In the examples on their website, PostSharp has a demo of intercepting calls in main system assemblies. I have tried a few times to setup and replicate said intercept calls
You can trace methods of other assemblies by specifying:
[assembly: Trace("MyCategory",
AttributeTargetAssemblies="xyz",
AttributeTargetTypes = "My.BusinessLayer.*")]
However, the external assembly will not be modified! Only calls from the current project to the external assembly can be modified.
It is currently not easy to modify assemblies you don't have the source of. This is possible, but is considered an advanced scenario and requires custom coding.