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Nahuatl has two sibilant fricatives, now pronounced something like [s] and [ʃ]. The standard orthography was developed by Spanish colonizers, who wrote /ʃ/ as x, and /s/ as c before a front vowel, z elsewhere. (There's also [t͡ʃ], written ch.)

But since all stages of Spanish definitely had s for [s], it seems clear that the sound the first transcribers heard definitely wasn't [s].

Do we know what this sound was? There unfortunately weren't trained linguists around transcribing Classical Nahuatl, but the Spanish transcription might be enough to make a good guess.

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    Please do not use monospace for IPA. Not only is it nonstandard and completely redundant as the IPA is already distinguised from the running text by the brackets and slashes, it makes some IPA symbols appear as empty boxes on some devices. – Nardog Apr 21 at 18:29
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    @Nardog I generally use codetags for IPA because it instructs screenreaders to read out the individual letters rather than guessing a language and mangling it, which is helpful for me. It's much more helpful to treat each IPA character separately. See linguistics.stackexchange.com/questions/31113/… – Draconis May 1 at 2:47
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    (While some fonts don't support Unicode, that issue isn't restricted to monospace, it can in theory happen with any font on the site—and I don't think that's a problem the site can solve. End-users not having IPA fonts doesn't seem like a reason for us to avoid IPA transcriptions.) – Draconis May 1 at 2:49
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The reason that Spanish linguists transcribed the phoneme /s/ in Nahuatl as z/c(i/e) rather than s is because at that time Spanish had two alveolar sibilant phonemes, an apical /s̺/ written s and a laminal /s̻/ written z/c(i/e), and that the dental or alveolar sibilant in the Nahuatl spoken at that time was acoustically closer to the laminal than apical /s/. Since that time, in much of the Spanish spoken in Spain, /s̻/ has developed into /θ/, leaving only one alveolar sibilant.

There is a similar reason for why post-alveolar /ʃ/ is written x in the Classical Nahuatl orthography the Spanish introduced. At the time, in Early Modern Spanish, what is now for the most part written j and pronounced /x/ was actually pronounced /ʃ/ and written x. This and /ʒ/, written g(i/e), later went on to merge with one another.

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all stages of Spanish definitely had s for [s], it seems clear that the sound the first transcribers heard definitely wasn't [s].

This seems like an oversimplification. Fricatives developed in different ways in different Spanish dialects: some had seseo (both <s> and <c/z> merged as [s]) some had ceceo (both <s> and <c/z> merged as [θ]) and some had distinction. The use of [θ] for <c/z> is thought to be a later development from some kind of sibilant distinct from the one used for <s>. The Iberian (but not Romance) language Basque still uses <z> for a voiceless sibilant with a quality distinct from <s>. IPA [s] isn't precise enough to notate the difference between the two Basque sounds: it's necessary to resort to diacritics. The IPA symbol [s] seems likely enough as a broad transcription of the Classical Nahuatl sound.

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