Apple's position is that the system libraries are the API and stable ABI, syscalls are not. They discourage their direct use, as they can change from release to release of the OS.
So, the best documentation you'll see is the man pages in section 2 or, in some cases, the headers in /usr/include. Of course, you can also look at the XNU sources for the implementations of the syscalls to see how they work.
Note that many of the system calls in syscalls.master are for internal use only and have no documentation. Also, syscalls.master contains only the Unix syscalls, not, for example, the Mach syscalls.
man 2 functionname
where functionname is the system call function.You can also look up the functions here: freebsd.org/cgi/man.cgi – Gilcrest