When Synchronous mode is used (UMSEL = 1), the XCK pin will be used as either clock input (Slave) or clock output (Master). The dependency between the clock edges and data sampling or data change is the same. The basic principle is that data input (on RxD) is sampled at the opposite XCK clock edge of the edge the data output (TxD) is changed.
Figure 1. Synchronous Mode XCK Timing
The UCPOL bit UCRSC selects which XCK clock edge is used for data sampling and which is used for data change. As the figure above shows, when UCPOL is zero the data will be changed at rising XCK edge and sampled at falling XCK edge. If UCPOL is set, the data will be changed at falling XCK edge and sampled at rising XCK edge.