Even if you could determine whether a column had been used in the past X period of time, would that be good enough? There may be some obscure program out there that populates a column once a week, a month, a year; or once every time they click the mystery button that no one ever clicks, or to log the report that only Fred in accounting ever runs (he quit two years ago), or that gets logged to if that one rare bug happens (during daylight savings time, perhaps?)
My point is, the only way you can truly be certain that a column is absolutely not used by anything is to review everything -- every call, every line of code, every ad hoc Excel data dump, every possible contingency -- everything that references the database . As this may be all but unachievable, try to get a formally defined group of programs and procedures that must be supported, bend over backwards to make sure they are supported, and be prepared to fix things when some overlooked or forgotten piece of functionality turns up.