Converting RAW to PNG 8 bit vs 16 bit

When I open a 16 bit raw file in PS and save that via File-> Save for Web & Devices and choose PNG-24, it becomes an 8 bit file. When I instead just go File-> Save As and choose png from the Windows standard format dropdown menu it becomes 16 bit. Why is this? 
I also wonder what's the max. bit for the PNG format.
PS CS4
W-XP SP3

Thanks for answering Andrew. I appriciate that. Yes, in this case my 8-bit PNG is 532kb and the 16-bit is 2,3mb. They share pixel size, so that's compression. It's weird that PS doesn't have more flexible PNG "save functions" cause what ended up generating the 16-bit file was my OS, if you know what I mean.
I know that JPEG doesn't support 16-bit but I'm only referring to PNG here. I also checked the PNG-8 option in the Save for Web & Devices function, but that removed the RGB color space and made it Indexed Color like a gif. I've tried to find out what the max bit value for PNG is but it's not clear to me. Does the format support 64-bit? So if I had let's say Windows 7 I could have a 64-bit PNG by saving that RAW file like I did trough File-> Save As? 

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