Documentation
It says here:
This mapping is captured the first time the os module is imported, typically during Python startup as part of processing site.py. Changes to the environment made after this time are not reflected in os.environ, except for changes made by modifying os.environ directly.
It should mention the caveat that such cashing would cause undefined behavior or/and crashes when other threads would be setting environment values. This would be true at least on Linux and FreeBSD.
The same should be mentioned in the documentation of the function that initializes the Python interpreter and caches environment.
These functions are not thread-safe.