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Yes, you can certainly do that. Breast milk has amazing anti-bacterial properties. . .it can be left out without growing bacteria, I did use it to treat pink eye (and yes, it worked better than the meds), and I probably would've tried it in an ear if the infection showed up over the weekend.
HOWEVER, in my own kids, ear infections were accompanied by high fever, and a slew of other symptoms. On top of that, one of my children was actually speech delayed because he had a series of bad ear infections that we didn't catch in time.
With pink eye, it was immediately apparent after 12 hours of treatment whether or not it was working (and it did always work). I would be inclined to try the breastmilk in the ear if my pedi's office was closed but if I had an option to take her to a doctor, that's what I'd do.
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