Four other ships carrying grain and sunflower oil left Ukrainian ports via a safe sea corridor. The ships are bound for Turkey where they will be inspected under an agreement with Russia and the United Nations.
The Joint Coordination Centre, the body set up under the Black Sea Grain Initiative to monitor its implementation, has authorized departures through the maritime humanitarian corridor.
Ships leaving Ukrainian ports are heading for China, Italy and two destinations in Turkey.
A fifth ship has been allowed to sail to Ukraine to pick up goods.
They left the ports of Odessa and Chornomorsk on Sunday, and will all cross the Bosphorus Strait.
Millions of tonnes of grain have remained stuck in Ukraine due to Russian blockades, leading to shortages and rising food prices in other countries: last week the first ship left Ukrainian ports since February.
Under a deal brokered by Turkey and the UN last month, Russia agreed not to target ships in transit, while Ukraine said it would guide vessels through mined waters.
The agreement, intended to last 120 days, can be renewed if both parties agree. If the deal holds, Ukraine expects to export up to three million tonnes of grain per month. President Zelensky welcomed the resumption of exports, but said security concerns remained.
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