The first shipment of grain to leave Ukraine under a deal to ease Russia's naval blockade was expected in Istanbul "after midnight," as Kyiv said Tuesday it had begun mandatory evacuations from the war-torn Donetsk region.
The Sierra Leone-registered ship, Razoni, set sail from Odessa port for Lebanon Monday under an accord brokered by Turkey and the United Nations that it is hoped will get millions of tonnes of trapped Ukrainian produce to world markets and curb a global food crisis.
Turkish officials said it would arrive in Istanbul "after midnight".
The ship had cautiously made its way through a specially cleared corridor in the mine-infested waters of the Black Sea.
The Marine Traffic website showed the vessel -- which is carrying 26,000 tonnes of maize -- off the coast of Bulgaria by 0900 GMT.
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It will be inspected by a special coordination centre involving representatives of Ukraine, Russia, Turkey and the UN at sea in the mouth of the Bosphorus before being allowed to progress.
The five-month halt of deliveries from Ukraine -- one of the world's biggest grain exporters -- has contributed to soaring food prices, hitting the world's poorest nations especially hard.
Kyiv says at least 16 more grain ships are waiting to depart but President Volodymyr Zelensky cautioned it was too early to celebrate.
"Let's wait and see how the agreement works and whether security will be really guaranteed," Zelensky said in a video address late Monday.
The breakthrough pact signed in July was the first significant accord involving Ukraine and Russia since Moscow invaded its neighbour on February 24.
Yet Russia has continued to pound cities and towns across Ukraine's sprawling front line.
Kyiv said it had started mandatory evacuations from the eastern region of Donetsk bearing the brunt of the Russian offensive after Zelensky urged the estimated 200,000 remaining residents to leave.
Ukrainian Deputy Prime Minister Iryna Vershchuk said a train carrying "women, children, elderly people, many people with reduced mobility" arrived in the central city of Kropyvnytskyi on Tuesday morning.
Officials have said they want to get residents out of the battered region before the start of winter as gas pipes for heating have been severed.
In the south of the country, the head of Ukraine's Kryviy Rig military administration said Russian shelling had killed two civilians in a minibus trying to leave the Moscow-controlled Kherson region.
Oleksander Vilkul said two other passengers were in serious condition in hospital with burns.
The mayor of the city of Mykolaiv, the closest to where Ukrainian forces are looking to launch a counter-offensive in Kherson, said Russian strikes had damaged a university dormitory.
More Western arms
He said in a briefing that 403 people had been killed in his region since the invasion but that a looming Ukraine counter-offensive for the neighbouring Kherson region "will result in a decrease of shelling".
Ukraine was bolstered by more supplies of Western arms -- particularly long-range artillery -- as it looks launch a major push in the south to retake Kherson.
The United States announced a new tranche of weapons worth $550 million for Ukraine's forces, including ammunition for increasingly important rocket launchers and artillery guns.
"Our artillerymen are ready to turn night into day to expel the Russian invaders," Ukraine's Defence Minister Oleksiy Reznikov said.
On the diplomatic front, Washington, London and Paris used a review of a key United Nations nuclear treaty to rebuke Moscow for "irresponsible and dangerous" talk about possibly deploying nuclear weapons.
Russian President Vladimir Putin rebuffed the accusation, telling the Tenth Nuclear Proliferation Treaty Review Conference there could be "no winners" in a nuclear war and it should "never be unleashed".
The Kremlin nevertheless accused Britain, one of Kyiv's most vocal supporters, of deliberately worsening relations between Russia and the West.
It blacklisted 39 British citizens, including Labour Party leader Keir Starmer and former prime minister David Cameron, saying they "contribute to the hostile course of London, aimed at the demonisation of our country and its international isolation".