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The top uniformed officer of the New York City Fire Department was relieved of his duties on Thursday amid accusations of “inappropriate behavior” toward subordinates and co-workers, including the most senior woman at the agency.

Chief James E. Leonard, a 39-year veteran of the department, was accused of bullying and screaming at several people at the agency, and attempting to freeze out the highest-ranking nonuniformed woman at the department, Laura Kavanagh.

Ms. Kavanagh, who had worked on Bill de Blasio’s mayoral campaign and then served as a special assistant to the mayor, moved to the Fire Department to become its head of external affairs and was promoted to first deputy commissioner in January. She is the second woman to hold that job.

Chief Leonard will be placed on modified duty while the city Law Department investigates his conduct around both men and women.