Why? Pittsburgh's steel industry, which had tons of well-paid blue-collar union jobs, collapsed in the early 1980s: 'Following the 1981–1982 recession, for example, the mills laid off 153,000 workers.'[0] A lot of the working-age population left in the following years. The main thing remaining were a lot of world-class institutions in healthcare & education (much better than a lot of the Rust Belt, e.g. Detroit/Toledo/Milwaukee), so the people that come to & stay in Pittsburgh today are very well-educated[1]. The older population that had pensions or savings to fall back on when the steel collapse came, and didn't need to relocate for work, is a lot less educated.
[0]http://en.wikipedia.org/wiki/History_of_Pittsburgh#Collapse_... [1]http://nullspace2.blogspot.com/2013/06/education-examined.ht...