I believe, although I can't say that I've given a rigorous proof, that for a free group $F_r$, and an element of it $a$, $C_{F_r}(\langle a \rangle)=$ the group generated by the elements $b \in F_r$ such that $a=b^n$ for some integer $n$ (I will say: the group of powers and roots of $a$).
One may similarly ask (and this is my interest in this), given $ a\in \hat{F_r}$ (the free profinite group on $r$ generators), what is $C_{\hat{F} _r}(\langle a \rangle)$? In particular, is it the profinite completion of the group of powers and roots of $a$?