Amihai Mazar makes reference to a pick from the 11th century B.C. "made of real steel."
Amihai Mazar, Archaeology of the Land of the Bible, 10,000-586 B.C.E. (New Haven: Yale University Press, 1990), 361
A pick found in the eleventh century B.C.E. fortress at Har Adir in the Upper Galilee is the earliest known iron implement made of real steel produced by carbonizing, quenching, and tempering. This technological revolution opened the way for the widespread use of iron.