City public information officer Shannon Haigh says the officer was arriving at the fire before midnight Tuesday when something exploded and he suffered a minor hand cut.
Three people from the Cascade West apartments were treated for smoke inhalation at Skagit Valley Hospital.
Haigh says a man was found about two hours later and was flown to Harborview Medical Center in Seattle with burns to his airway and other parts of the body.
The three-alarm fire caused heavy damage to the top two floors of the three-story building.
About 200 residents have been displaced, and about 75 of them are being sheltered at nearby Skagit Valley College with help from the Red Cross.
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