Jawz is right about the mechanics of skimmers....the water density is higher so smaller bubbles are formed in very high numbers, and they ascend slightly slower too.
BUT....I remember reading about this subject in one of my mags....I believe what they said was the biggest problem with using it in freshwater was the contact time. DOC's (dissolved organic compounds) have both a negative and positive charge. Now, I get confused as to which is which, but one side let's say the negative is attracted to air, and the positive side is attracted to water. This is why you get a scum on the surface of the water. In order for the skimmer to work in freshwater you have to give the DOC's time to adhere to the bubbles. Since you have fewer, larger bubbles you have to slow down their ascent. You would have to build the skimmer yourself, and the tube would have to be close to twice the size of a regular skimmer (for your size tank) and it would have to be a strong counter-current type to give a "drag" to the bubbles. I believe someone wrote in saying that they had built one, but that even though it worked, it wasn't removing that much from the water.
I do wonder though if you couldn't use an overflow (like used in saltwater) hooked up to a large canister filter. The overflow would in effect skim the surface water taking it to the canister where it could be removed.....