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From here

珍道中 読み方：ちんどうちゅう

めずらしい旅。旅の途中で珍奇な出来事にまま遭遇するような旅のこと。

What does まま modify here, what clause(word?) is it part of?

user12127
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    多分これです。普通は「ままある」の形でしか使わないんですが。 https://kotobank.jp/word/%E9%96%93%E9%96%93-635665#E5.A4.A7.E8.BE.9E.E6.9E.97.20.E7.AC.AC.E4.B8.89.E7.89.88 – marasai Jan 17 '16 at 18:37

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As pointed out by @marasai in the comment, 「まま」, in this context, is an adverb meaning "once in a while". One could say it is synonymous to 「ときどき」、「[時]{とき}として」, etc.

Since it is an adverb, it modifies the following verb 「[遭遇]{そうぐう}する」(= to encounter).

This 「まま」 and the particle 「まま」(as in 「[立]{た}ったまま[食]{た}べる」) are two different words and they are pronounced differently.

Adverb: 「まま{HL}」

Particle: 「まま{LH}」

Not to sound irrelevant: 「ママ{HL}」

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    +1, but I personally say like [まま]{LH} even when it's an adverb. (it's a rare adverb and I may be wrong) – naruto Jan 18 '16 at 03:26