eastern Ghouta area in Syria during the first daily five-hour "pause" ordered by the government's ally Russia.
Activists said there were government air and artillery strikes, while Russia said rebels shelled a "humanitarian corridor" meant to let civilians leave.
As a result, there were no UN aid deliveries or medical evacuations.
Some 393,000 people are trapped in the enclave near Damascus, which has been besieged by the government since 2013.
Medics say more than 500 people have been killed since the government and its allies intensified their bombardment nine days ago in an attempt to retake the enclave.
Meanwhile, France urged Russia to use its influence over Syrian President Bashar al-Assad to secure a 30-day truce covering the whole country.
The UN Security Council unanimously passed a resolution demanding a nationwide cessation of hostilities on Saturday, but it did not specify a start date.
"Russia is one of the only actors that can get the regime to implement the resolution," French Foreign Minister Jean-Yves Le Drian told his Russian counterpart Sergei Lavrov at a meeting in Moscow.
A spokesman for the UN Office for the Co-ordination of Humanitarian Affairs (OCHA) said it had received reports that fighting continued after the Russian-ordered pause began on Tuesday morning.
"Clearly, the situation on the ground is not such that convoys can go in or medical evacuations can go out," Jens Laerke told reporters in Geneva.
The Syrian Observatory for Human Rights (SOHR), a UK-based monitoring group, said the situation in the Eastern Ghouta had been relatively calm overnight.
But it reported that in the first two hours of the Russian-ordered "humanitarian pause", a number of shells hit the towns of Douma, Harasta and Misraba.
Later, it reported air strikes, including the dropping of two barrel bombs on the town of al-Shifuniya, and rocket fire.
The Syrian Civil Defence, whose volunteer rescue workers are widely known as the White Helmets, said one person was killed in Douma by shellfire. But the Syrian Observatory said the attack happened before the pause began.
Ambulances were seen waiting at the government-controlled al-Wafideen checkpoint
The Syrian state news agency, Sana, reported that "terrorists" had shelled the route of the humanitarian corridor leading to the government-controlled al-Wafideen Camp, which is north-east of Douma, and were using "human shields".
Russian media said not a single civilian left the besieged area as a result.
The accusation of firing mortars was denied by the rebels, while the Syrian military said it had not carried out air strikes.
The Russian defence ministry announced that government forces would "cease strikes on terrorists" from 09:00 until 14:00 local time (07:00-12:00 GMT) daily "with the aim of immediately saving the peaceful population".
One "humanitarian corridor" had been prepared, with help from the Syrian Arab Red Crescent, to allow civilians to leave and the sick and wounded to be evacuated, it said.
Residents would be informed via leaflets, text messages and videos, it added.
Buses and ambulances were waiting at the al-Wafideen checkpoint on Tuesday.
Humanitarian organisations say they need to be sure the truce is taking effect on the ground before sending in aid workers and vehicles.
Dr Mohamad Katoub, a Turkey-based doctor with the Syrian American Medical Society (SAMS), which supports hospitals in the Eastern Ghouta and other rebel-held areas, told the BBC: "We don't believe that this truce will bring any benefits for the civilians inside Eastern Ghouta. Five hours is not enough to do anything.
"This truce doesn't mean that we NGOs there will have any access to bring any items inside Eastern Ghouta.
"The only access is the UN inter-agency convoys. Their access there is very limited due to the restrictions from the Syrian government.
"Only 10 convoys entered Ghouta in 14 months and those convoys brought less than 10% of the needs."
Al-Wafideen has long been the formal point for people to enter and exit Eastern Ghouta.
But Reach Initiative, which is monitoring the humanitarian situation in the enclave, said earlier this month that less than 10% of the enclave's population - made up of public sector employees and males over 40 - were permitted to leave. Women and children reportedly continued to be forbidden by rebel groups from leaving for security reasons, it added.
The organisation said people attempting to leave the area faced sniper fire, landmines, shelling, verbal and physical harassment, detention and, in the case of women, sexual harassment, humiliating inspections and beatings.
A journalist for the pro-opposition Ghouta Media Center who lives in Douma told the BBC that it was too dangerous to venture outside, let alone try to reach al-Wafideen.
"I went outside but only for a while," Firas Abdullah said. "After half a minute of this ceasefire, shells were dropped. Even if anyone tries to leave, he will be shot by the snipers of the regime checkpoint."
No. The Security Council resolution demanded that "all parties cease hostilities without delay for at least 30 consecutive days" to allow humanitarian aid deliveries and medical evacuations of critically ill people.
UN Secretary-General Antonio Guterres said on Monday that the resolution needed to be implemented immediately, warning: "Eastern Ghouta cannot wait. It's high time to stop this hell on Earth."
But Russian Foreign Minister Sergei Lavrov told reporters that the UN-mandated truce would "start when all sides of the conflict agree on how to introduce it".
The jihadist groups Islamic State (IS) and al-Qaeda are excluded, as well as the major Islamist rebel factions Ahrar al-Sham and Jaysh al-Islam.
Mr Lavrov called them "partners of al-Nusra Front" - the name of a former al-Qaeda affiliate whose latest incarnation is an alliance of jihadists called Hayat Tahrir al-Sham (HTS). It has a small presence in the Eastern Ghouta.
