The short answer is 'not really' but that's not the whole story here. You need to understand how sessions work.
When you call [man]session_start[/man] and stores some variables in $SESSION, by default PHP will [man]serialize[/man] and those $SESSION values and write them to a file in the TMP folder.
Generally speaking the name of the TMP file that is created is somehow derived from the session ID that PHP generates to track the session. This session ID must be repeatedly handed back to your server by the visitor's browser so that PHP knows which $_SESSION vars belong to that client. In order for the browser to do this, it must either store the session ID in a cookie or, if cookies are off, PHP may be able to keep adding the session ID to the end of each URL that it feeds to the visitor.
There's nothing you can do to stop some visitor from handing your some different session ID than the one you gave them. When malicious programmers find somebody else's session ID and use it, this is called session hijacking. You might want to google it.
Anyways, it's not impossible for someone to mess around with the session concept. The only ways that they could set some value in $_SESSION are:
1) to get some script to run on the server that would do it. i have no idea if your scripts have some security holes or whatever that might make this possible.
2)write that TMP file by some other means -- i don't know how difficult this might be but it would also require some other kind of security hole somewhere.
3) hijack somebody else' session id. If someone has cookies turned off and PHP has enable_trans_sid set to TRUE then PHP may append a session id to the end of a URL and that clueless user might copy-and-paste a url into a forum posting or something where a malicious hacker might say AHA LOOK A SESSION ID. If the session had not expired, someone might 'log in' simply by copying a URL that contains a session id.
Anyways, it's a pretty involved discussion but you should feel safe using sessions as long as you follow good practices. Don't store sensitive information in cookies, for instance.