StingingVelvet: You really do have to wonder how many Steam users are actually buying and playing "real" games on it on a regular basis. I know a lot of people in real life who have a Steam account because of some sale on some game a blog linked to and they bought it even though they play on consoles 99.9% of the time. I am sure there are others only playing popcap stuff, only chatting or only using it for Steamworks games.
Anyway... it's interesting, and Valve will never tell.
I did notice the other day that when the Betrayal of Jimmy DLC for Mafia 2 came out it was the top seller all day and then when I played it late that night the leaderboards had 8,000 or so people on them total. So, 8,000 was an easy top seller that day, take that for what you will.
You cannot tell exactly but looking at their stats page, one sees that the number of concurrent steam users oscillates between 1.4 and 2.7 millions but when adding up the number for top games by current player count (top 100) you obtain less than 400k (current) up to 700k (peak today). I made this just now and used blocks of 10 and took always the maximum in each group to get an upper bound while speeding up calculation. What does it mean: approx. 70% of concurrent steam users are not playing a game. Thats my interpretation.
http://store.steampowered.com/stats/
For the estimated 3.500 Win 2000 users, the number of users wanting to play a game at some point and not having another computer with another OS available... thats really something nobody knows.
Mafia II users (peak today) were at most 20k simultaneously, now its down to 13k, and probably declining. If you would now know how long people play the game on average you could maybe infer estimates of sales numbers.
At least one can say that CS and CS:Source are still the most popular games on Steam.