It is possible to trigger an out of boundary access with specially
crafted files. If a line consist of only a key and spaces, then
op will point to '\0'-ending of the buffer. Since p is iterated by
one byte right past this ending '\0', the next read access to p is
effectively out of bounds.
Theoretically this can also lead to out of boundary writes if spaces
are encountered.
Proof of concept (I recommend to compile with address sanitizer):
$ echo -n a > poc.pc
$ dd if=/dev/zero bs=1 count=65533 | tr '\0' ' ' >> poc.pc
$ pkgconf poc.pc
92745ad9cb