A tank car containing a hazardous flammable chemical derailed and caught fire just south of Knoxville, Tenn., causing the evacuation of 5,000 residents within a two-mile radius of the crash.

The train was traveling to Waycross, Ga., from Cincinnati, Ohio, when a single tank car derailed and caught fire around midnight in the area of Maryville, Tenn., rail operator CSX Corp. said in a statement.

No civilians were injured by the fumes, but 10 law enforcement officers helping with the evacuation were taken to a nearby hospital to be treated for exposure to the fumes, said Marian O'Briant, spokeswoman for the Blount County Sheriff's Office. Their injuries weren't considered serious, she said. By about 8:30 a.m. EDT Thursday, the one railcar that caught fire was still burning and the people evacuated were being told they couldn't return to their homes for 24 hours to 48 hours, she said.

The tank car contained acrylonitrile, used in the manufacturing of plastics, which can be dangerous when inhaled, according to CSX. Additional tank cars containing the substance are located on either side of the derailed car, with a total of 27 out of 57 cars carrying hazardous materials on the train.

The railroad said it is working with first responders and relief agencies in Maryville, which has a population of more than 27,000. A local high school was established as an outreach center for evacuees. Federal Railroad Administration officials were on scene and will begin an investigation to determine the cause of the derailment once the site is safe, Acting Administrator Sarah Feinberg said in a statement.

The train wasn't carrying any crude oil, CSX said. The U.S. Department of Transportation recently established new rules for the carrying of hazardous flammable materials, aimed at making rail transportation safer. The new rules call for installing new braking systems on trains carrying more than 70 cars of flammable materials, as well as phased-in upgrades to tank cars.

Communities, environmental groups, the rail industry and others have all challenged the new rules.

Write to Laura Stevens at laura.stevens@wsj.com and Cameron McWhirter at cameron.mcwhirter@wsj.com

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