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頭 usually refers to a physical head, and here it is used in an extended, more abstract, meaning, front position. Compare with the use of the English head in a programming context: C++ header files. There's also the linguistic term head-initial. Thus, 声母とは頭に付く子音 says that a 声母 is a 子音 placed at the the beginning of a 音節. A few more examples: ...
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