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CS5 without a doubt. I used CS4 till it stopped working and reluctantly purchased PE10 as that was all I could afford. Evidently a backward step as I knew it would be, just for starters there's no Curves adjustment layers; no 16bit mode; Convert to Black and White is very limited; no Channel Mixer; no 'Soft-Proofing'; ACR is lacking and so on.
Okay you get what you pay for but I wasn't fully aware of how much I'd miss some of the things i've listed, but I was just getting used to CS4. If you've never used CS4/5 then you may not want or need some of its capabilities. If you've exhausted PE9 then I doubt it'll take long for you to do the same with PE10. For me though I'm saving frantically for an upgrade.
I did look at Lightroom's latest version but correct me if I'm wrong but it can't run on XP.
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