Mike,
As Long mentioned, the lat/lon for a satellite pixel is the center of the pixel.
You
could do a crude estimation of the pixel boundaries using half the
distance between the neighboring pixels. Or you could use the information
in
this post on computing pixel area to estimate pixel boundaries
...I'll leave the exercize to the reader

I would not recommend doing validation at the individual satellite pixel level,
although the results
should be OK if you do the variability test for the
surrounding pixels. You might get more mileage using a 3x3 pixel box - or,
since you're going to calculate the pixel boundaries, you can do the validation
on a 3x3 km average (or 5x5, 7x7, etc.) Using more satellite data values for each
matchup will allow you to estimate (if crudely) the satellite uncertainty - which
would go nicely with the in situ uncertainty you'll get with the multiple in situ
record averages.
Regards,
Sean