Arduino communicates with both the W5100 and SD card using the SPI bus (through the ICSP header). This is on digital pins 11, 12, and 13 on the Duemilanove and pins 50, 51, and 52 on the Mega. On both boards, pin 10 is used to select the W5100 and pin 4 for the SD card. These pins cannot be used for general i/o.
The extended API can use pins 4, 10, and 52 for CS.