At any point if you make the raw bytes accessible to someone, even if it's just to copy them somewhere, it becomes possible to mutate an immutable value and users will eventually take advantage of it, if only because they came up with a really good reason why they need to (like for example, initializing readonly values in a deserialization function).
I don't think .NET could have ever adopted true immutability for structs because the rules would be so easy to break. There are "readonly" fields but they're at best a railing to keep you from falling off - there are trivial ways to bypass those protections.
I do think immutability can be a valuable property though so it's cool to see the Java folks doing the hard work to execute on it.