offsetof is something to be very careful with in C++. It's a relic from C. These days we are supposed to use member pointers. That said, I believe that member pointers to data members are overdesigned and broken - I actually prefer offsetof.
Even so, offsetof is full of nasty surprises.
First, for your specific questions, I suspect the real issue is that they've adapted relative to the traditional C macro (which I thought was mandated in the C++ standard). They probably use reinterpret_cast for "it's C++!" reasons (so why the (size_t) cast?), and a char& rather than a char* to try to simplify the expression a little.
Casting to char looks redundant in this form, but probably isn't. (size_t) is not equivalent to reinterpret_cast, and if you try to cast pointers to other types into integers, you run into problems. I don't think the compiler even allows it, but to be honest, I'm suffering memory failure ATM.
The fact that char is a single byte type has some relevance in the traditional form, but that may only be why the cast is correct again. To be honest, I seem to remember casting to void*, then char*.
Incidentally, having gone to the trouble of using C++-specific stuff, they really should be using std::ptrdiff_t for the final cast.
Anyway, coming back to the nasty surprises...
VC++ and GCC probably won't use that macro. IIRC, they have a compiler intrinsic, depending on options.
The reason is to do what offsetof is intended to do, rather than what the macro does, which is reliable in C but not in C++. To understand this, consider what would happen if your struct uses multiple or virtual inheritance. In the macro, when you dereference a null pointer, you end up trying to access a virtual table pointer that isn't there at address zero, meaning that your app probably crashes.
For this reason, some compilers have an intrinsic that just uses the specified structs layout instead of trying to deduce a run-time type. But the C++ standard doesn't mandate or even suggest this - it's only there for C compatibility reasons. And you still have to be careful if you're working with class heirarchies, because as soon as you use multiple or virtual inheritance, you cannot assume that the layout of the derived class matches the layout of the base class - you have to ensure that the offset is valid for the exact run-time type, not just a particular base.
If you're working on a data structure library, maybe using single inheritance for nodes, but apps cannot see or use your nodes directly, offsetof works well. But strictly speaking, even then, there's a gotcha. If your data structure is in a template, the nodes may have fields with types from template parameters (the contained data type). If that isn't POD, technically your structs aren't POD either. And all the standard demands for offsetof is that it works for POD. In practice, it will work - your type hasn't gained a virtual table or anything just because it has a non-POD member - but you have no guarantees.
If you know the exact run-time type when you dereference using a field offset, you should be OK even with multiple and virtual inheritance, but ONLY if the compiler provides an intrinsic implementation of offsetof to derive that offset in the first place. My advice - don't do it.
Why use inheritance in a data structure library? Well, how about...
class node_base { ... };
class leaf_node : public node_base { ... };
class branch_node : public node_base { ... };
The fields in the node_base are automatically shared (with identical layout) in both the leaf and branch, avoiding a common error in C with accidentally different node layouts.
BTW - offsetof is avoidable with this kind of stuff. Even if you are using offsetof for some jobs, node_base can still have virtual methods and therefore a virtual table, so long as it isn't needed to dereference member variables. Therefore, node_base can have pure virtual getters, setters and other methods. Normally, that's exactly what you should do. Using offsetof (or member pointers) is a complication, and should only be used as an optimisation if you know you need it. If your data structure is in a disk file, for instance, you definitely don't need it - a few virtual call overheads will be insignificant compared with the disk access overheads, so any optimisation efforts should go into minimising disk accesses.
Hmmm - went off on a bit of a tangent there. Whoops.