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Until the modern era, human use of toxic weapons -- biological or chemical -- was sporadic, unorganized and often inadvertent. One instance of its impromptu use, however, set off the Great Plague of the 14th century, which killed a third of the population of Europe. A Mongol army besieging the Genoan trading outpost at Caffa in the Crimea (1346-1347) suffered an outbreak of the plague, apparently of natural cause. Using the plague-infected corpses of their comrades as biological weapons, the Mongols catapulted them over the walls of Caffa.
www.news.cornell.edu/Chronicle/99/11.4.99/bio_warfare.html

This tactical strategy was a great success. The Genoans, who were soon decimated by the plague, fled Caffa by sea -- but they took the plague with them, stopping in Naples long enough to establish the plague there, and then going on to Genoa. From Caffa, Naples and Genoa, the plague spread throughout Europe.