DD1 watches more TV than I am personally comfortable with, but she seems to learn so much from it. And is exposed to many more topics than I could strew about in any given week.  I am surprised at how many things she has learned from TV that she intertwines into our daily activities. It has really provided a great jumping off point for discussions and library book choices and whatnot.
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Shows that we have found particularly interesting:
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Curious George- great for science and math
Sid the Science Kid- ditto above
Dragonfly TV- aimed for older kids than my 4yo, but she enjoys the 'newsy, information' style
Dinosaur Train-dinos, but also things like interpersonal relationships, dealing with siblings, science, history, nature