My understanding is that atmospheric Co2 will cause an open bottle of the 10 solution to degrade fairly quickly. I read somewhere that once you open the bottle, it will degrade to a ph of 9.6 within two days, and continue downward from there. As PH is a log, even a .4 difference is signficant when calibrating.
The solution should be buffered enough to maintain shelf life, I never tested the test solution, I just assumed. I do check my meter reading with a salifer test kit every now and then and always find the freshly calibrated probes are pretty on, but then again a .2 difference is hard to see in those color charts.
Might I suggest a little experiment. As you indicated that you are in need of some new PH calibration fluid, but still have some of the old stuff left, why not calibrate with the new fluid (when you get it) then test the PH of the old fluid. This should give us an idea, about whether there is any real change in the PH over time. The only problem that I see, is that the old fluid has expired.