The 64-year-old driver, identified as Robert Martinez, was struck in the eastbound Gowanus Expressway during the morning rush hour.
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He was traveling in the HOV lane when the large spare tire came loose from a private sanitation vehicle that was traveling in the opposite lanes of traffic.
The tire struck and shattered the windshield of the Chevrolet Tracker, which then crashed into the divider.
Martinez sustained severe head trauma and was pronounced dead at the hospital.
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The 45-year-old operator of the private sanitation truck remained at the scene. No charges were initially filed.
The victim was a civilian employee of the NYPD, who worked in building maintenance at police headquarters.
Century Waste Services issued the following statement:
"Our hearts go out to the family of the victim. This event was an unfortunate accident. We are fully cooperating with the investigation of this tragic event."