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(covers information from several alternate timelines)
In 2154, while trapped aboard the Romulan drone ship and with their EV suits running out of oxygen, Trip Tucker and Malcolm Reed hastened to find the ship's life support systems. Having already been temporarily abandoned by the Enterprise and having endured a bumpy ride, Reed quipped that with their luck, whatever aliens operated the drone ship probably breathed fluorine. (ENT: "Babel One")
When the USS Defiant suffered a hull breach after descending into the atmosphere of a class J planet in 2372, Lieutenant Commander Dax was nearly overcome after taking several lungfuls of fluorine after the turbolift shaft became flooded with the gas. (DS9: "Starship Down")
In an alternate timeline where the Borg assimilated Earth after stopping Zefram Cochrane's warp flight, the planet had an atmosphere of methane, carbon monoxide, and fluorine in 2373. (Star Trek: First Contact)
In 2375, when the Delta Flyer got caught in an ion storm and crash landed under several kilotons of rock on a unnamed class M planet, the atmosphere surrounding the Flyer was flooded with fluorine gas. (VOY: "Once Upon a Time")