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Volodymyr Zelenskyy has said 500 tonnes of wheat flour are on their way to Syria.
Ukraine had vowed to supply Syria with grain after the fall of dictator Bashar al Assad and said it was in active talks with the Middle Eastern country's administration.
Russia - the world's largest wheat exporter and chief Assad regime backer - had dominated sales to Syria, but supplies were suspended after two vessels carrying Russian wheat failed to reach the country.
In their place, Ukraine said it is sending stocks through its Grain From Ukraine scheme with the help of the World Food Programme.
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