In particular, the sense of “natural” having to do with something’s unaltered/innate condition – as compared to some result of human interference – dates back at least to Plato [well, there the word was the Greek phusis, whereas natura is the Latin word used to translate it, but you get the idea]. Or if you want examples in English, at least to Chaucer.
Note, if you want a much fuller idea of what “nature”/“natural” means and meant in the past, I highly recommend the CS Lewis book Studies in Words which devotes a 50 page chapter to comprehensively exploring the subject.