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When the early settlers arrived in this country, they had little time for school. They is correct pronoun used in the sentence given .
Noun and Pronoun :
By definition, a noun is termed as a name of a person, animal, place or things. Example of nouns included Peter, Paul, Sophia, and Cat, Table, New York, or Texas, e.t.c
Now,a Pronoun could be a subcategory of nouns and it is commonly a word that can restore a noun to avoid repetition. considering example , instead of calling someone by his name like Peter, you'll say;
Peter wants to return but "he" said he's is tired. So we conclude that the word he has put back Peter to avoid repetition.
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