LONDON—A heat wave swept the U.K. on Monday, with the country set to have its hottest day on record this week—an unprecedented 104 degrees Fahrenheit—causing the government to declare a national emergency.

Across the country, schools, sports facilities and summer camps shut down, train companies canceled services and health authorities prepared for a surge in calls. The national meteorological service triggered its first-ever “red extreme heat warning” across England.

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