User blog comment:Xilinoc/Ch. 533 Everything but the Rain op. 6 - "The Gravitation"/@comment-7092747-20130411011045

It may be that Urahara is working on something; or he not only realized Masaki is a Quincy, but he also may have sensed the traces of a Hollow on her that had similar rieatsu to that Hollowfication process that was done on Shinji and the gang (which by now Urahara has had decades to study and analyze).

All in all seeing Urahara at the end was a refresher and certainly will steer this in an interesting path especially with Isshin being familiar with Urahara. Also was good to see Aizen for once was *gasp* all-knowing, all-seeing of the plot line.