<cfscript>
if (ArrayLen(StructFindValue(SESSION.Auth.AccessA[ApplicationArea], '3', 'ALL'))) {
// it exists
} else {
// it does not
}
</cfscript>
EDIT: non-cfscript as requested
<cfif ArrayLen(StructFindValue(SESSION.Auth.AccessA[ApplicationArea], '3', 'ALL'))>
<!--- it exists --->
<cfelse>
<!--- it does not --->
</cfif>
StructFindValue returns an array of structures containing information about the keys that match the value.
https://wikidocs.adobe.com/wiki/display/coldfusionen/StructFindValue
You don't need any of the #
chars in your question (I know you asked about when and when not to use them recently)