It's shocking when little ones get plaque when all the usual causes aren't there, isn't it?? I was horrified when my breast fed, tooth brushing, no (or little) sugar, milk or juice 15 month old started getting weird looking teeth. I ignored it and it got worse and now she has some serious decay on her 4 front teeth and 2 of her molars. We did take her to the dentist and my dentist said a lot of it is genetic and that sometimes the enamel is just not very strong or present so it can cause problems. We're treating it with MI Paste, lots of brushing, CLO, xylitol and cell salts.
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When I first asked my dentist about plaque she said if you can scrape it off then it's just plaque and not to worry about it. Have you tried scraping it off with your fingernails?
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There is a lot of great info in the dental forum on here for healing cavities and avoiding them naturally.
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eta: my dentist just looked at the teeth and was amazing about it...she didn't suggest any work at all at this point because DD is so young.