Step 1: Use the triangle side relation.
Since
\[
\overrightarrow{BC}=\vec{a}, \qquad \overrightarrow{CA}=\vec{b}, \qquad \overrightarrow{AB}=\vec{c}
\]
and these are the directed sides of triangle \( ABC \), we have the standard vector relation
\[
\vec{a}+\vec{b}+\vec{c}=0
\]
because
\[
\overrightarrow{AB}+\overrightarrow{BC}+\overrightarrow{CA}=0
\]
Equivalently,
\[
\vec{c}=-(\vec{a}+\vec{b})
\]
Step 2: Interpret the given lengths.
We are given
\[
BC=AC=3
\]
Now,
\[
|\vec{a}|=|\overrightarrow{BC}|=BC=3
\]
and
\[
|\vec{b}|=|\overrightarrow{CA}|=CA=AC=3
\]
Thus,
\[
|\vec{a}|=|\vec{b}|=3
\]
Step 3: Use the given dot product \( \vec{b}\cdot\vec{c}=-9 \).
From
\[
\vec{c}=-(\vec{a}+\vec{b})
\]
we get
\[
\vec{b}\cdot\vec{c}
=
\vec{b}\cdot\bigl(-(\vec{a}+\vec{b})\bigr)
\]
\[
= -(\vec{b}\cdot\vec{a}+\vec{b}\cdot\vec{b})
\]
Since dot product is commutative,
\[
\vec{b}\cdot\vec{a}=\vec{a}\cdot\vec{b}
\]
and
\[
\vec{b}\cdot\vec{b}=|\vec{b}|^2=3^2=9
\]
Hence,
\[
\vec{b}\cdot\vec{c}=-(\vec{a}\cdot\vec{b}+9)
\]
Step 4: Substitute the given value.
It is given that
\[
\vec{b}\cdot\vec{c}=-9
\]
So,
\[
-(\vec{a}\cdot\vec{b}+9)=-9
\]
Step 5: Solve for \( \vec{a}\cdot\vec{b} \).
Multiply both sides by \( -1 \):
\[
\vec{a}\cdot\vec{b}+9=9
\]
\[
\vec{a}\cdot\vec{b}=0
\]
Step 6: Interpret the result geometrically.
Since
\[
\vec{a}\cdot\vec{b}=0
\]
the vectors \( \vec{a} \) and \( \vec{b} \) are perpendicular.
That means the sides \( BC \) and \( CA \) are mutually perpendicular, so the angle at \( C \) is a right angle.
Step 7: Final conclusion.
Therefore,
\[
\boxed{\vec{a}\cdot\vec{b}=0}
\]
Hence, the correct option is
\[
\boxed{(4)\ 0}
\]