They use ML, I believe. It used to be sold separately, but that was a long time ago. They still offer an older version under a MSDN membership higher than 'professional', but it's not what they currently use. If you download Visual Studio 2010 or 2012, you should be able to find ML.EXE underneath their VC/bin directory in the install directory (usually c:\program files (x86)\Microsoft visual Studio xx.0.)
For example, I get this when I run the one under 11.0:
C:\Program Files (x86)\Microsoft Visual Studio 11.0\VC\bin>ml
Microsoft (R) Macro Assembler Version 11.00.60315.1
Copyright (C) Microsoft Corporation. All rights reserved.
usage: ML [ options ] filelist [ /link linkoptions]
Run "ML /help" or "ML /?" for more info
C:\Program Files (x86)\Microsoft Visual Studio 11.0\VC\bin>
ML supports protected modes, 32 and 64 bit modes, and flat models as well as the usual segmented models. It also supports (or did) specialized AMD instructions. It's been awhile since I used to write x86 operating system code, though. So I don't know if Microsoft keeps a special copy of their assembler privately and doesn't release it at all, anymore.
It's not used as much as you may think, though. A lot of the development occurs in other languages.
One of the bigger problems you have ahead of you, if you are looking to do operating system coding for the PC workstation, is to fully apprehend the entire Intel architecture. It's very complicated and includes the ability to update the CPU microstore (a secure process is involved there.) There is the various power modes (which the CPU powers up into, but the BIOS will isolate you from if you don't know how to defeat it), as well as protected mode. There is no real mode anymore, though the CPU emulates one using specialized protected mode settings. There's a lot to learn about setting up DRAM (sizing it and configuring the chipset to operate it), the many buses, inbound and outbound queues, read-around-writes, the MTRRs, and so on. It is a massive study. I did chipset testing for Intel and I can assure you there is a lot to study. Some of it not published by Intel, by the way. Oh, and pay some attention to the BIOS, as well. Did you know you can boot code into ram and execute it through the keyboard interface?
Enjoy.