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Thain is a variant spelling of Thane or Thegn, an Anglo-Saxon term for a minor noble, probably best known from Shakespeare's Macbeth. (Thane is the usual spelling in modern English.) The Oxford English Dictionary explains why the modern spelling has diverged from what would have been expected had the word continued in common use:

The regular modern repr. of OE. {th}e6n, if the word had lived on in spoken use, would have been thain (cf. fain, main, rain), as it actually appears in some writers, chiefly northern, from 1300 to near 1600. But thain was in 15-16th c. Sc. [Scottish] written thane (in L. thanus), and this form, being used by Boece, Holinshed, and Shakespeare (in Macbeth), was adopted by Selden, Spelman, and the legal antiquaries and historians of the 17th c. to represent the Anglo-Saxon {th}e6n, and became the usual form in Eng. history. Recent historians, as Stubbs, Freeman, and Green, in order to distinguish the Anglo-Saxon use from the Sc. in sense 4, have revived the OE. en as THEGN, q.v.

In J. R. R. Tolkien's fictional universe of Middle-earth, the Thain was the traditional military leader of the Hobbits of the Shire. The Hobbits first chose a Thain to "hold the authority of the king" when Arvedui, last King of Arnor, was lost and the kingship in the North discontinued. The Thainship was originally held by the Oldbuck Clan. In 1740 SR, it passed to the Tooks, and has remained a hereditary position in their clan ever since. Though a viceregal position, the Thain never wielded significant political authority, as the Shire remained a very loosely organized society and rarely faced military threats from outside.

Other offices in the Shire include the Master of Buckland, the mayor of Michel Delving in the White Downs, and (in the Fourth Age) the Warden of Westmarch created by King Elessar.

• Bucca of the Marish (first Thain, elected in T.A. 1979 after Arvedui of Arnor died)
• Eleven additional Thains of the Oldbuck clan (the clan was probably named for Bucca)
• Gorhendad Oldbuck (possibly the 12th Thain), crossed over the Brandywine and became the first Master of Buckland
• Isumbras Took I (became 13th Thain and first of the Took line in 2340)
• Eight Took Thains (including Isengrim I, Isumbras II, Ferumbras I, and Paladin I)
• Isengrim Took II (22nd Thain and 10th of the Took line. Died 2672)
• Isumbras Took III (23rd Thain in 2672)
• Ferumbras Took II (24th Thain); older brother of Bullroarer Took.
• Fortinbras Took I (25th Thain)
• Gerontius Took, the Old Took (26th Thain in 2848)
• Isengrim Took III (27th Thain)
• Isumbras Took IV (28th Thain)
• Fortinbras Took II (29th Thain)
• Ferumbras III Took (30th Thain, died childless in 3015)
• Paladin II Took (31st Thain in 3015); cousin of Ferumbras III

• Peregrin "Pippin" Took I (became 32nd Thain in 13 F.A., abdicated 63)
• Faramir Took I (became 33rd Thain after his father left for Gondor in 63 F.A.)

The line of Thains continued in the Fourth Age of Arda until the end of the Shire.