Please note that writing to $_ENV does not actually set an environment variable, i.e. the variable will not propagate to any child processes you launch (except forked script processes, in which case it's just a variable in the script's memory). To set real environment variables, you must use putenv().
Basically, setting a variable in $_ENV does not have any meaning besides setting or overriding a script-wide global variable. Thus, one should never modify $_ENV except for testing purposes (and then be careful to use putenv() too, if appropriate).
PHP will not trigger any kind of error or notice when writing to $_ENV.